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157.Журнал Сибирского федерального университета. Сер. Химия №2 2013

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Журнал Сибирского федерального университета
2013
Journal of Siberian Federal University
6 (2)
Химия
Chemistry
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Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Vladimir V. Zuev
CONTENTS / СОДЕРЖАНИЕ
Alexander D. Vasiliev and Nicolay N. Golovnev
Ciprofloxacinium Malonate Dihydrate: Preparation, Crystal
Structure, Thermal Stability
? 107 ?
Abdulgalim B. Isaev, Naida K. Tajibova,
Farid F. Orudjev, Patimat M. Salikhova,
Ruslan V. Ilkanaev and Marat N. Medjidov
Photoelectrocatalytic and Photocatalytic Oxidation of Azodye at
High Oxygen Pressure
? 114 ?
В.И. Шарыпов, И.П. Иванов, О.Ю. Фетисова,
О.П. Таран, В.Д. Страховенко, Б.Н. Кузнецов
h?????%"=?,? 2?!?,???*,. C!?"!=???,L ?=C!%C???L %??!
j=?*3??? , a=!?,? m%"%?,K,!?*%L %K?=?2, ??2%?=?, d?cdqj , pt`
? 122 ?
В.М. Денисов, Н.В. Белоусова, Л.Т. Денисова
a%!=2/ ",??32=
? 132 ?
Editorial Board:
Editor-in-Chief
Mikhail I. Gladyshev
Founding Editor
Vladimir I. Kolmakov
Managing Editor
Olga F. Alexandrova
Executive Editor for Chemistry
Boris N. Kuznetsov
Д.В. Кузьмин, В.И. Кузьмин
q%!K?, ?"?2?/. ??2=??%" ,? C3??C .??=2%?=?,
? 151 ?
Н.Ю. Васильева, А.В. Левданский, А.С. Казаченко,
Л. Дьякович, К. Пинель, Б.Н. Кузнецов
q3??-=2,!%"=?,? ??.=?%=*2,",!%"=??%?% =!=K,?%?=?=*2=?=
*%?C??*?%? ??!?/L =??,?!,? $ C,!,?,? " ?!??? C,!,?,?=
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Editorial board for Chemistry:
Nikolai V. Chesnokov
Lubov? K. Altunina
Natalia G. Bazarnova
Vasiliy A. Babkin
Vicente Cebolla
Viktor M. Denisov
Zinfer R. Ismagilov
Sergey V. Kachin
Sergey D. Kirik
Wolfgang Klose
Vladimir I. Kovalchuk
Vladimir A. Likholobov
Yuri L. Mikhlin
Gennady L. Pashkov
Anatoly I. Rubailo
Tatyana V. Ryazanova
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Valeri E. Tarabanko
Tatyana G. Shendrik
Jean V. Weber
Д.С. Калякин, Н.С. Елисеева,
Ю.Е. Ананьева, А.А. Кузубов, А.О. Лыхин
j"=?2%"%-.,?,???*%? ,?3???,? C!%????= ?%!K?,, , ?,?!=?,,
=2%?= 3???!%?= ?= C%"?!.?%?2, ?!=-??= , K,?!=-??=
? 170 ?
Я.И. Якимов, С.Д. Кирик,
Е.С. Семенкин, Л.А. Соловьев, И.С. Якимов
}"%???,%??/L ??2%? ?%???,!%"=?,
*!,?2=??,???*%L
?2!3*23!/ "????2"= C% ?=??/? C%!%?*%"%L ?,-!=*?,,
? 180 ?
С.А. Кузнецова, Т.П. Шахтшнейдер,
М.A. Михайленко,Ю.Н. Маляр,
А.С. Замай, В.В. Болдырев
l?.=?%*%?C%?,2 ?,=??2=2= K?23?,?= , ??% C!%2,"%%C3.%??"=
=*2,"?%?2?
? 192 ?
А.К. Старков, Г.А. Кожуховская
q,?2?? , -,?,*%-.,?,???*%? ,?????%"=?,? ???,???2!,??/.
*%?C??*?%" 2!=??-?,.?%!%?,=?,?C?=2,?/(II)
????????????? ? ??????????? ???
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????????? ????» (???????? 2010 ?.)
? 203 ?
Т.А. Леонова, А.И. Дудник,
Н.Г. Внукова, И.В. Осипова,
Г.А. Глущенко, Е.В. Томашевич, Г.Н. Чурилов
q!="???,? ?%!K?,%??%L ??*%?2, C% ,%?=? ?,2, ?!=-,2%"/.
, -3???!??-?,2,?"/. =?%?%"
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Journal of Siberian Federal University. Chemistry 2 (2013 6) 107-113
~~~
??? 548.737
Ciprofloxacinium Malonate Dihydrate:
Preparation, Crystal Structure,
Thermal Stability
Alexander D. Vasilieva,b and Nicolay N. Golovneva*
a
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Kirensky Institute of Physics SB RAS,
50/38 Akademgorodok, Krasnoyarsk, 660036 Russia
Received 14.11.2012, received in revised form 23.01.2013, accepted 11.02.2013
Ciprofloxacinium malonate dihydrate (I), C17H19FN3O3+·C3H3O4?·H2O, (C17H18FN3O3 ? ciprofloxacin,
CfH; C3H4O4 ? malonic acid) has been crystallized from the mutual solution of malonic acid and
ciprofloxacin in ambient conditions. It has improved aqueous solubility against the ciprofloxacin.
The colourless crystals have been investigated using X-ray single crystal and powder techniques,
and characterized by differential scanning calorimetry and thermogravimetry. The obtained
compound can be considered as a salt with ciprofloxacinium in the role of a cation and malonate
as an anion. The compound is crystallized in the triclinic lattice with a = 7.283(2), b = 10.090(3),
c = 15.104(5)Е, ? = 102.711(4), ? = 103.328(4), ? = 94.261(4)°, Z = 2, V = 1044.5(6)Е3, S.G. P 1 . The
crystal structure determination reveals the importance of inter- and intramolecular interactions in
the crystal formation. Thermal behavior and solubility of I provided complementary evidences of
salt formation.
Keywords: ciprofloxacinium malonate dihydrate, crystal structure, thermal behavior.
Ciprofloxacin (CfH), 1-cyclopropyl-6-fluoro-4-oxo-7-piperazin-1-yl-quinoline-3-carboxylic
acid, is a fluoroquinolone antibiotic approved for the treatment of several types of infections [1].
In aqueous solutions CfH exists mainly in its zwitterionic form, due to the acid base interaction
between the piperazine basic nitrogen and the carboxylic group. As a consequence the aqueous
solubility of CfH at pHs close to 7 (isoelectric point of the molecule) is low (0.088 mg/ml) [2]. This
property makes it difficult to formulate optimized liquid dosage forms such as parenteral, ototopic
or ophthalmic solutions. Moreover, ciprofloxacin is characterized by a bitter taste [3], which is an
additional complication for the oral administration of it. It has been proposed that CfH bioavailability
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: ngolovnev@sfu-kras.ru
# 107 #
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Alexander D. Vasiliev and Nicolay N. Golovnev. Ciprofloxacinium Malonate Dihydrate: Preparation, Crystal Structure?
can be limited by both solubility and permeability [4]. For active pharmaceutical ingredients (APIs)
with solubility-limited bioavailability, a challenging task in the development of the product is to
improve their solubility without compromising other performance. Indeed, a widely accepted
approach to overcome poor solubility of an API is the preparation of their salt forms [5]. Organic
salts are generally the preferred crystal form of active pharmaceutical ingredients because of their
higher solubility and/or increased degree of crystallinity. Crystalline APIs are strongly preferred
due to their relative ease of isolation, the rejection of impurities inherent to the crystallization
process and the physicochemical stability that the crystalline solid state affords. The malonic acid
is one of active pharmaceutical ingredients [6], and it can be used for preparation soluble forms
fluoroquinolone [7].
The aim of this work is to present a new compound CfH2Mal (Mal? = C3H3O4?, anion of malonic
acid) with improved degree of crystallinity and aqueous solubility.
Experimental
CfH was obtained from the hydrochloride salt (ciprofloxacin hydrochloride monohydrate,
CfH·HCl·H2O, Ranbaxia, India, pharmaceutical grade). Ciprofloxacin hydrochloride monohydrate
was dissolved in the solution of concentrated ammonia. Then few drops of 4 M HCl were added
(pH 8) and white microcrystals of anhydrous ciprofloxacin have precipitated. For the preparation of
ciprofloxacinium malonate dihydrate (I), a mixture of anhydrous ciprofloxacin (0.20 g, 0.60 mmol)
and malonic acid (0.065 g, 0.63 mmol) in water (5 ml) was dissolved. The solution has been kept in a
fume hood and colorless crystals have grown in several days. These crystals were used to determine
the crystal structure of the compound by X-ray diffraction and to carry on the analysis through the
other techniques.
The TG and DSC (Fig. 1) curves show mass losses at least in four steps for I. The first mass loss
between 80 and 170єC corresponds to an endothermic peak (DSC) and the extremum (DTG) at 90єC
is due to dehydration. Estimated (6.37 %) and calculated (7.64 %) mass losses for two water molecule
Fig. 1. TG and DSC curves for ciprofloxacinium malonate dihydrate
# 108 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander D. Vasiliev and Nicolay N. Golovnev. Ciprofloxacinium Malonate Dihydrate: Preparation, Crystal Structure?
are in fair agreement. The anhydrous compound is stable up to 190 °? and between 190 and 230 °? the
thermal decomposition occurs in a single step. In this step the DSC curve shows a strong endothermic
peak at 210 °?. The mass loss (estimated 21.82 % and calculated 22.07 %) corresponds to the lost of
malonic acid molecule. The thermal decomposition of this acid occurs with decarboxylation followed
by the formation of acetic acid [8]. The constant mass of the substance in temperature range 220-290 °?
is received. The third endothermic peak at 278 °? is attributed to the melting of formed ciprofloxacin
and its position coincidents with the melting point of ciprofloxacin (277 °?) [9]. Estimated (28.2 %)
and calculated (29.7 %) mass losses in this step are in good agreement. The pyrolysis of CfH starts
at 290 °? with simultaneous evolution of water and carbon dioxide [9]. The process is not finished at
900 °? (the mass loss is equal to 93 %, Fig. 1).
The solubility of I at 298 K was estimated in distilled water using the shake-flask method over 24
h. The concentration of the compound in the filtrate was quantified using UV spectroscopy [10]. The
solubility of I at 298 K is equal 0.024 M (pH 5.5) that higher than of the corresponding ciprofloxacin
[2]. Also, the pH of the malonate solutions is higher than used in pharmacology of the corresponding
hydrochloride.
So, the thermal behavior and solubility of I provided complementary evidences of salt formation.
The product showed improved properties with respect to water solubility and increased degree of
crystallinity. This salt would be a good way forward to developing more suitable formulation of this
APIs.
Single crystal X-ray diffraction data were collected with MoK? radiation on a Bruker SMART
APEX II CCD diffractometer using a crystal sample of dimensions 0.381Ч0.316Ч0.260 mm.
Experimental absorption corrections were performed using the multi-scan method and the program
SADABS [11]. Structure was solved by direct methods using the program complex SHELXS [12]
and was refi ned with the program complex SHELXL [12]. The asymmetric unit of the crystal
cell contains ions of CfH 2+, C3H3O4? one by one and two molecules of water. All H atoms were
subsequently located on difference electron density maps and then refi ned in idealized positions
with constrained mode. The main crystallographic data and refi nement parameters are gathered in
Table 1.
Due to the presence of NH2 group in CfH2+, oxygen atoms in CfH2+ and in C3H3O4? as well as
H2O molecules in the structure arose a net of intermolecular H-bonds of N?H?O and O?H?O
type which don?t involve O3 and O5 atoms only (Fig. 2 and 3). The H-bond paramers are presented in
Table 2. The main features of the bonds are centrosymmetric cycles of four water molecules (Fig. 3).
Molecules of the cycle are hydrogen bonded with each other and also involved in the same bonds
with four C3H3O4? ions and two CfH2+ ions. As a result the Ow1 atom is twice hydrogen-bond donor
and twice hydrogen-bond acceptor whereas the Ow2 atom is twice hydrogen-bond donor and once
hydrogen-bond acceptor.
CfH2+ ions are packed up in infinite stacks along the crystallographic a-axis (Fig. 4) in the crystal.
Each stack consists of molecules united in pairs by inversion centers with [n; 1/2; 1/2] coordinates,
where n is integer, and the pairs are fastened by two additional C12?H8??1 H-bonds (Table 2). The
pairs are connected with each other by inversion centers with [n+1/2; 1/2; 1/2] coordinates. As a result,
additional supramolecular interactions present at the stack between ?-conjugated orbitals of plane
molecular cycles; their parameters are shown in Table 3.
# 109 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Table 1. Experimental details and refinement parameters for CfH2Mal Ч2H2O
Chemical formula moiety
C17H19N3O3FЧC3H3O4Ч2H2O
Temperature (K)
298
Space group
Z
P1
2
2?max, (°)
52
a, b, c (Е);
7.283(2); 10.090(3); 15.104(5)
?; ?; ? (°)
102.711(4); 103.328(4); 94.261(4)
V, Е
1044.5(6)
3
d, (g/cm3)
1.499
?, (mm-1)
0.124
Reflections measured
8386
Reflections independent
4076
Reflections with F>4?F
2508
R int / R?
0,030 / 0,049
?8 ? h ? 8; ?12 ? k ? 12; ?18 ? l ? 18
h, k, l ? limits
Refinement results
Refinement parameters
w = 1/[?2(Fo2)+(0,0617P)2+0,06P];
P = (Fo2+2Fc2)/3
320
R1 [Fo > 4?(Fo)]
0.0478
wR2
0.1371
Extinction coefficient
0.012(2)
GooF
1.04
Refinement on F2
(??)max, e/Е
3
0.215
(??)min, e/Е3
?0.224
(?/?)max
0.000
Fig. 2. The structure of C17H19N3O3F+ and C3H3O4? with
atom numbering scheme. The intramolecular H-bonds
are shown as dotted lines
Fig. 3. H-bonds (dotted lines) with the participation of
CfH2+ and Mal?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Table 2. Geometrical parameters of H-bonds, D?H???A, and short contacts in the structure. Bond lengths (Е) and
angles (°)
D?H
d(D?H)
d(H???A)
?DHA
d(D???A)
A
transformation
for ?-atom (acceptor)
O2?H1
0.91(1)
1.65(1)
161(3)
2.531(2)
O1
x, y, z
N3?H2
0.90
1.89
158
2.746(3)
O7
1+x, 1+y, 1+z
N3?H3
0.90
2.00
166
2.880(3)
Ow1
x, 1+y, 1+z
O4?H20
0.91(1)
1.62(2)
159(3)
2.489(3)
O6
x, y, z
Ow1?Hw11
0.90(1)
1.88(1)
168(2)
2.757(3)
Ow2
1?x, ?y, ?z
Ow1?Hw12
0.90(1)
1.99(1)
161(3)
2.853(3)
O7
x, y, z
Ow2?Hw21
0.90(1)
1.86(1)
171(3)
2.745(3)
O6
1+x, y, z
Ow2?Hw22
0.90(1)
2.04(1)
154(2)
2.875(3)
Ow1
x, y, z
C14?H13
0.97
2.13
129
2.846(3)
F
x, y, z
C12?H8
0.97
2.24
170
3.202(3)
O1
?x, 1?y, 1?z
Fig. 4. H-bonds (dotted lines) of water molecules. There shown
N3 atom with its environment only instead of CfH2+ ion, for
clarity
Table 3. Parameters* of ???-interactions between (cfH2)+ ions in the structure
Cgi?Cg j
Cg1?Cg1
Cg1?Cg2
Cg1?Cg2
Cg2?Cg1
Cg2?Cg1
Cg2?Cg2
Symmetrical
transformation
of ring j
?x,1?y,1?z
?x,1?y,1?z
1?x,1?y,1?z
?x,1?y,1?z
1?x,1?y,1?z
1?x,1?y,1?z
d (Е)
? (°).
? (°).
Cgi_p (Е)
Cg j_p (Е)
Slip (Е)
3.821(2)
3.796(2)
3.618(2)
3.796(2)
3.618(2)
3.680(2)
?
2.7(1)
2.7(1)
2.7(1)
2.7(1)
?
23.4
20.2
19.9
22.2
22.5
22.5
3.5056(9)
3.5154(9)
3.3435(9)
3.5572(9)
3.4030(9)
3.3996(9)
3.5057(9)
3.5572(9)
3.4030(9)
3.5154(9)
3.3435(9)
3.3996(9)
1.52
?
?
?
?
1.41
* d ? distance between ring centroids; ? ? dihedral angle between planes i and j; ? ? angle between Cgi?Cg j vector and normal
to plane i; Cgi_p ? perpendicular distance of Cgi on ring j; Cg j_p ? perpendicular distance of Cg j on ring i; Slip ? distance
between Cgi and perpendicular projection of Cg j on ring i. ?g1: N1-C2-C3-C4-C10-C9; ?g2: ?5-?6-?7-?8-?9-?10.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander D. Vasiliev and Nicolay N. Golovnev. Ciprofloxacinium Malonate Dihydrate: Preparation, Crystal Structure?
Fig. 5. The molecular packing of the CfH2+ ions in the
unit cell. Dashed lines are C12?H8????1 bonds
Table 2. Selected bond distances (Е) and angles (°)
bond
d
bond
d
O1??4
O2?C1
O3?C1
O4??18
O5??18
1.263(3)
1.324(3)
1.203(3)
1.304(3)
1.205(3)
O6??20
O7??20
C19?C18
C19?C20
1.252(3)
1.243(3)
1.493(3)
1.496(3)
angle
?
angle
?
O1?C4?C3
O2?C1?C3
O3?C1?C3
O2?C1?O3
122.5(2)
115.8(2)
123.6(2)
120.6(2)
O4?C18?O5
O4?C18?C19
C18?C19?C20
O6?C20?C19
O6?C20?O7
120.8(2)
121.9(3)
119.7(2)
117.5(2)
124.7(2)
References
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properties of saccharin salts of fluoroquinolones // J. Pharm. Sci. 2009. V. 98. N 10. P. 3788-3801.
3. Pisal S., Zainnuddin R., Nalawade P. Et al. Molecular properties of ciprofloxacin-indion 234
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characterization of a ciprofloxacin saccharinate polymorph // Int. J. Pharm. 2010. V.391. P. 197?202.
# 112 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander D. Vasiliev and Nicolay N. Golovnev. Ciprofloxacinium Malonate Dihydrate: Preparation, Crystal Structure?
6. Gauniya A., Das S., Mallick S., Basu S. P. Comparative bioavailability studies of citric acid and
malonic acid based aspirin effervescent tablets // J. Pharm. Bioapplied Sci. 2010. V. 2. N 2. P. 18?120.
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Application WO/2009/136408 Application Number: IN2009/000233 Publication Date: November 12,
2009 Filing Date: April 09, 2009.
8. Caires F.J., Lima L.S., Carvalho C.T. et al. Thermal behaviour of malonic acid, sodium malonate
and its compounds with some bivalent transition metal ions // Thermochim. Acta. 2010. V. 497. P. 35?40.
9. Turel I., Bukovec P. Comparison of the thermal stability of ciprofloxacin and its compounds //
Thermochim. Acta. 1996. V. 287. P. 311?318.
10. Golovnev N.N., Kirik S.D., Golovneva I.I., Nishnevich M.E. Synthesis and characterization
of ciprofloxacin compounds with chlorides of cadmium(II) and mercury(III) // Russ. J. Inorg. Chem.
2006. ?.51. N 3. P. 463?468
11. Sheldrick G.M. SADABS. Version 2.01. Bruker AXS Inc. Madison, Wisconsin, USA, 2004.
12. Sheldrick G.M. A short history of SHELX. Acta Cryst. 2008. A64. P. 112?122.
???????? ???????? ??????????????????:
?????????????, ??????????????? ?????????,
??????????? ????????????
?.?. ?????????,?, ?.?. ?????????
????????? ??????????? ???????????,
?????? 660041 ??????????, ??. ?????????, 79
?
???????? ?????? ??. ?.?. ?????????? ?? ???
?????? 660036, ??????????, ?????????????, 50/38
?
???????? ???????? ?????????????????? (I), C17H19FN3O3+·C3H3O4?·H2O, (C17H18FN3O3 ?
ciprofloxacin, CfH; C3H4O4 ? malonic acid) ??????? ??? ?????????????? ? ?????? ????????
????????? ??????? ? ??????????????? ??? ??????? ????????. ?????????? ??????????
????????? ??????????? ? ???????????????? ???????? ???????????????? ???, ???,
???????????????? ??????????? ???????????? ? ???????????. ?????????? I ???????? ?????,
????????? ?? ??????? ?????????????????? ? ???????-??????. ??? ??????????????? ? ?????
?????????? ?????????? ? ??????????? a=7.283(2), b=10.090(3), c=15.104(5)Е, ?=102.711(4),
?=103.328(4), ?=94.261(4)°, Z=2, V=1044.5(6)Е3, ??. ??. P 1 . ?????? ??????????????? ?????????
????????? ?? ???????? ??????- ? ??????????????? ?????????????? ??? ???????????
?????????. ?????? ?? ??????????? ???????????? ? ????????????? I ????????????
??????????? ????.
???????? ?????: ???????? ???????? ??????????????????, ??????????????? ?????????,
??????????? ????????????.
# 113 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 114-121
~~~
??? 544.526.5
Photoelectrocatalytic and Photocatalytic Oxidation
of Azodye at High Oxygen Pressure
Abdulgalim B. Isaev, Naida K. Tajibova,
Farid F. Orudjev, Patimat M. Salikhova,
Ruslan V. Ilkanaev and Marat N. Medjidov*
Dagestan State University,
43a M. Gadjieva Str., Makhachkala, 367001 Russia
Received 14.09.2012, received in revised form 26.12.2012, accepted 14.01.2013
Influence of dissolved oxygen at different pressure to photocatalytic and photoelectrocatalytic azodye
C.I. direct black 22 (DB) oxidation is investigated. It is shown, that at the presence of dissolved oxygen
photocatalytic and photoelectrocatalytic DB oxidation rate on TiO2 increases. The azodye decolouration
higher than 98 % by photoelectrocatalytic oxidation at oxygen pressure was 0.42 MPa.
Keywords: photocatalytic, photoelectrocatalytic, azodye, oxygen pressure, oxidation, C.I. direct
black 22.
Introduction
The textile activities have a high potential environmental impact, principally due to the release
of large volumes of wastewaters that contain high organic charge and strong coloration. Many dyes
used in textile processes show toxicity to the aquatic biota (or can be biologically transformed to toxic
species) and could cause interference in natural photosynthetic processes.
The problem of colour in textile dyehouse effluent and the possible problems associated with
the discharge of dyes and dye degradation products are of concern. Traditional methods for dealing
with this kind of wastewater are usually the biological, physical and chemical techniques as well as
the various combinations of theses. It has been widely reported that many dye chemicals are difficult
to degrade using conventional biological treatment processes. It is more important to reuse this kind
of wastewater than to discharge it after treatment in that the costs of chemicals, energy and water
continually increase.
Heterogeneous photocatalytic processes, especially with use of titanium dioxide, have been
extensively applied in the treatment of wastewater [1]. Numerous studies have shown that the
application of this method can lead to complete color removal, detoxification and mineralization of
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: abdul-77@yandex.ru
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Abdulgalim B. Isaev, Naida K. Tajibova? Photoelectrocatalytic and Photocatalytic Oxidation of Azodye at High Oxygen?
textile dyes wastewater [2-5]. In the last decade, advanced oxidation processes (AOPs) were used
widely in the treatment of wastewater since they were able to handle the problem of organic pollutants
destruction in aqueous solution [6, 7]. Among AOPs, there was a great interest in the development of
photocatalytic and photoelectrochemical methods for degrade pollutants [8-10]. Several pollutants,
such as azo dyes [11, 12], have been degraded by advanced oxidative processes that produce hydroxyl
radicals as the primary oxidant. Hydroxyl radicals are very efficient oxidizers; the oxidation potential
of OH· is as high as 2.80V. Therefore, photoelectrocatalytic degradation has been widely established as
an alternative electrochemical process for environmental remediation [13, 14]. The use of UV-light and
semiconductor photocatalysts such as TiO2 immobilized films [15, 16] can degrade and even mineralize
these dyes. In this work, photocatalytic and photoelectrocatalytic oxidation of azodye C.I. Direct Black
22 (DB) in 0,1M Na2SO4 solution at high oxygen pressure are described.
Experimental
Photocatalytic and photoelectrocatalytic oxidation of azodye was carried out in a avtoclaveelectrolyser (Fig. 1) in which there is a teflon cylindrical vessel cell with a quartz glass window and
volume 250 ml ahd to electrodes (Pt ? cathode, Ti/TiO2 ? semiconductor anode) lowered in a solution.
The autoclave is equipped with gates for input and output of gas, the manometer for measuring of
pressure and lead wires for current supply [17, 18].
Ti sheet were first cleaned in alcohol and acetone solutions, respectively, and then mechanically
polished with different abrasive papers followed by washing with distilled water. The cleaned Ti sheet
was submerged in the mixed solution (HF/HNO3 is 1:4 in volume) for 10 min to polish its surface
chemically. The Ti/TiO2 prepared in a oxygen low-pressure system within 0.74 Pa and current 160 mA
technique at the temperatures 600-660 °C. Cooling of a Ti sheet up to a room temperature was made
6
9
5
1 2 34
O2
7
8
Fig.1 Schematic representation of the autoclave-electrolyser: 1 ? quartz glass window; 2 ? washer; 3 ? Ti/TiO2
anode; 4 ? Pt cathode; 5 ? lead wires; 6 ? manometer; 7 ? teflon case; 8 ? bolts; 9 ? gate
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Abdulgalim B. Isaev, Naida K. Tajibova? Photoelectrocatalytic and Photocatalytic Oxidation of Azodye at High Oxygen?
in vacuum ~10 -3 P?. The low pressure system for preparation of metal oxide thin films are described
[19].
For the determination of concentration of dye Spekord UV VIS spectrophotometer was used.
Aliquot of the reaction mixture was withdrawn and concentration of azo dye diluted from with a
distillation water so that concentration made 20 mg·l-1 in recalculation on initial compounds.
Results and discussion
Concentration,mg?l?1
In a photocatalytic process, oxygen is necessary to form superoxide radical anions that will further
generate other active radicals to promote the degradation reaction [20].
Furthermore, the distribution of the intermediates is different in the presence and absence of
oxygen [21]. Although the use of anodic bias obviates the need of oxygen as an electron acceptor in
photoelectrochemical catalysis, the presence of molecular oxygen affects both the degradation rate
and the degradation pathways of organic pollutants [22]. As stated above, the compressed oxygen was
sparged into the reactor from the gate. Thus, the photocatalytic and photoelectrocatalytic oxidation of
C.I. direct black 22 was conducted at different oxygen pressure.
Obviously, the oxygen have an important role in the photocatalytic process [23]. When oxygen
was submited at pressure 0.18 MPa, the reaction rate was relatively slow.
However, the reaction rate increased significantly with the increase the oxygen pressure. Fig. 2
presents the azodye removal with different oxygen pressure under UV-light illumination.
From the Figure 2, we can see that, when the oxygen pressure to increase from 0.32 to 0.42 MPa,
the photocatalytic reaction rate changed slightly. This is because further increasing the pressure the
16
1
8
2
3
0
1,0
2,0
Time, h
Fig. 2. DB removal with different oxygen pressure at photocatalytic oxidation under UV-light illumination: 1 ?
0.18 MPa; 2 ? 0.32 MPa; 3 ? 0.42 MPa
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Abdulgalim B. Isaev, Naida K. Tajibova? Photoelectrocatalytic and Photocatalytic Oxidation of Azodye at High Oxygen?
Decoloratration,%
60
40
20
0,1
0,2
0,3
0,4
Oxygen pressure, MPa
Fig. 3. Effect of oxygen pressure on the decoloration of azodye solution at photocatalytic oxidation under UVlight illumination. [DB]0 =20 mg·l-1, t = 2 h, V=250 ml
dissolving oxygen will reach an equilibrium, resulting in a slight change of reaction rate. The effect
of oxygen pressure on the decoloration of azodye solution at photocatalytic oxidation are shown in
Fig. 3.
It can be seen that the degree of DB degradation varied with the oxygen pressure. In the
photocatalytic oxidation reaction, the efficiency of DB degradation increased with the increase of
oxygen pressure significantly, since the oxygen served as an electron acceptor in photocatalysis with
generation active particles. Above oxygen pressure 0.4 MPa, the degree of DB degradation only further
increased slightly.
The DB degradation in the photoelectrocatalytic reaction was also investigated using TiO2/Ti
electrode. In the photoelectrocatalytic reaction, the TiO2/Ti electrode was used as the anode and the Pt
electrode was used as the cathode. Aqueous DB solution was prepared with an initial concentration of
20 mg·l-1 and 0.1 M Na2SO4.
The photoelectrolysis reaction tests were carried out for DB degradation when oxygen pressure
was 0.1 MPa and 0.42 MPa. The experimental results are presented in Fig. 4 as curves ?1? and ??2??,
respectively. It can be seen that the overall removals of DB after 30 min at oxygen pressure 0.1 MPa
were 85 % and 98 % when oxygen pressure 0.42 MPa. These experiments demonstrated the significant
enhancement of DB photoelectrocatalytic degradation under UV illumination.
The increases removal of DB at photoelectrocatalytic process is due to dissolved oxygen reduction
up to hydrogen peroxide or active particles on the Pt-cathod and oxygen reduction could be utilized to
exercise indirect oxidation and to improve photoelectrocatalytic efficiency.
Dissolved oxygen can be reduction with the formation of superoxide, hydroperoxide radicals
and hydrogen peroxide:
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Abdulgalim B. Isaev, Naida K. Tajibova? Photoelectrocatalytic and Photocatalytic Oxidation of Azodye at High Oxygen?
Concentration,mg?l?1
20
15
10
5
1
0
15
30
2
Time, min
Fig. 4. DB removal with different oxygen pressure at photoelectrocatalytic oxidation under UV-light illumination:
1 ? 0.10 MPa; 2 ? 0.40 MPa
O2ads + e ? O. ?2ads
O. ?2ads+ H+ ? HO2ads
O.?2ads + e + 2H+ ? H2O2ads
The concentration of hydrogen peroxide or active particles increased due to the cathodic reduction
of dissolved oxygen at 0.42 MPa and these active particles were consumed in the oxidative degradation
of azodye in the volume of solutions. The peroxide hydrogen existing in solution is consumed for
oxidation of azodye.
The reaction mechanism of the photocatalytic and photoelectrocatalytic degradation of organic
pollutants was discussed in literatures [24-26], and the degradation mechanism is believed to involve
many oxidation ways, such as anodic oxidation, oxidation of electrogenerated H2O2, oxidation of
photogenerated hole and OH., and the photoelectrocatalytic synergetic effect, etc.
The UV-visible spectra of the initial, photocatalytic and photoelectrocatalytic treatment of DB
solution are presented in Fig. 5. Two absorbance peaks were observed during the scanning of DB solution
at 540 and 680 nm which was due to green and blue color of the chromophore. At photocatalytic treatment
of DB solution with oxygen pressure of 0.42 MPa in the UV region at 280 nm appears new peak was due
to the aromatic fragments of degraded DB molecule, and in the visible region ? at 370 nm.
Conclusions
A new way to photocatalytic and photoelectrocatalytic oxidation of azodye was investigated.
Photoelectrocatalytic degradation of DB at high oxygen pressure is faster and more efficient than
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Abdulgalim B. Isaev, Naida K. Tajibova? Photoelectrocatalytic and Photocatalytic Oxidation of Azodye at High Oxygen?
D
0,8
1
0,6
0,4
2
0,2
0
100
3
300
500
700
900
?,nm
Fig. 5. UV-visible spectra during different treatment of DB: 1 ? initial; 2 ? photocatalytic (t = 2 h); 3 ?
photoelectrocatalytic (t = 30 min)
photocatalytic degradation. Increasing the oxidation rate at high oxygen pressure is due to dissolved
oxygen reduction up to hydrogen peroxide or active particles, and oxygen reduction could be utilized
to exercise indirect electrochemical oxidation and to improve photoelectrocatalytic efficiency.
It is clear that both the colour removal (75 %) and the degradation of aromatic structure is achieved
at photoelectrocatalytic treatment of DB solution with oxygen pressure of 0.42 MPa. However, new peak
was observed at 220 nm, which were due to the absorbance the lowmolecular organic compounds.
Acknowledgment
We are grateful the Ministry of Education and Science of Russian Federation (projects ?
14.B37.21.0824.) for financial support of this work with program «Scientific and pedagogical cadres of
innovative Russia».
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Journal of Siberian Federal University. Chemistry 2 (2013 6) 122-131
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Received 17.01.2013, received in revised form 01.02.2013, accepted 20.02.2013
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*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: sharypov@icct.ru
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?????????? ????? 93 ??? ?3 [2].
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?????? ??????? ?????????? ? ??? ???????????? ??????? ????? 15 % ? ??????? ?? ?????????
????? ????? ?????????? [3]. ?? ?????????? ? ??????? ??????????? ????? ????????? ??????
????????? ?? ????????? ?????: ???????????? (????????? 6-30 ???. %), ??????????????, ??????????? ? ????????? (????????? ?? 30 ?? 85 ???. %) [4].
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? ?????????????? ????????, ????? ??????? ????? ???????? ????????? ?????????????????
????????? [4, 6-8]; ?????? (???? ??????????????) [8], ??????? ??????????????? ?????? [9],
?????? ?????????????? ???????, ??????? ????? ???? ???????????? ? ???????? ?????????
??????, ???? ????? ??? ???????????? ?????????? ??????? ? ??????????? ???????? ?????? [8,
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??????????? ??????????? ? ???????? ???????????? ????????? [12, 13].
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???? ?? ??????????? ????????? ????? ????? ? ??????? ??????? [14], ??????? ??????????? ?
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??????????? ???????????? ???????? ??????? (825 ± 25) °? [15]. ?????? ???????????? ???? ???????? ???? ?????????? ? ?????? [16], ? ??????? ??????? ????????? ??????? ??? ??????????
??????????? ?? ????????? ?? 500 °? ? ??????????? ??? ???? ??????????? ? ??????? ????. ????? ??????????? ????? ??????? ????????????? ??????????? ??? 950 °? ? ??????? ????. ????# 123 #
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16,3 ???. %; 81,3 ???. % ?????????? ???????????? ????????. ????????? ????????? ?-2 ?????????
???? (43,8 ???. %), ??????? ?? ????? ???? ??????? ? ?????????????????? ????. ??????????
???????????? ??????? ???????????? ?? ??????? ???? ????????? ? ???????? ??????? ????? ???????????? ??? 500 °?.
????????????? ???????????? ??????????? ??????????? ?????????? ????????????? (?-1)
? ?????????????????? (?-2) ????? ???? ????????? ? ??????????? ?????? ?????????? ???????????? ???????, ? ???? ???????? ???????? ???????????? ???????? ? ??????????? ?????????
???? ???????? ??????????.
??????? ???????????? ?????????? ????????? ????????????? ???? ?-1 ? ???? ?????? ??????????????? ????? ?????????????? ??????????? ??????????? ?????? ?????, ??????? ??????????? ? ???? ????????? ?? ???????????? ?????? ? ??????????????? ?? ????????? ??
???????????????? ?????? ?????? ????? (???. 1).
?????? ?? ???, ??????? ???????????? ???????? ?????? ????? ??? 86 °?, ????????,
?????????? ????????? ?? ????????? ???? ? ???????????????? ???????. ?????? ????????, ??????????????? ????????? ?????????? ???????????? ????? ?????????, ?????????? ??? ??????????? 261 °? ? ????????????? ??? 447 °?. ? ???? ????????????? ????????? ????? ???????
???????. ????????? ? ?????????? ?????? ????????????? ???????? ??????????
???????
?????????? ?????????*, ???. %
?????????, ???. %
??? ??????????? ????????
500 °?
830 °?
950 °?
?
?
S
O
N
????????? ????? ????????? ?-1
43.26
5.05
4.6
32.16
3.01
18,7
16,3
16,3
????????? ????? ?????? ?-2
22.75
3.27
3.2
18.59
1.99
58,7
42,4
43,8
*? ??????? ?? ????????? ????? ????? ?????????.
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?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
???. 1. ??????? ???????????? ?????????? ????????? ?-1 ? ???? ??????: 1 ? ????????????????;
2 ? ????????????
???. 2. ??????? ???????????? ?????????? ????????? ?-2 ? ???? ??????: 1 ? ????????????????;
2 ? ????????????
????????? ?? 49 % ?? ?????????. ???????????? ???????? ?????? ????? (2 %/???) ????????????? ??????????? 346 °?.
??????? ???????????? ?????????? ?????????????????? ????????? ?-2 ????? ?????
??????? ??? ?? ????????? ? ??????????? ??? ????????????? ????????? ?-1 (???. 2).
? ????????? ?????????? 259?487 °?, ??????????????? ????????? ?????????? ???, ??
???????????????? ?????? ????? ??????????? ??? ???????? ? ???????????? ????????? ?????? ????? ??? 286 ? 456 °?. ????? ???????, ??????? ???????????? ?????????? ?????????????????? ????????? ?-2 ? ????????? ????????????? ????????? ???????? ??? ???????? ??????. ??
# 125 #
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?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
???. 3. ??????? ???????????? ?????????? ????????? ?-1 ? ???? ???????
?????? ?????? ???????????? ?????????? ????????, ?????????? ???????? ?????? ??????????
?????, ???????? ?-?, ?-?, S-S. ?? ?????? ?????? ??????????? ????? ??????? ???-?????. ??????? ????????? ????????? ?? ???? ??????? ????????? 32 ???. %.
????????? ????????????? ???????? (708?778 °?) ????????????? ???????????? ??????????????? ??????????? ??????????? ?????????, ?????? ?????? ????? ??????? ? ???? ????????? ????????? ????? 20 ???. %. ???????? ???????? ?????? ????? ????????? ?????????????
??????????? 766 °?.
???????????????? ?????????? ? ???? ??????? ???????? ???????????????. ??? ????????? ????????????? ???? ?-1 ??????????? ?????? ???????? ????????????? ????????? ??????????? ?????? ????? (???. 3).
?????? ? ? ?????????? ??? 72 °?, ????????, ?????????? ????????? ????????????? ????.
?????????? ??????? ??????????????? ???????????? ????? ????????? ???????? ??? ???????
??? ??????. ????????????? ????????????? ????????? ?-1, ?????????? ? ???? ?????? ? ???????, ??????????, ??? ?????? ???????????????? ? ?????????? ??? 317 °?, ?????????????????
???????????? ????????? ?????????? 2,2 ???. %/???, ????????????? ?????????????????? ???
??????????? ??????????? ????? ????????? ? ???? ?????? (???. 1) ?, ????????, ??????? ? ??????????? ???????? ????? ?????????.
???????? ??? 492 ? 587 °? ? ???????????? ????????? ?????? ????? 1,3 ? 1,0 ???. %/???
??????????????, ?????????????????? ??? ??????????????? ??????? ?-1 ? ???? ???????, ??????????? ?? ??????????????? ?????????? ????? ????????? ? ??????. ?? ?????????, ????????,
??????? ? ?????????? ?????????? ??????? ?????????? ?????????? ??????????? ????????????? ???????? ???? ????? ????????? ?????????? ??????????? ???, ??? ???????????????, ????????????? ?????????? ? ????.
?????? ???????? ???????????? ?????????? ?????????????????? ????????? ?-2 ? ????
??????? ??????????, ??? ???????? ?????? ??? ?????????? ? ????????? ?????????? 187?442 °?
? ?????????? ???????? 15 % ?? ????? ????? ??????? ??? 27 % ?? ??? ???????????? ?????
(???. 4). ??????????? ?????? ??????????? ??? ? ?????????? ??? 490 ? 580 °?, ????? ??# 126 #
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?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
???. 4. ??????? ???????????? ?????????? ????????? ?-2 ? ???? ???????
???????????? ? ???????? ??????????? ????????? ?-1, ??????????? ?? ?????? ??? ?????????
?-2 ?????? ? ???? ?????????.
??? ???????? ??????????????? ?????????? ?-1 ? ?-2 ? ???? ?????? ??????? ???????????????? ??????????? ???????????? (???) ?????????? ??????? ???????????????
???????? ? ??????????? ??? 79 ? 95 °? ??????????????, ????????, ????????? ? ?????????? ??????????????? ?????. ??? ?????????? ????????? ??????????? ?? 750 °? ????????
??????? ?? ???? ??????????. ??????, ??? ??????? ? ????????????? ??????????? ??????????????? ? ??????????????? ?????????, ?????????????? ?????? ?????????? ? ????????? ?????.
??? ???????? ???????????????? ?????????? ?-1 ? ?-2 ? ???? ??????? ?? ?????? ???
?????????????? ??????????????? ???????, ????????? ??????? ? ????? ????????????? ???????????? ???????????? ???????? ?????? ????? ?? ?????? ???. ??? ????????? ?? ??, ??? ?????? ????? ?????????? ?????????? ? ?????????? ??? ???????????? ???????????, ??? ? ?????????
????????????? ???????? ????????? ??? ????????? ??? ??????????. ??? ???? ?????????????
???????????? ??? ????????? ?-1 ??????????? ????, ??? ??? ????????? ?-2, ???????? ??? ???????????? 480 ? 570 °? (???. 5).
????????????? ???????????? ????????? ?????????????????? ?-2 ???????? ??????? ??
??? ?????????????? ??????? ??????????? ?????? ????? ? ????????? ?????????? 710-780 °?
(???. 2), ??????? ????? ??????? ? ?????????? ??????????? ??????????? ?????????.
???????? ??????????? ???????????????? ??????? ??????????? ?????????? ????????? ?-1
???????????? ??????? ??????? ??????? ? ????????? ???????? ??????, ???????????, ?????
(???. 6). ? ??????? ????? ????????? ?????????? ???????????? ????????, ?? ??? ????????? ??????? ???? ? ?????????? ? ??????? 20?. ??? ?????? ?????? ??????????? ? ???????????? ??????????? ????????? ?????????? ? ?? ??????????? ??????? (??. ???????).
? ????????? ?-2 ?????????? ???????????? ?????????? ????????????????? ??????????. ?
??? ??????????? ????? ?????????? ?????????????? ??????? (~80 % ?? ????? ???????????
# 127 #
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?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
???. 5. ?????? ??? ?????????? ? ????????????? ?????????: 1 ? ????????? ?-1; 2 ? ????????? ?-2
???. 6. ?????????????? ????????? ?-1 (1) ? ?-2 (2): † ? ?????; Ќ ? Mg ? ???????; ? ?????; } ? ?????;
S ? ??????????
?????), ? ?????????????? ??????????? ?????????? ????? ~ 10 ???. %, ????? ~ 5 ???. %, ?????,
??????????.
???????? ?????????? ?????? [17] ?????? ???????? ???????? ? ????????? ????????????
?? ??? ? ??2 ? ????????? ?????????? 800?1000 °?. ?????????? ??????? ???????? ???g(??3)2
?????????? ? ???? ????????????? ????????: ??? 720-870 °? (? ???? ?? ????????? ??????????
??????????? ??????????? ?g??3) ? ??? 870?1000 °? (? ???? ????????? ???????????? ????3).
?????? ???????????? ?????????? ??????????, ??? ?????????? ???????????? ??????????? ? ????????? ???????????, ??????? ????????? ? ???????? ?????????? ????????? ?????????? ???????, ???????????? ? ?????? ???????, ??? ????? ???? ??????? ? ????????? ? ?????????
??????????? ???????? (???????? ?? ????????????????????, ????????, ????????????? ? ?.?.)
# 128 #
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?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
[18-21]. ? ?????????, ??????????, ??? ??????? ????????? ??????????? ??????? ????????? ??????? ?????? ????????????? ?? ???? ????? ??????? ?????? [22]. ? ?????? ????? ????? ????????,
??? ??????????? ? ?????? ?????? ????????? ???????? ?????? ????? ????????? ?-2 ? ???????
708-778 °? ????? ???? ?????????? ???????????? ??????????????? ????????, ???????????? ?
?????????? ?????.
??????
??????? ????????? ???????????????? ? ??????????? ???????????? ???????????, ???
??????????? ??????????? ? ???? ?????? ???????????? ????? ????????? ????????????? ????
(????? ?????????) ?????????? ? ???? ?????? ? ????????????? ????????? 261-447 °? ? ???????????? ????????? ?????? ????? (2 ???. %/???) ??? 346 °?. ??????????? ????????? ?????????????????? ???? (????? ??????) ? ??????????? ???????? ??????????????? ????? ????????
?????????? ??? ???????????? ????? ? ???????????? ????????? ?????? ????? ??? 286 ? 456 °?.
??????????? ??????????? ??????????? ?????????? ? ???? ??????? ???????? ?????? ?????????? ???????? ????? ??? ? ???????????? ????????? ???????????? ???????????????? ?????????.
??????? ???????????????? ??????? ???????????, ??? ??????????? ????? ????????? ?????
?????? ????? ?? 80 ???. % ??????? ?? ??????????????? ????????, ??????????????? ???????? ?????????? ? ????????? ?????????? 708?778 °?, ??? ???????????? ???????? ?????? ?????
2,3 ? 3,2 ???. %/???, ??? ???????????? 751 ? 765 °?.
??????????? ??????????? ??????? ???????? ????????? ???????????? c ??????????????
??????????? HCNS-0 EA FLASHTM1112 ????????????? ????????????? ?????? ?????????????
??????????? ?? ???.
?????? ??????????
1. ????? ?.?. ?????????. ???????, ??????????, ???????????. ???.: ?????. 2007. 224 ?.
2. ?????????? ?.?., ??????? ?.?. ??????? ????????? ????????????? ? ?????? ???????? // ???????? ??????????????? ????? ???????? ??????. ???????????: ?????. 1985.
?. 39-45.
3. ????? ?.?., ?????? ?.?., ?????? ?.?. // ????? ????????????? ?????. 2012. ? 2.
?.1 55-163.
4. ????? ?.?., ???????? ?.?. ??????? ? ??????? ?????????? ??????????. ?????: ????? ?
???????, 1989. 176 ?.
5. ??????? ?.?., ?????????? ?.?. ????????? ? ???????? ?? ?? ??????. ?????: ????? ?
???????, 1986. 192 ?.
6. ????????? ?.?., ?????????? ?.?. // ?????????????? ???????. 2001. ? 4. ?. 38-39.
7. ??????? ?.?., ????????? ?.?., ???????? ?.?. // ?????? ??????? ???????. 1998. ? 4.
?. 88-91.
8. ??????? ?.?., ???????? ?.?. ??????????????? ??????????? ??????? ??????????: ?????? ? ????????. // ???. ???. ??????. 2007. ?. LI. ? 4. ?. 140-147.
9. Kozlovska J.1, Valan?ius K.2 and Petraitis E. Sapropel use as a Biofuel Feasibility // Studies
Research Journal of Chemical Sciences. 2012. Vol. 2. ? 5. P. 29-34.
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?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
10. ???????? ?.?., ?????????? ?.?., ?????? ?.?., ??????????? ?.?., ??????? ?.?., ????????? ?.?., ??????? ?.?. ???????????? ????????? ????????? ? ???????????????? ????????
????????? // ????? ????????????? ?????. 2004. ? 1. ?. 35-39.
11. ?????????? ?.?., ??????????? ?.?., ??????? ?.?., ????????? ?.?., ???????? ?.?. ??????????? ??????????? ????????? ? ????? ???????? ???? ? ??????????? ???????????? ????????????? // ????? ????????????? ?????. 2006. ? 1. ?. 21-23.
12. Kovalenko G.A., Adeeva L.N. Carbon-Mineral Sapropel Sorbent for Comprehensive Waste
Water Purification // Chemistry for Sustainable Development. 2010. V. 18. P. 181-188.
13. ??????? ?.?., ?????????? ?.?., ??????? ?.?. ? ??. ??????? ??????????? ???????
?????????? ?? ?? ??????????? ?????????????? // ????? ?? ????, ????? xi?. ?????. 1985. ?6.
?. 20-25.
14. ???? 11022-75. ???? ?????, ????????, ???????? ? ?????? ???????. ????? ??????????? ?????????. ?.: ???-?? ??????????, 1986. 5 ?. (? ???. ? 1, 2, ???? ???????? ??? 1985).
15. ???? 11306-83. ???? ? ???????? ??? ???????????. ?????? ??????????? ?????????.
?.: ???-?? ??????????, 1984. 5 ?. (? ???. ? 1, ???? ???????? 01.01.90).
16. ???????????? ?.?., ????? ?.?., ????? ?.?. ????? ???????????? ??????? ? ??????? ????????????? ??????? ?????????? // ????? ???????? ???????. 2001. ? 2. ?. 73-83.
17. ??????? ?.?., ??????? ?.?., ????????? ?.?. ? ??. ??????????? ?????? ????????? ? ?????? ?????. ?.: ?????, 1974. 399 ?.
18. Rubiera F., Fuertes A.B., Pis J.J., Artos V., Marban G. Changes in textural properties of
limestone and dolomite during calcinations // Thermochim. Acta. 1991. V. 179. P. 125.
19. McCauley R.A., Johnson L.A. Decrepitating and thermal decomposition of dolomite //
Thermochim. Acta. 1991. V. 185. P. 271-282.
20. Shoval S., Gaft M., Beck P., Krish V. Thermal behavior of limestone and monocrystalline
calcite tempers during firing and their use in ancient vessels // J. Thermal Anal. 1993. V. 40. ?. 263273.
21. Xiao X., Du S. C., Sohn H.Y., Seetharaman S. Determination of kinetic parameters using
deferential thermal-analysis application to the decomposition of CaCO3 // Metall. and Mater. Trans.
1997. V. 28. P. 1157-1164.
22. Criado J.M., Ortega A. A study of the influence of particle size on the thermal decomposition
of CaCO3 by means of constant rate thermal analysis. Thermochim Acta. 1992. V. 195. P. 163-167.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ??????? ???????????? ??????????? ??????????? ?????????? ???? ????????? ? ???????
Study of Thermal Conversions of Sapropels
from Kachkulnya and Barchin Lakes
of Novosibirsk Region by DTG-DCK
and XRD Methods
Victor I. Sharypova, Ivan P. Ivanova,
Olga Y. Fetisovaa, Oxana P. Taranb,
Vera D. Strakhovenkoc and Boris N. Kuznetsova,d
a
Institute of Chemistry and Chemical Technology SB RAS,
Akademgorodok 50/ 24, Krasnoyarsk, 660036, Russia
b
Boreskov Institute of Catalysis SB RAS
pr. Lavrentieva 5, Novosibirsk, 630090, Russia
c
V.S. Sobolev Institute of Geology and Mineralogy SB RAS
Koptyuga 3, Novosibirsk 630090, Russia
d
Siberian Federal University,
79, Svobodny pr., Krasnoyarsk, 660041, Russia
The comparative study of thermal decomposition of organic type sapropel (Kachkulnya lake) and
organo-mineral type sapropel (Barchin lake) from Novosibirsk region was carried out by DTG-DCK
and XRD methods.
It was established that the chemical composition of sapropel has the significant influence on their
behavior. In argon stream the thermal conversion of organic mass (OM) of organic type sapropel
is a one-step process in the temperature range 261- 447oC, with a maximum speed of weight loss
2 wt. % / min. at 346oC. At the same conditions two stages of OM decomposition with a maximum rate
of weight loss at 286 and 456oC are observed during the thermal conversion of sapropel of organomineral type. The process of thermal conversion of sapropels in the air stream is characterized by a
number of stages, including thermal decomposition of the OM and the subsequent oxidation of the
formed heavy organic products.
It was established by XRD method that the mineral part of sapropel from Barchin lake consist of low
magnesium calcite (up to 80 wt. %) which dissociates in the temperature range 708-778oC, with a
maximum rate of mass loss 2.3 and 3.2 wt. %/min., at 751 and 765oC, respectively.
Keywords: lake sapropel, thermal conversions, analysis, DTG-DCK, XRD.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 132-150
~~~
??? 546.873.273:535.37:548.57
?????? ???????
?.?. ???????*,
?.?. ?????????, ?.?. ????????
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79
Received 13.11.2012, received in revised form 15.01.2013, accepted 20.02.2013
??????????? ?????? ?? ??????? ??????????? ? ????????????????? ????????? ?????????????? ???????. ???????? ?????? ??????? ????????? ??????? ???????. ????????? ??????
?? ????????? ??????? ??????????, ? ????? ???????? ?? ??????????????????, ???????? ?
?????????????? ????????? ?????? ??????? ???????.
???????? ?????: ?????? ???????, ?????? ?????????, ??????? ??????????, ?????????.
????????
????????? ?? ?????? Bi2O3 ???????? ????? ????? ?????????? ???????: ????????
?????????? ?????????? ???????????, ??????? ???????? ???????????? ? ??????? ? ????????????. ??? ??? ?????? ?? ????? ?????????????? ??? ?????????? ?????? [1?4]; ? ?????????, ??? ????? ???? ???????????? ? ???????? ?????????-?????????? ????? ??? ????????????? ??????? [5].
??????????? ????????? ????????? ??????? Bi2O3 ? B2O3 ????????? ??? ? 1962 ?. (???. 1)
[6]. ??? ??????????????? ???????? ???? ??????????: Bi24B2O39 (12:1), Bi4B2O9 (2:1), Bi3B5O12
(3:5), Bi2B6O12 (1:3) ? Bi2B8O15 (1:4). ??????? ????????? ?????????????? ????????? ???????
Bi2O3?B2O3 ????????? ? [7]. ??? ?????? ???????? ?? ???. 2. ?????, ??? ? ???? ?????? ?????????? ?????? ??? ??????????: Bi5B3O12 (5:3) ? BiBO3 (1:1). ????? ????, ?????????? ?????????
????????? ??????? Bi2O3?B2O3 ????? ??????? ?????????? ??? 81?100 ???. %, ????? ??? ? ?????????????? ????????? ??? ??????? ???????????? ?? ~ 60 ?? 100 ???. % B2O3.
??????? ?????????? ????? ?????, ??????????? ???????? ??????? ??????? Bi2O3-B2O3 ?
??????? ? ?????? ??????????. ??? ?? ????? ??? ??????????, ??????? ???????? ?? ????????? ?????? ?? ?????????? ???? ???????.
???? ????????? ?????? ? ??????? ????? ????????? ????????????????? ?????, ??????????? ???????????? ??????-?????????? ??????? ??????? Bi2O3-B2O3.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: antluba@mail.ru
# 132 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???. 1. ??????????? ????????? ????????? ??????? Bi2O3 ? B2O3 [6]
???. 2. ?????????????? ????????? ????????? ??????? Bi2O3 ? B2O3 [7]
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
1. ????????? ??????? ???????
???????? ????????? ????????? ??????? Bi2O3?B2O3 (???. 1) ?????????? Bi24B2O39 ????????
????????????? ??? 905 ?. ?????????? ????? ??? ?? ????? ???? ???????? ?? ????????. ??? ???
????????? ?????????? ????? ??????????? ?? ???????? ? ???????? [8, 9] ??? ????? ????????????? ???????. ? [9] ????????, ??? ????????? ?????????????? Bi24B2O39 ?? ???????? ? ????????
????? ??????????? ???????????: ????? ?????????????? ????????? ? ????? ????????????????
(14?18 ???. % B2O3) ? ????????????? (622?628 ?) ??????????.
???????? [10, 11] ????????? ??????? ??????????????? ? ??????? 0?20 ???. % B2O3 ??????????, ??? ?????????? ?? ?????????? ????????? ? ???? ??????? ????? ?????? 12Bi2O3:1B2O3.
??????? ???????? ???? 25Bi2O3:1B2O3, ???????? ?? ??????? ??????????? ?? ?????????? ????????? ? ??????? ?????????????? ??????????, ?????? ?? ?????. ??????? ??????? 25:1, ?????????? ?? ??????? ?????? ??? ???????????? 893?913 ? ??? ??? ?????????????? ?? ????????,
?????? ???? ?????????? ????? ?-Bi2O3 + Bi24B2O39.
????????????? ?????????? Bi24B2O39 ? ????????? ????? 1 ??3 ???? ??????? ???????? ?
???????????? [100], [110] ? [111] ? ?????????????? ???????????????????? ?????? ???????????
?? ???????? [12]. ????????? ???????? ???????? ?????????? ?? ????????? ???? ??????????? ??????? ????????????? ?????????.
??????????? ??????????? ?????????? ?? ?????????????? ??????????????????? ???????????????? ? [13, 14]. ? ?????????? ??????? ????????????? ????????? ????? ????????? ?????????? ? ???????????????? ?????????? ????????? ????????????, ???????????? ?? [BO3]3- ?
[BO4]5-. ???????, ??? ??????????????????? ? ??????????? ??????? ??????????? ???????????
? ??????? ???????? ????? ????????? ? ????????????????? ??? ?????????? (?????????? ??????
[15], ??? ? ??????? Bi2O3?B2O3 ?????? ?????????? ??? ?????????? B2O3 < 50 ???. % ??????????
????????? ??????? ? ????????????? ????? ?????? ? ???????????? ?????? B ? O ? Bi). ?? ?????? [9], ???????? ?????????? Bi3B5O12, BiB3O6 ? Bi2B8O15 ????? ??????? ???????? ? ???????
? ?????????????????, ? ??????????? ?????????? BiB3O6 ? Bi2B8O15 ??????????? ???????????
????????. ??? ??? ????????? ?????????? ??????? ?? ???????? ???????????? ??????????.
????????????????? ???? ?????? [9] ??? ??????????? ??????? ??????????? ??????????. ??? ????????? ??????????? ???????? ? ?????????? ?????? ????????? ??????? ??????????????? ?????, ?????????? ??????? ????????????? ???????. ????????????? ?? ?????????? ????????? ?????????? ??????? ????????, ???? ?? ?????? ???????? ???????????? ?
???????? ???????? ????????. ????? ??????? ???????????? ???????????? ??????????? ?????????????? ??????? ???????. ???????? ??????????? ???? 0?0,2 ??/?, ? ???????? ???????? ?
1,5?6,0 ??/???.
????????????? ??????????????? ?????????? BiBO3 ? [9] ???????? ?? ????? ?????????????????? ???????. ??? ????? ??????? ????????? ?? ? = 1073 ?, ? ????? ????????? ?? ????????? 5 ?/?.
? [16] ????????????? Bi4B2O9 ???????? ??????? ????????????? ???????. ?????????????
????? ?????????? ?????????? ????????? ??????????? ???????? ????????????????? ?????
Bi2O3 ? H3BO3. ??????? ? Pt ????? ????????? ?? 20 ? ???? ??????????? ?????????. ????? ?
??????? ???? ????? ????????? ?? 893 ? ?? ????????? 1,5 ?/?, ????? ???? ? ??????? 4 ? ? ?? ????????? ???????????. ? ?????????? ?? ??????????? ????? ?????????????? ?????????? ???????
# 134 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
??????? ?????????, ? ????? ? ?????? ? ????? ????????????. ???????? ??? ??? ?????????
???? Bi4B2O9. ?? ???????? ?? ????? ? [16] ???? ??????? ? ??????????? ?? ??????? ?????????.
???????? ????????????? Bi4B2O9 ?????? 80 ?? ? ????????? 15 ?? ???????? ???????
???????????? [17]. ???? ????????? ???????????? ?? ????????? 0,75?1,25 ??/? ??? ????????
??? 25 ??/???.
? [18] ????????? ????????? ?? ???????? ??????? ?????????????? ? ??????? Bi3B5O12 ?
B2O3. ????????, ??? ??? ??????? Bi2O3 ? B2O3 ?????????? ??????? ???? ???????????, ??????????? ???????????? ?? ????????? ??? ?????????? ?????????? ????? ? ???? ??? (????????
?? 6 ?/??3). ??? ???? ??? ???????? ?????????? ?????????: ??????? ? ????????????? B2O3 ??
????? 50 ???. % ????? ?????????? ??? ???????? ????????? ??????????. ??? ???????????
?????????????? ??? ???????? ???????? ????? ?? ????? ??????? ??????????????? ??????? (??
???? ?????????? ? ? ?????? [9]).
? ??????????? ?????????????? Bi3B5O12 ??????? ???????????? ???????? ? [19]. ? ?????????, ?????????? ? ??????????????? ?????????? ????? ?????????? ???.
???????? ? ????????? ?????????? Bi2B6O12 (BiB3O6) ? ???????????? ?? ??????? ?????????
? ??????? [9, 20?30].
????????? Bi2B8O15 ???????? ???????? ????? [31-33]. ?.?. ????????? ? ???????? [33]
???????? ????????? ????? ?????????? ??????? ???????????? ?? ????? ?????????????????? ??????? ??? ?????????? ????????????. ??? ??????????? ???????????? ???????? ? ?????? ??
Pt ????????? ??????? ??????????, ??????????? ???????????? ????????. ???????????, ???
????????? ??????????? ?????????? Bi2B8O15 ??????? ? ??????? ????????? ????????, ??????????? ? ????????????????? ? ??????????? ????????. ????????? ???????? ??? ?????????? ??????????? ??? ???????????. ???????? ???????? ????????, ? ???????? ??????? ???????????? ??????????????????? ???????, ????????? ? ???????????? ????, ??? ????????? ?? Pt, ??????????
10 ??/???, ?????????????? ???????? ???????????? ??????????: 17 ? (???????????????????
?-????) ? 20 ? (?????????????????? ?-???? Bi2B8O15). ? ????? ??????? ???????? ??????? ??
?????????? ?- ? ?-???????????, ?????????????? ????? ????????? ???????? ?? 0,5 ?? ? ???????????? ???????? ?? 2 ??2.
2. ????????? ? ????????? ???????? ??????? ???????
? ?????? [34] ?? ?????? ??????? ??????????? ????????? ? ?????????? ?????????? ?????
??, ?? ? ? ? Bi2O3 ???????? ?????? ???????????? ??? ? ???????? ??????? ????????? ? ???????
Bi ? O. ???????????, ??? ? ???? ? ?, ? ? ? ? ? Bi2O3 ???????????? ???????????. ??Bi2O3 ???????? ??????????? ????????? ?????? ??????? ??????????????? ????????? ? ???????? ?????????????? ?????. ????????????? ????? ? ???? ???????????? Bi2O3 ????????? ??????, ? ????????
???? ? ?????????? ?????????? ??????????? ?????? Bi ? O.
???????????????????? ????????? ??????? ??????? [30] ????????? ? ????. 1.
???????? [5] ???????? ??????? ??????? ??????? ?? ?????? ?? ?? ???????, ?? ? ?? ??????????????? ?????????, ? ??? ????? ? ?? ????????? ??????????? ??????????, ?????????????
?? ?????????????? ?????????? ???????. ???????????, ???????? ????????? ???????? ?????????? ?????????? ?????? ? ?????? ???? ??????????. ??? ????? ????????? ???????? ????????????????????? ????????? ??? ? ??????? nBi2O3?mB2O3 ?? ?????? ????????? ???? ? ?????# 135 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
??????? 1. ???????????????????? ????????? ????????? ??????? ???????
??????????
????????
??.??.
????????? ??????
a, Е
b, Е
c, Е
?, ?, ?, ????
Z
?????????,
?/??3
Bi24B2O39
cubic
I23
10,123
?
?
?
1
9,189
Bi4B2O9
monoclinic
P21/c
11,107
6,627
11,011
?=91,04
4
8,184
Bi3B5O12
orthorhom-bic
Pnma
6,530
7,726
18,578
?
2
6,188
BiB3O6
monoclinic
C2
7,116
4,993
6,508
?=105,62
2
5,033
??Bi2B8O15
monoclinic
P21
4,314
22,150
6,469
?=105,49
2
4,150
2
4,103
6,803
P1
4,3159
6,4604
22,485
?=87,094
?=86538
?=74,420
monoclinic
P21/c
6,585
5,027
8,349
?=108,91
4
monoclinic
P21/n 14,1664 6,7514
4,4290
?=102,125
4
5,411
monoclinic
P21/n
8,4992 11,7093 4,2596
?=121,141
4
6,177
orthorhom-bic
Pca21
18,448
?
4
6,378
1
6,021
2
3,761
3
6,196
?? Bi2B8O15
triclinic
??BiBO3*
?? BiB3O
**
6
?? BiB3O6**
?? BiB3O6**
Bi3[B6O13(OH)]**
4,4495
4,2806
triclinic
P1
6,6257
6,6238
6,6541
Bi3[B4O6(OH)2]OH** triclinic
P1
4,300
8,587
10,518
BiB2O4F
P32
6,7147
?
6,4688
trigonal
?=89,998
?=89,982
?=119,992
?=113,11
?=100,50
?=90,36
?
???? ???????. ????? ??????? ??????????????? ???????? ???? ?????????? ?????????, ??? ?
??????????? ????????? m:n ??????????? ???????? ???????? ??????????? (Bx+yO3x+4y-?) (x ? ?????????? ????????????? (BO3), y ? ?????????? ?????????? (BO4)), ????????????? ????? x, ?
????? y ??????? ?????? (?? m:n =1,67), ? ????? ???????? ?????????? (???. 3). ????????, ??? ???
???? ??????????? ??????? ?? ????????? ???????? ? ????????. ????????? ?????? ??? Bi24B2O39
?? «????????????» ?? ????????????? ??????????? (???. 3), ?? ? [5] ??????? ??????????, ???
??? ???? ?? ????????? ? ???????, ? ??????????? ? ????????? ?????????.
????????, ??? ???????????? ???? ?????????? (?-????) ? ???????????????? p-????????
(Bi3+) ????? ???? ??? ????????, ??? ? ?????????. ? ????????????? ??????????? ?-???? ?
???????? ???????, ???, ?? ?????? ??????? [5], ?????????? ????? ????? ????????? ??????
????????? (??(Bi)) ? ???????? ????? ??????????????? ????????? (??(Bi)) ?? ???????????
??????.
??? ??????????? ??(Bi) ? [5] ??????????? ????? ????????? ??????. ?? ????????? ??????????? ???????? ???? ??????????? ??????????? ???????? ???????????????? ????? ?? Bi ? ????????? ?????????? ?????? ??????? nBi2O3:mB2O3 ?? ??????????? m:n. ???????, ??? ???
?????????? ?????????? ??????????? ?? Bi ????? ????????? ? ??????????. ????? ????, ??
???? ?????????? ???????? ??????????? (Bx+yO3x+4y-?) ????????????? ??????? ????????? ?? Bi (???. 4).
????????? ?????????????? Bi4B2O9 ? [16] ??????????? ??? ???????????? 293, 473 ? 723 ?.
????????, ??? ????????? Bi4B2O9 ???????? ????????? ? ???????????? ? ????????????? ?????# 136 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
???. 3. ????????? ?????????? ????????????? (BO3) ?????????? (BO4) ? ?????????? ????????????? ???????
? ??????????? ?? ????????? m:n
???. 4. ????? ????? ???????? ????????? K?(Bi) ? ????????? ???????? ???????????
???????? ????????????? BO3, ????????? ?? ????????? ??????????? Bi-O-????????? ? ???????
? ???????????????????? ???????. ??? ????????? ??????????? ????????? ? ??????? ?????
?????? ???????? ????? ?? ?????? ? ????????????? BO3, ?? ? ? ?????????? ?????????: ???????
????? ????? Bi ? O ???????? ? ????????? 293?723 ? ????? ??? ?? 0,01 Е.
???????? [5] ????????? Bi3B5O12, ??? ? ????????? Bi4B2O9, ?????????? ????, ?? ??? ????
«????????» ? Bi3B5O12 ????? ???????? ???????. ??? ??????? ?? ???? ???????? ????? 3 : [2? + T]
? 3 : [? + 2T] (? ? ???????????, ? ? ????????). ??? ?????? ??????????? ?????????? ? ???????????? ??????????? ????????? [B5O11]7- ? ????????????? ??????. ????? ???????? [5], ??? ????????????? ???? ? ????????????? ???? ?????? ?????? ? ?????? ?????????.
# 137 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
? ????????? BiB3O6 ??????????? ??????? ?? ???????????? ????????????? ? ??????????
????????????? ????? ??????????? <110> [5]. ? ????????????? ????????? BiB3O6 (???????? ????
?????????? ?? ?????? Bi) ???????? ??????????? ????????? ? ???? ????? (6 : [4? +2T]), ??????? ?????????? ?? ???? ??????????? ???? 3 : [2? + T] ? ??????????????? ?????????? (BO4).
????????? ? ???????????????????? ????????? BiB3O6 ????????????? ???????.
?? ?????? [33], ???????? ????????? BiB3O6 ????????? ?? ???????????? ???????????????
??????? [BO3]3- ? [BO4]5- ? ?????? Bi. ??? ???? ?????? BO3 ? BO4 ???????? ?? ???? ??????????
?????? ????????? ????????? ????? ?? ???????????? ??????? ? ?????????? ? ???????????
2?:1?.
? [29] ??? BiB3O6 ???????? ????????? ??????????? ???????????.
???????? ? ????????? Bi2B8O15 ????????? ? ??????? [5, 31-33]. ?? ?????? [33], ??? ?????
?????????? ??????????? ???????? ??????? ??? ????????? ?????????, ? ??????? ????????
????????? ????? ??????????? ?????. ? ?? ?? ????? ?????? ? ?????????? ????????? ??Bi2B8O15
???????? ????? 4-, 6-, 8-, 12- ? 24-??????? ?????.
?????????? Bi2B8O15 ??????????????? ? ???? ??????????? ???????????? [5]. ??????????????????? ??????????? ?-Bi2B8O15 ????? ?????????? ???????? ? ??????????? ??????????????? ??????????. ????????? ?????????????????? ??????????? ??Bi2B8O15 ???????????
???????? ?????? [33].
????????????? ??????? ?????????? ??????? ??????? ????????? ? [9]. ??? ?????? ???
??-???????? ??????????? ???????? ?? ???. 5; ????????? ?????, ??????????? ? ??- ? ??????????, ? ???????? ??????? ????????? ??? Bi24B2O39 ? BiB3O6 ? ????. 2.
???????, ??? ??? ??????? ???????????? ???????? ???????? ?????????? ??????????
Bi24B2O39 ??????????? ??????? ??????????????? ????????? ????? [35], ??????? ??????? ?????????? ? ????????? ????????? ? ??????? ???? ???????????????? ?????????? [36].
??????? 2. ????????? ????? (??-1), ??????????? ? ??- ? ??-???????? ??????? ???????
Bi24B2O39
??
54
63
83
97
129
141
206
232
275
341
372
458
??
??
BiB3O6
?????????
??
480
522
532
553
528
576
624
696
723
853
1121
1201
1280
1398
1443
698
722
1116
1276
1406
? (Bi(3) ? O)
?s (Bi(3) ? O)
133
167
192
209
269
315
369
394
?as (Bi(3) ? O)
2?
# 138 #
??
453
577
650
667
685
718
742
860
942
1065
1097
1194
1293
1380
1401
1452
1484
??
447
574
645
671
?????????
? (Bi(4) ? O)
? (Bi(3) ? O)
? (Bi(4) ? O)
? (Bi(3) ? O)
725
738
855
949
1066
1101
1209
1389
1406
1448
1487
?s (Bi(3) ? O)/ ?s (Bi(4) ? O)
? (??????????)
?as (Bi(4) ? O)
?as (Bi(3) ? O)
? (??????????)
2?(Bi(3) ? O)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
???. 5. ??-??????? ??????????? ??????? ???????
????????????? ?????? 4Bi2O3·B2O3 ????????? ? ?????? [37], ? ?????? xBi2O3(100-x)B2O3
(x = 60, 70 ? 80 ???. %) ? [38].
?????? ????? [39] ? [40] ??????????? ??????? ??????????? ????? (99,5 %[xB2O3(1-x)
Bi2O3]0,5 % CuO) ??? 0,07 ? x ? 0,625 ? ??????? (95 % [xB2O3(1-x)Bi2O3]0,5 % Fe2O3 ??? 0,07 ? x 0,90
?? ????????? ?????? Bi2O3 ? B2O3.
?????? ?? ?????????? ????????? BiB3O6 ????????? ? [28].
????????????? ???????? ?????? Bi2O3 ? B2O3 ????????? ??????????????? [41, 42], Bi2O3 ?
B2O3 ? PbO, Bi2O3 ? B2O3 ? MoO3 ? ???????? ????? [43] ? [44] ??????????????.
? [45] ???????? ?????? ??????????? ???????????? ? ???????? ?????????????? ??????
Bi2O3 + 30 ???. % B2O3.
?????? [46] ????????? ???????? ???????????? ??????? ?????? 20PbO·xBi2O3·(80?x)B2O3
(x = 20?60 ???. %).
??????????????????? ???????????? ?????? ??????? ??????? ???????? ???????? ??????
[47]. ?? ???. 6 ????????? ??? ??????. ?????????? ???? Cp ???? ?????? ?? ?????? Cp = f(T) ???
?????? ? ???????????? ??????, ???????????????? ??????????????? ???????? [48, 49].
??? ?????????? Bi3B5O12 ? BiBO3 ???????? Cp ?? ??????????? ??????????? ????? ????
??????? ?????????? ??????????? ??????????????:
Cp
369,26 156,1 � 103 T 115,49 � 105 T 2 ,
# 139 #
(1)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
C?, ??/?�?
C?, ??/?�?
?.?. ???????, ?.?. ?????????? ?????? ???????
1,0
0,8
1,0
0,9
0,8
0,7
0,6
0,6
1
2
0,4
300
500
600
700
5
0,4
3
400
4
0,5
800
0,3
300
400
500
600
T, K
700
800
T, K
C0P, ??/(? �?)
???. 6. ????????????? ??????????? ???????????? ???????? ??????: 1 ? 35 ???.% Bi2O3 ? 65 ???.% B2O3;
2 ? 40 ???.% Bi2O3 ? 60 ???.% B2O3; 3 ? 48,5 ???.% Bi2O3 ? 51,5 ???.% B2O3; 4 ? Bi3B5O12; 5 ? BiBO3
1,0
1
2
3
0,8
4
0,6
0,4
0,2
0
B2O3
20
40
60
???. %
80
100
Bi2O3
???. 7. ??????????? ??????????? ???????????? ??????? ??????? ?? ???????: 1 ? [50], 2 ? [22],
3 ? ???? ?????? [47], 4 ? [51]
Cp
80,39 65,5 � 10 3 T 4,52 � 105 T 2 .
(2)
? [47] ???????????, ??? ??????? ???????????? ?????????? ????? ???????? ???????
o
Bi2O3 ? B2O3 ? ??????????? ????????????? (???. 7). ?? ???? ?????? ???????, ??? ???????? C p
??????? ?? ???? ????? ?????????? Bi2O3. ??? ??????? ???? ??????? ? ???????? ??????? ????:
???????? ??????? ?????? ?????? ???? ??? ??????? ? ??????? ??????????? Bi2O3, ??? ?????
? ?????????? ??????????? ????? ?, ??????????????, ???????????? ??????? ? ????? ???????
??????????? ??????? ??????.
3. ???????? ??????? ??????? ? ?????? ?????????
????????? ?????????????? ??????? ?? ????????? ? ????????? ? ??????? ????????????,
???????????, ??????? ???????? ? ????????? ????????? Bi2O3 ? B2O3. ? ?????????, ????? ??????
# 140 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
?? ???? ????????? ?????? ????. ? ???? ????? ???????? ?? ???? ???????? ?????? [52], ? ??????? ????????, ??? ????????? ? ???????? ????????? ??????? ??????? ????? ????? ????????? ??????????
?? ??????? ??? ????????, ??????? ??? ???????? ? ??????? ??????????? ??????? (????. 3).
?? ????. 3 ???????, ??? ? ??????????? ??????? ???????? ???????? ??? 1123 ? ???????????
??????????? ?????????????. ?????????? ??????? ??????? ????? ???? ??????? ? ???????????
?????????? ??????????? ?? ????????. ? [52] ??????? ?? ????????, ??? ???????? ????????????
Bi2O3 ? ??????? ??????? ??????? ???????? ? ?????????? ????????? ? ?????????? ??????????? ???????????. ??????????? ?????? ???????, ??? ? ???????? ?????? ???????????? ?????????? ??????? ?? ???? ?????? ?????????. ??? ?????? ??????????????? ? ???, ??? ?????????
Bi2O3 ????? ?????????. ? ?? ?? ????? ????????? B2O3 ?? ???????? ??????? ?? ? ????????????
?????????? ???? ??????? ? ???????? ?, ?????????????, ? ?????????? ????????? ??????. ??
????. 3 ?????, ??? ??????????? ???????????????: ?????????? ?????????? ????????? ??????
?? ???????? ???????? ????????. ?? ????? ???????, ??? ??? ????????? ????????? ?? ????????, ?
??????? ???????? ????????? ??????????? ??????????? ????????? ??????? ???????.
????????????? ????????? ????????? Bi2O3-B2O3 ???????? ?????? ?????? [53]. ?????????? ?????????? ????????? ? ????. 4.
???? ???????? ???????? ? ?????????????????? ????????? Bi2O3 ? B2O3. ??? ???? ?? ???????? ??????????? ?????????. ? ?????????? ??????? ????????????? ????????? ????? ???-
??????? 3. ???????? ?????? Bi2O3 + 60 ???. % B2O3 ????? ????????? ???????? ???????? ??? 1123 ?
?, ???
CBi, ????. %
d, ?/??3
u·103, ?/?
Tg, oC
15
45
132
190
220
73,3 ± 1,5
74,6 ± 1,5
73,1 ± 1,5
74,5 ± 1,5
72,9 ± 1,5
5,837
5,647
5,165
5,051
4,970
3,846
3,894
3,962
3,995
4,021
455
458
470
470
474
??????????: d ? ?????????, u ? ???????? ???????????, Tg ? ??????????? ???????????.
??????? 4. ????????????? ????????? ????????? Bi2O3 ? B2O3
?, ???/?2 ??? ?, ?
Bi2O3,
???. %
973
1023
1073
1123
1173
1223
1273
1323
1373
0
10
20
30
40
50
60
70
80
90
100
214,8
221,0
227,4
-
78,9
77,7
142,4
190,0
213.0
220,6
227,8
227,1
223,6
-
80,3
78,6
141,0
186,6
211,4
220,0
227,9
227,0
223,3
-
83,5
82,6
81,7
140,4
183,8
209,6
220,1
227,6
226,6
222,4
217,1
84,8
84,2
84,2
139,0
181,5
208,2
219,6
227,1
226,1
221,9
216,1
86,4
86,1
86,2
138,4
179,8
206,9
218,4
226,2
225,6
221,2
215,6
88,3
88,1
87,9
138,8
177,6
205,5
217,5
224,6
225,4
220,5
214,8
90,2
90,0
89,3
139,4
175,4
203,7
215,2
222,8
224,2
219,2
213,1
91,7
91,3
90,3
140,2
173,3
200,9
212,3
219,6
223,3
218,4
211,7
# 141 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
???. 8. ??????? ??????? ????????? Bi2O3 ? B2O3 ?? ????????. ?, ?: 1 ? 1000; 2 ? 1100; 3 ? 1273
?????? ?????????? ? ???????????????? ?????????? ????????? ????????????, ???????????? ?? [BO3]3- ? [BO4]5- [13, 14]. ?????????, ??? ??????????????????? ? ??????????? ???????
??????????? ??????????? ? ??????? ???????? ????? ????????? ? ????????????????? ??? ??
?????????? (?????????? ?????? [54], ??? ? ??????? Bi2O3 ? B2O3 ?????? ?????????? ??? ?????????? Bi2O3 ?????????? ????????? ??????? ? ????????????? ????? ?????? ? ????????????
?????? B ? O ? Bi). ?? ?????? [9], ???????? ?????? ??????? ??????? ????? ??????? ????????
? ??????? ? ?????????????????, ??? ????????? ??????????? ??????????????.
????????? ???????? ????????? Bi2O3 ? B2O3 ????????? ? ?????????????? ?????????????? ???????????? ????????????? [55]. ???????? ????????????? ?????????? ????????? ????? [56, 57].
?? ???. 8 ???????? ??????? ??????? ????????? Bi2O3 ? B2O3 ?? ????????.
????? ????????, ??? ? ??????????? ?????????? ? ????????? ?? ~ 50 ???. % B2O3 ???????? ? ?????? ?????????????, ? ?????, ? ?????????? ?????? ???????????? B2O3, ??????????
???????????? ?????????? ???????? ?????????. ?????????, ??-????????, ????? ???? ???????,
??? ??? ????????????? ????? ???? ????? ????? ??????? ???????? [58]. ????????????? ???????
??????? ????????? Bi2O3-B2O3) ?? ? (???. 8) ????? ???? ??????? ?? ?????????? ?????????.
???????? [52] Bi2O3 ????? ????????? ? ???????? ????????????????? ??? ??????? ?????????????. ???????? ? ???????? ?????????????????, ????? Bi ????? ????????? ? ??????????? ?????? ? ????????? (BO3), ? ?? ? ???????????????? ? (BO4). ??-?? ??????????? ??????????? ???
????????????????? ????? Bi ????? ??????????? ? ????????????? ??????????? ????????????,
???????????? ? ????????, ? ??????? ???????. ??????????????? ??????? ???? ??????????? ?
??????????? ????? Bi3+, ? ?????????? ????? ?????????? ?????????? ???? ???????????????????????? ????. ? ????????? ??????????????? ? ?????? [53].
???? ?????? ?? ?????????????????? ????????? Bi2O3 ? B2O3 ???????? ?? ???. 9.
??? 1000 ? ???????? ж ??????? ?????? ??????? ?? ?????????, ??? ??? ??? ???????????
????????? ????? 1098 ? [6, 59]. ????? ????, ??? ?????????? ? ????????? ????? 75 ???. % B2O3
?????????? ?????????? [6], ??????? ? ???? ??????? ???????? ????????? ж ?? ???????????.
?? ???. 9 ???????, ??? ? ??????????? ?????????? ? ???????? B2O3 ???????? ж ???????????
???????????.
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???. 9. ??????? ??????? ????????? Bi2O3 ? B2O3 ?? ??????????????????. ?, ?: 1 ? 1000; 2 ? 1100; 3 ? 1200;
4 ? 1273
????? ???????? ??????? ???????? ж ??????? Bi2O3 ? ????????? (18,5 ???. % B2O3) ???
1100 ?. ????????? ??? Bi2O3 ???????? ???????????? ????? ????????? ????????? ????? 2 ?, ? ???
????????? ~ 205 ?, ?? ????? ???? ???????, ??? ? ????????? ?????? ???????? ж ?????? ????
????. ??? ?? ????? ????? ? ????????????? ?? ???????????. ?? ?????????, ??? ??? ??????? ?
???, ??? ??????????? ? Bi2O3 ????? ???? ???????? ????? ?????? ??????????????????? [60, 61].
??????????? ?????????? ???????? ж ? ??????? ??????? ?? ?????????????? ?????????, ???
??? ??? Bi2O3-B2O3 ? ?????? ?? ?? ?????? ????? ???????? ????????? ??? ?????? [41-44].
????????????? ??????? ??????? ?? ?????????????????? (???. 9) ? ???????? (???. 8)
??????????, ??? ??? ???????? ?????????: ???? ???????? ?????????????? ????????
?????????????????? ? ??????????? ?????????? ? ????????? ?????? ????. ??? ???????????????
? ???, ??? ?????????? ??????????? ????????? ???? ? ?? ???????????? ????????????
??????????? ???????? ?????????, ??? ??? ????? ????????? ??? ?????? ж ????? ??? [62]
ж = enu,
(3)
??? e ? ????? ?????????, n ? u ? ?????????????? ????? ????????? ???? ? ?? ???????????, ???????
??????????? ? ??????????? B2O3 ? ???????.
????????? ? ???????? ??????? ?????? ???? ?????????? ?????? ??????? [48, 56, 58, 60, 61,
63?65], ? ?? ????? ??? ??? Bi2O3 ????? ???????? ?????? ?????????? [8, 66].
???????, ??? ?????? ????????? ????????? Bi2O3 ? B2O3 ????? ??????? ?? ?????????
????????? ??????. ? ?????? ?????? ????? ??????? ?? ???????? ????????????????? ??????
? ??????????? ??????? ????????? ? ??????, ?????? ? ??????????? ???????????? ?????????
???????? ?? ????????? ???????????? ????????????????? ????????? [60]. ? [48] ????????????,
??? ?????? ? ??????????? ? ?????????????????? ????? ? ??????????????? ?????????
????? ???? ? ?????????? ?????????? ?????????? ? ?? ?????????????? ????????? ?????????.
????? ????????????, ??? ??????? ???????? ???????? ? ??? ???????? ??????. ? ???? ??
? [52] ????????? ?????????????? ????, ??? ???????? ??????? ????????????? ?????? ? ?????
?????????? ??????? (? ??? ????? ????????).
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?????????? ???? ???????? ж ??????? Bi 2O3 ????????? ? ??????? [67] ? ?????? ?
????????? [68]. ???????? [68] ?????????? ???????? ж ?? ??????????? ???????? ??? Bi 2O3
?? ???? ??????????? ?????????? ??????????, ?????? ??? ???? ???? ??????????? ? ??????
????????????. ? ?? ?? ????? ?? ????????? ?????????????? ?????????????? ????????????
???????? ?????????????????? ????? ??????? ??????? ? ????????? ??????????. ?????
???????? ????????? ??????? Bi 2O3 ? Bi ?????? ????? ? ??????? ??????? ???? ??????
???????????? ? ???????? Bi 2O3 [66], ???? ?????? ?????? [69] ??????? ? ???????????????
??????????? ????????? ????? ? ??????? Bi 2O3 ? ??????? ?????????????. ?????????????????
???????? ???????????? Bi 2O3 ? ??????? ?????????? ?? ????????? ?? 870 ? ??????? ? ?
?????? [70]. ? ?????????? ???? ??????? ????????, ??? ??? ??????????? ????? ??????
???????? ???????????????????? ?????? Bi 2O3-x [71]. ??????? ??????? ??????????????
??????? ? Bi 2O3, ???????? [72], ????? ????????? ?? ????????????????? ??????????? ??
??????????????????. ???????, ??? ????? ??????????? ???????????? Bi 2O3 ??????????
????????? ? ?????? ??????? ????????? [73]. ???????? ?? ???????? ?????? [66, 74], ?????
????????????, ??? ? ?????? ????????? ? ????????? ??????? ????????? ???????????? Bi 2O3
??????????? ?? ??????????.
????????????? ??????? ??????? ????????? ??????? ??????? E? ? ?????????????????? Eж
??? ????????? ??????? ?????????? [75], ???
n = E?/Eж > 1,
(4)
?.?. ??????? ????????? ??????? ??????? ??????, ??? ??????? ????????? ??????????????????.
?????? ??????? ??????? ? ???, ??? ?????? ??????? ??????????????? ????? ???????? ?????????,
????? ??? ??????????????????, ????????, ?????????, ??????????? ?????????? ????????????.
?????????? ????? ?????????? ???????????? ?????? ?? ???????? ? ??????????????????
????????????? ??????? ????????? ?????? ?? ?? ????????? ? ????????. ??? ??????? Bi2O3
???????? n < 1, ? ??? ?????????? ? ???????? 18,5 ???. % B2O3 ??????????? ??????? ? ?????????
??????????? n > 1. ???????? [62] ??? ????? ???? ?????, ????? ??? ?????????? ???????????? ?
???????? B2O3 ?????????? ???? ?????? ????????????. ??? ????????? ????????????? ????????
????????? ???????? E? ? Eж ?????? ????? ?????, ?.?. n ? 1. ????????? ????????, ??? ????????????
???? ???? ??????????? ???? ?? ?????????, ??????? ?????????? ???????? [62, 75].
4. ??????? ???????????????
? ????????????????? ???????? ?? ?????? Bi2O3 -B2O3
???????? ??????? ?????????? ? ??????? Bi2O3 ? B2O3 ? Li2O (0?70 ???. % Li2O) ?????????
? ???????? ? ????????????? ??????? [76]. ???????????, ??? ??????? ?????????? ? ???????
?? ??????????. ??????? Bi2O3 ? 1Li2O·1B2O3, Bi4B2O9 ? LiBO2, Bi4B2O9 ? 1Li2O·2B2O3, Bi3B5O12 ?
1Li2O·2B2O3 ???????? ?????????????? ? ??????????????. ??????????? ?????????????? ?????????????? ??????????? ? ???? ???????? ????? 888, 897, 913 ? 968 ? ??????????????.
??????? ?????????? ? ??????? Bi2O3 ? B2O3 ?Na2O ??????????? ???????? ?????? [77].
????????, ??? ? ??????? ???????????? ????? 50 ???. % Na2O ???????? ??????? ?? ???????
??????????? ??????????? ????????? ????????? ??????? ? ???????????? ???????????????
?????????? ??????. ????????? ??? ????? ??????? ??????????? ??????? ? ???????? Bi2O5, ??
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??????????? ???????????? ?????????? ???????? Bi2O3 ? NaBiO2 ?NaBO2 ? B2O3. ????? ??????? ?????????? ? ???? ??????? ?? ??????????.
? ??????? Bi2O3-B2O3-K 2O ???? ??????? ????? ??????? ?????????? K6Bi(BO3)3 [78]. ???????????, ??? ??? ?????????? ??? ??????????? ???? 898 ? ? ???????? ??????????? ??? 1043 ?.
???????? ? ??????? ??????????????? ? ??????? CaO ? Bi2O3 ? B2O3 ????????? ? [79, 80]. ?
????? ??????? ??????????? ??????????? ?????? ???????? ?????????? CaBi2B4O10 ? ???????????? ????????????? CaBi2B2O7. ????? ????, ? ?????? [80] ????????, ??? ????????? ??????????
CaBi2B4O10 ? ??????????? ?????????????? ???????? ???????? ? ??????????? ?????????? ????? ?? ??????? CaB2O4 ? BiBO3.
?? ?????? [81], ? ??????? BaO ? Bi2O3 ? B2O3 ?????????? ?????? ??????????: Ba3BiB3O9
????? ??????? ??????? ??? 1123 ? ? ?????????? ?? ??????????? 1158 ?, ??? ??????? ??????????? ? ??????? ?????????; BaBiB11O19 ???????? ??????????? ??? 1080 ?; BaBi2B4O10 ????????
??????????? ??? 1003 ?; BaBiBO4 ???????? ????????????? ??? 1053 ?.
??????? ??????????? ? ??????? CaO ? Bi2O3 ? B2O3 ??????????? ? [82], ? ?????????? ? ?????? ???????? ???? ?????? ? ? ?????? [83].
??????? ?????????? ? ??????? Al2O3 ? Bi2O3 ? B2O3 ??????? ? ????????????? ??????? [84].
??????????? ????? ??????? ?????????? ??????? Bi2Al4B8O21, ??????? ?????????? ?? ???????????????? ????.
? ?????????? ???????, ??? ? ???? ????? ???? ??????? ?????? ?? ?????? Bi2O3 ? B2O3:
Bi2O3 ? B2O3 ? SiO2 [85], Bi2O3 ? B2O3 ? TiO2 [86], Bi2O3 ? B2O3 ? WO3 [87], Bi2O3 ?B2O3 ? PbO [88].
?????? ??????????
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# 148 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
73. ??????? ?.?., ???????? ?.?., ????? ?.?. ? ??. ????????????????? ????????????? ????????? ??????? Bi2O5, BiO2, Bi2O3, BiO ? Bi8O11 ? ????? ?????? ? ?????????. I. ???????????
???????????? ? ?????????? ????????? // ??????. ????. «??????????? ? ??????». 2007. ?. 10. ?.
1105-1110 // http:// zhurnal.ape.relarn.ru/articles/2?7/105.pdf.
74. ????????? ?.?., ??????? ?.?., ??????? ?.?. ? ??. ?????????????? ?????? ???????? ?
??????? ? ??????????. ????????????: ??? ???, 2004. 285 ?.
75. ???? ?.?., ????? ?.?. ?????????? ????? ???????????????????? ?????????. ?.: ???????????, 1966. 704 ?.
76. ?????? ?.?., ????????? ?.?. ??????? ??????????????? ? ??????? Li2O-Bi2O3-B2O3 //
???. 2002. ?. 47. ? 12. ?. 2038-2040.
77. ?????? ?.?., ????????? ?.?. ??????? ??????????????? ? ??????? Na2O- Bi2O3-B2O3 //
???. 2005. ?. 50. ? 12. ?. 2068-2071.
78. ????????? ?.?., ?????? ?.?., ???????? ?.?. ??????? ?????????? ? ??????? K 2OBi2O3-B2O3 // ???. 2005. ?. 50. ? 11. ?. 1851-1854.
79. ????????? ?.?., ??????? ?.?., ???????? ?.?. ?????? ??????? ? ??????? ? ???????
CaO- Bi2O3-B2O3 // ???????. ?????????. 2008. ?. 44. ? 1. ?. 76-81.
80. ?????? ?.?., ??????? ?.?., ???????? ?.?. ? ??. ??????? ??????????????? ? ???????
CaO- Bi2O3-B2O3 ? ????????????? ??????? // ???. 2008. ?. 53. ? 9. ?. 1614-1618.
81. ????????? ?.?., ???????? ?.?., ??????? ?.?. ? ??. ??????? ?????????? ? ???????
BaO- Bi2O3-B2O3 // ???. 2006. ?. 51. ? 12. ?. 2078-2082.
82. ????????? ?.?., ??????? ?.?., ???????? ?.?. ????????????????? ? ??????? Bi2O3B2O3-BaO // ???????. ?????????. 2008. ?. 44. ? 11. ?. 1397-1401.
83. ??????? ?.?., ??????????? ?.?., ???????? ?.?. ?????????? ?????????? ? ?????????
?????? ?????????????? ?????? ??????? BaO- Bi2O3-B2O3 ? La2O3- Bi2O3-B2O3 // ???. 1982. ?. 8.
? 3. ?. 347-350.
84. ????????? ?.?., ?????? ?.?. ??????? ?????????? ? ??????? Bi2O3-Al2O3-B2O3 // ???.
2004. ?. 49. ? 3. ?. 522-526.
85. Nie Q.H., Chen Y.F., Xu T.F. et al. Nonlinear optical properties of Bi2O3-B2O3-SiO2 glasses //
J. Wuhan University Techn. 2007. V. 22. ? 4. P. 806-808/
86. Xu T.F., Chen F.F., Dai S.X. et al. Third ? order optical nonlinear characterization of Bi2O3B2O3-TeO2 ternary glasses // Phys. B. 2009. V. 404. P. 2012-2015.
87. Zhang J., Nie Q., Dai S. et al. Nonlinear optical properties in bismuth ? based glasses //
J. Wuhan University Techn. 2011. V. 26. ? 1. P. 61-64.
88. Ehasanulla M., Srikanth K., Rao A.V. et al. Spectroscopic and magnetic properties of
PbO- Bi2O3-B2O3 glasses doped with FeO // RAS?YAN J. Chem. 2011. V. 4. ? 2. P. 343-353.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ?????????? ?????? ???????
The Bismuth Borates
Viktor M. Denisov,
Natalia V. Belousova and Liubov T. Denisova
Siberian Federal University,
79 Svobodny, Krasnoyarsk 660041 Russia
Data on phase equilibriums and thermodynamic properties of bismuth-borate system are considered.
Methods of obtaining bismuth borates are analyzed. Data on the structure of solids as well as the
electrical conduction, viscosity and surface tension of liquid bismuth borates are given.
Keywords: bismuth borates, methods of obtaining, phase equilibriums, structure.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 151-157
~~~
??? 669.334:669.24
??????? ??????? ????????
?? ????? ??????????
?.?. ???????*, ?.?. ???????
???????? ????? ? ?????????? ?????????? ?? ???,
?????? 660036, ??????????, ?????????????, 50/24
Received 07.11.2013, received in revised form 20.01.2013, accepted 06.02.2013
??????????? ??????????? ???????????? ?????????? ?????? ? ???? ?? ????? ?????
????????????????? ?????? ?????????? ???? ??????????? ????????????? (??????). ?
???????? ???????? ???????????? ???????? ????-1 ? ????????? 930. ?????????????? ??????
?????????????? ?? ?? ? 2,6-2,7 ??? ???????????????? ????????? ??????(3+). ????????, ???
??? ???????? ?????????? ????????? ???? ? ?????? ?? ??????????? ?????????. ??????,
???????????????? ?? ?????????? ??? ?????????????????, ?? ?????? ??????????. ??
????????? ????????? ??? ?????????? ???? ? ?????? ?????????? 3 ? ??????????????? ????????
? ??????????. ??? ???????? ? ??????? ???????? ??????? ??????????? ?????????, ??? ???????
? ???????? ?????????? ???????, ??????? ? ???????? ?????????? ?????????????? ? ???????.
??? ????????? ???????? ?????????? ?????????? ??????? ????????? ??? ?????????? ?? 55 °?.
????-1 ???????? ??????????? ????????? ? ????????????? ??? ?????????? ?? ?????. ??????
????????? 930 ?? ???? ????????? ????????? 0,019 %/?.
???????? ?????: ???????, ????????, ??????, ??????, ????.
????????
??? ?????????? ? ??????? ?????? ? ???? ?? ??????????????? ????????? ?????? ???????????? ?????????? ? ???????. ?????????????? ??????? ????? ??? ??????????? ????? ???????? ?
??????? ???????? ????????, ??????????? ???????? ???????????????? ????????????? ????????? ? ??????? ??????????????????? ? ??. ? ?? ?? ????? ??? ??????????? ?????????? ???????
?????????????? ????????? ?????????? ??????????? ??????? ???????? ??? ??????????? ????????? ?????????? ????????????? ?????????? ???, ? ????????? ?????????? ???, ????????????? ? ??. ????? ????, ?????????? ??????????? ?? ???????? ??? ?????????? ???????? ??????????????? ?? ????????????????? ?????, ????? ??? ??????? ??? ????? ?????? ????????????
??? ???? ????. ???????? ???????????? ?????????? ?????? ? ???? ?? ?????, ? ?????????, ?????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: kuzmin-dv@mail.ru
# 151 #
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?.?. ???????, ?.?. ???????. ??????? ??????? ???????? ?? ????? ??????????
?? ??????????? ????????? ??????????? ???????????????? ??? ??????????? ?????????????
?????? ??????? ????????????????? [1].
?????????? ???? ???????????? ?????????????? ? ???????????? ?????????? ??????
(??????????) ? ???? (???????????). ??? ????????????????? ???????? ?????????? ? ????????? ?????? ? ???? ? ???????. ???????????? ??????? ???????????? ?? ???? ???????????? ??????? ? ?????? ??????. ????????? ??????????? ???????? ??????????? ? ???????????? ?????
?????? ? ?????????? ???????, ???????, ??????? ?????????? ?????, ???? ? ?? ???????? ????,
??????????? ????????? ?????????? ??????????? ?????.
??? ??????? ???? ???????? ?????? ????????????? ?????????????? ??????? ???????? ??
????? ?????????? (??????????). ???? ????? ????????? ?????? ????????? ???? ? ??????? ??
????????? ???? 2, ?????? ? ??????? ? 3-4. ?????????? ?? ?????? ??????? ?????????? ???????? ? ???????-????????? ????????.
? ?????? [2] ????????? ????????????? ???????????? ??????? ?????? ? ???????? ?????????? Dowex M4195, Amberlite IRC748 , IONAC SR-5 ? Purolite S930 ?? ????????? ????????? ?????????? ?????????????. ????????, ??? ??? ?????? ???????? ??? ?????????? ?????? ? ???????? ?? ??????????? ?????????. ?? ???? ????????? ?????????? ?????????? ?????????? ????????
??? Dowex M4195. ?????????? ????????, ??? ?????? ???? ?? ??????????????? ? ????????????
Dowex M4195 ?? ????????? ? ??????? ????????, ????????? ?? ????? ??????? ???????????
???????? ????????????? ? ????????????? ????????? ?????????. ????????? ???????? ???????? ?????? ? ????????: ??? ?????? ??????? ?????????? ?? ?????? ???????, ??? ????? ????????????? ??????? ??????????? ?????? ??? ?????????.
? ?????? [3] ??????????? ?????????? ?????? ? ???????? ?? ????????? ????????????????
?????????? ????????? ??? ?????????? Purolite S930 ? S950 ? ??????????????? ? ??????????????? ?????????? ??????????????? ????????. ????????, ??? ???????? ????????? ???????
?? ??????????? ????, ? ????????? ??????????? ?????????? ??????? ??????? ??????????. ????????? ???????? ?????? ? ???????? Purolite S950 ????????? ? ??????? ???????? ? ????????
??????? ???????? ? ??????????.
???? ??? ???????? ??? ????? ?????????? ????????? ???? ?? ????????? [4], ??? ?????????
??????? ?????? ????????????? ??? ??? ??????? ???????? ???.
? ?????? [5] ???????? ??????????? ????????????? ???????? S930 ??? ?????????? ?????? ?
???????? ?? ????? ????? ?????????? ????????????? ?????????? ????????? ???. ??????????
?????? ??????? Fe(2+), Fe(3+), Cr(3+) ? Al(3+). ? ???? ????? ?? ?????????????? ?????????????
??????????????? ????????? ?? ?? = 4,3-4,7.
? ????????? ?????? ???????????? ?????????? ???????????? ?? ?????????? ?????? ? ????
?? ????? ????????????????? ?????????? ???? ?????????? ????-1 ? Purolite S930.
????????? ? ??????
? ?????? ????????? ??????????? ???????, ?????? ? ?? ???? ???????????? «?.?.» ?
«?.?.?.», ? ????? ???????? ???????? ????-1 ? S930 (?????????).
? ????????????? ???????????? ???? ??????????? ?????-?????????? ?????????????
(???????????? ????), ?????????????? ???????????? ?? ????????? 74 ???. ?????? ???? ??
???????? ??????????? ???????? ????. ????? ?????????? ????????? ? ?????????? ???? ??# 152 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????. ??????? ??????? ???????? ?? ????? ??????????
?????? ? ? ??????? ?????????? ?? 2 ?? 4 % ??? ???? ? ??? ????????? ???? (???????????) ? ?????? (??????????) ????? 60 % ? 40 % ?????????. ?????? ??? ?????????? ????????? (?? 75 %).
?????????? ?????? ????? ??? ?????????? ?????? ?????????????
CaO
Fe2O3 Co
Ni
Cu
S
?????????
MgO Al2O3 SiO2
??????????, %
37,4
2,77
41,6
0,95
11,9
0,017 0,59
0,27
1,0
???? ????????? ??????? ????????????????? [1]. ????? ?????????? ???????? ???????? ??
?????? ??????? ??????? ????? ????????? ????????.
??????? ??????? ???????? ?? ?????? ????????? ? ??????????? ???????? ????? ????????????? ????????????? ? ????????? ??? ??????????? 20±2 °?. ????? ????????????? 3 ?.
??? ?????? ??????? ?? ???????? ?? ?????????? ???????? ???????? ???? ???????? ? ????????
???????? ?? ??????? ?????? ????? ??????????????? ?????? ? ?????????, ?????????? ????????? ?????????? ?????????? ??????. ????? ??????? ???????????? ??? ?????????? ???? ?
??????.
????? ???????????? ?????????? ????? ???????? ?? ?????? ? ??????? ???? ? ????????
?????? 0,5 ??, ???????? pH, ? ????? ????????????? ??????? ?? ???? ? ??????.
??? ?????? ???????????? ???????? ? ???? ?????? ??????? ????????????? ???????????
?????????? ???????? ????????? 2 ? ?????? ???????.
?????????? ???????? ? ????????? ?????????? ?? ??????-????????????? ????????????
Analist 400 (Perkin Elmer), ????? ?????? ?????????, ? ??? ????? ? ?? ???, ????????? ????????????? ICP-MS 7500? (Agilent).
?????????? ? ??????????
?? ???. 1 ????????? ??????????? ???????????? ???? ? ?????? ? ???????? ?? ???????
??????? ????????? ????-1. ??????? ????????? ??? ?? ????? 3 ??? ?:? = 1:5 ?? ?????????? ????????, ???????: CaCl2 ? 160 ?/?, MgCl2 ? 35 ?/?, NaCl ? 100 ?/?, KCl ? 25 ?/?, Cu2+ ? 0,3 ?/?,
Ni2+ ? 0,625 ?/?. ??? ????? ?? ?????????? ???????????, ??????? ??????? ???????? ? ???????????????? ????????? ?????????? ?? ?????? ?????????? ?????? ? ???? ???? ????? ?????????.
??????? ?????????? ???????? ?????????? ?? 1 ? ????? 98 %.
???????? ?? ???????? ?????????? ????????? ???????-????????? ?? ????????? ????? ??
??????????? ???????? ????-1 ???????? ??, ??? ?? ?? ???????????? ??? ?????? ? ???????.
??????????? ?????????????? ????????, ??? ??? ?????????? ???????? ?? ????? ??????????
??????? ????????? ????????, ??? ????????, ??-??????, ? ??????? ??????? ?????? ????????,
? ??-??????, ? ??????? ??????? ???????? ? ??????? ????????? ??????. ? ???? ????? ??????????? ??????????? ?????????? ???? ? ?????? ?? ????????? ????????????????? ?????????
Purolait S 930, ??????? ??? ?????????? ?????????? ?????? Purolait ??? ?????? ? ????????.
??????? Purolait S 930 ???????? ?????????? ???????????? ?????????? ? ????? ?????????? ?? ?????? ?? ????? ? ????????? ???? <1 ??. ????????? ???????? ???????? ??????????
0,74 ??/?, ???????????? (????????????) 45 %.
??????????? ??????? ????????? ???????? ??????????????? ???????? ? ????????? ? ?????????? ?????????? ??????, ???????? ?? 2,9 ????-???/? ???????? ??????. ??????? ?????? ?? ?????? ? ???? ? ???????????? ????? 5 % ?????????: ?????? ? 0,95 ????/? (56 ?/?); ???? ? 1,05 ????/?
(67 ?/?). ?????? ? ???? ??????????? ????????? ?????? ?????? ?? ???????? ???????.
# 153 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????. ??????? ??????? ???????? ?? ????? ??????????
0,7
????????????, ?/?
0,6
2
0,5
0,4
0,3
1
0,2
0,1
0
0
20
40
60
80
100
?????, ???
???. 1. ??????????? ???????????? ???? (1) ? ?????? (2) ? ???????? ?? ??????? ??????? ????????? ????-1
1,2
1
??2+, ?/?
0,8
0,6
1
0,4
0,2
2
0
0
50
100
?????, ???
???. 2. ?????????? ?????? (1) ? ???? (2) ?? ??????? ?? 4? ???????? ??????? ??????: ?? = 1,69-1,75;
?:v????. = 5:1; T = 20 °?
????????? ??????? ????? ???????? ?????????? ?????? (????? 1,5 ??), ????? ???? ???????, ??? ???????? ???????? ?????????? ???? ? ?????? ?? ??????????? ????????? ????? ?????????. ??????? ????????? ? ??????????? ???????? ?? ?????????? ????????, ???????? ??
??????? ? ????????? ????????????? ?????????? ???? ??????????????????: ?????? ?????? ?
4?, ?????? ? 1,11 ?/?, ???? ? 1,1 ?/?; ?? = 1,69-1,75. ?????????? ???????????? ????????? S 930 ?
????????? ????? ??? ?: v????. = 5:1 ? ??????????? 20 °?.
# 154 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????. ??????? ??????? ???????? ?? ????? ??????????
?????????? ????????, ??? ??????? ??????? ???? ????????? ?????????? ?????? ? 90 %-???
?????????? ??????????? ??? ?? 30 ???. ???????? ? ??????? ?????????? ?????? ???????????
????, ??? ????, ? ????????? 55 % ?? ?? ?? ????? (???. 2).
??? ????????? ??????????? ?? 50 °? ???????? ???????? ??????? ???????? ??????????? ??????????, ??????????????, ?? 30 ??? ?????????? ???? ?????????? ????? 95 %, ? ?????? ?
75 %.
?????????? ?????? ? ???? ? ??????????? ??????? ????????? ?? ???????????????? ?????????, ? ??? ??????????????? ???? ????????????? ????????????? ???????? ??? ????????
??????????? ?????????. ??? ?? ???????? ????? 1,8 ?????????? ???? ?????????? ????? 98 %, ???
?????? ? ????? 50 %; ??? ?????????? ?? ? 2,6 ?????????? ???? ?????????? ?? 99,7 %, ? ?????? ? ?? 95,5 %. ????????? ???????? ????????? ?????? ? ??????????? ??? ???????? ????????? ?
?????????? ?????? ??? ??????? ?????? ? ????????????? ????? 1 ?.
??? ???????????? ????????? ?????????? ???????? ?? ????? ????? ????????????????? ????????? ?????????? ???????????? ???????? ???????? ???????? ?????????? ???????? (???. 3). ?
???? ???????????? ?????????? ???? ? 4? ???????? ??????? ?????? ???????????, ?????????????? ?????? ?? ?? = 2,6 ??? ???????????????? ????????? ??????, ????? ?? ?????? ?????????
??????? ? ??????????? ???????? ????????? ?????? ?????? S 930 ??? ?:?:v????. = 1:5:0,3.
?? ??????????? ???????????? ???????????? (???. 3) ????? ??????? ??? ??????? ???????
????? 20 ???. ?????????? ??????? ?????????? ???????? ?????????? ? ????? ????????? ????
????????? ??? ?????? 99 %, ???????? ? 99 % ? ???? ? 99,5 %. ??? ???? ???????????? ? ??????????? ???????? ?? ???????? ????????????? ?? 3. ???????? ??????????? ??????? ??????,
????????????, ??? ?????? ???????? ?????????? ???????? ??????? ? ??????????? ???????????
???????? ?????? ? ?????? ????????? ????????.
??? ?????????? ???????? ??????? ???????? ??????? ??? 55 °?, ? ????????? ???????
???????? ???????. ???????????, ??? ??? ???? ???????? ?????????? ???????? ??????????? ?????????? (???. 4). ???, ???? ??? 55 °? ?? 2 ???? ?????????? ??? ?????? ????????? 85 %, ? ???? ?
97 %, ?? ??? 20 °? ?????????????? 46 ? 72 %.
??? ??? ??????????, ?????? ???????? ?? ???? ????????? ???????? ???????????? ???????????? ?????????? ???????? ??? ?????????? ???????? ?? ?????. ??? ?????? ????? ???????
????????? ?????? ????? ???????????? ???? ???-19 ? ???????? 4? ??????? ?????? ???????????? ? ??????? S 930 ??? ????????? ?:?:v????. = 1:5:0,3 ? ??????? 180 ?, ?? ???????? ???????????? ? ???????? 2,6-3,5.
?? ???. 5 ????????? ??????????? ????? ???????? ?? ??????? ??????? ? ??????. ????????????? ????? ????? ????????, ????????? ?? 180 ? ???????????? ????????, ????????? 0,035 ?
??? ? ??????? ?? 1 ? ???????? ???????? ? ??????? 1,95·10 -4 (???-1) (0,019 %/???). ??? ???????????? ???????? ??????? (????? ???????? ?????? ? ??????? 2 ?, ???????? ? ?:?:v????. = 1:5:0,3) ?????? ???????? ?? ??????????? 1 ? ???? ? ????????? ?? ????? ??????? ????? 46,5 ?.
??????
????? ???????, ??????????? ???????????? ???????? ??????? ????????????? ????????
Purolait S 930 ??? ?????????? ??????? ???????? ?? ?????. ??? ?? ???????? 2,7-3,0 ??????????
????, ?????? ? ???????? ??? ?????????? ???????? ????????? 99 %. ????????? ???????, ??# 155 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????. ??????? ??????? ???????? ?? ????? ??????????
1,2
1
1
0,8
??2+, ?/?
??2+, ?/?
0,8
0,6
1
0,4
1
0,4
2
0,2
0,6
0,2
3
2
0
0
0
50
100
0
50
?????, ???
100
150
?????, ???
???. 3. ????????? ???????????? ?????? (1), ????
(2) ? ???????? (3) ? ???????? ?? ??????? ???
??????? ??????? S 930 ? ????????? ????? ??
??????: ?? = 2,6; ?:?:v????. = 1:5:0,3; ???????????
-20 °?
???. 4. ????????? ???????????? ?????? (1), ????
(2) ? ???????? ?? ??????? ??? ??????? ???????
S 930 ? ????????? ????? ?? ??????: ?? = 2,7-2,8;
?:?:v????. = 1:5:0,3; ??????????? 55 °?
3,58
????? S930, ?
3,56
3,54
3,52
3,5
3,48
y = -0,0007x + 3,5896
3,46
3,44
0
50
100
150
200
?????, ???
???. 5. ????????? ????? ?????? Purolait S 930 ??? ?????????? ???????? ?? ?????: ?????? ?????
???????????? ?????????? ???? ? ???????? 4? ??????? ??????; ?:?:v????. = 1:5:0,3; ?? = 2,6-3,5
?????????? ?? ?????? ????????????????? ???? ? ??????, ??????? ???????? ?????????? ????????. ??? ??????????? ??????? ??????????? ?????????? ??????? ??????? ??????? ?????????
??? 50-55 °?, ????????, ? ??????????????? ????????????? ????????. ? ???? ???????? ?? 2 ?
?????????? ?????? ??? ??????????? ?:?:v????. = 1:5:0,3 ?????? ????????? ?????????? ??????????? ?????????? ?????? ? ? 85 ?? 90-92 %, ???? ? ? 97 ?? 98 % ? ?????. ?????????? ??????????
# 156 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????. ??????? ??????? ???????? ?? ????? ??????????
???????? ? ???? ???????? ?????? ? ??????. ?????? ????????? 930 ?? ???? ????????? ????????
? ?????????? 0,019 %/?.
?????? ??????????
1. ??????? ?.?., ?????? ?.?. , ???????? ?.?., ??????? ?.?. ?????? ??????????? ??????
??????????? ?????????? ??? ??????? ????????????????? // ??????? ??????? ???????2009:
??????? ???????? I ????????. ?????????. ??????????, 2009. ?. 366-369.
2. Mendes F.D., Martinsb A.H. Selective sorption of nickel and cobalt from sulphate solutions
using chelating resins // International Journal of Mineral Processing. 2004. Vol. 74, Issues 1?4. 19
November. P. 359?371.
3. Deepatana A., Tang J.A., Valix M. Comparative study of chelating ion exchange resins for metal
recovery from bioleaching of nickel laterite ores // Minerals Engineering. 19 (2006). P. 1280?1289.
4. Petru Bulai, Catalin Balan, Camelia Seripcarin, Matia Macoveanu. Equilibrium and kinetic
studies of copper(II) removal on Purolite S930 resin // Environmental Engineering and Management
Journal. Sept/Oct. 2009. Vol. 8. ?5. ?. 1103?1109.
5. Zaimawayi Zainol, Michael Nicol. Comparative study of chelating ion exchange resins for the
recovery of nickel and cobalt from laterite leach tailings // Hydrometallurgy. 96 (2009). P. 283?287.
Sorption of Non-Ferrous Metals
from Pulps by Chelates
Dmitrii V. Kuzmin and Vladimir I. Kuzmin
Institute of Chemistry and Chemical Technology SB RAS,
50/24 Akademgorodok, Krasnoyarsk, 660036 Russia
The possibility of nickel and copper sorption from pulps after hydrochlorination of poor sulphide
Kingash deposit (Russia) was considered. Chelatons ANKB-1 and Purolite-930 were used as the
sorbents. Previously, slurry was neutralized to pH ? 2,6-2,7 for hydrolytic precipitation of iron (3 +).
Shown that both sorbent effectively extract copper and nickel from weakly acid solutions. Magnesium,
which was extracted from serpentine by hydrochlorination did not interfere with the extraction. For
the extraction of copper and nickel the contacting time of the sorbent with solutions is about 3 hours for
model solutions. In the transition to a pulp, sorption rate is significantly reduced, which was associated
with the effect of silicic acid. It in appreciable amount leached into solution. To speed the process of
extraction it was proposed to carry out the process by heating to 55 °C. ANKB-1 was mechanically
unstable and unsuitable for extraction from pulps. Purolite 930 losses by abrasion were 0.019 %/h.
Keywords: sorption, chelates, pulp, nickel and copper.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 158-169
~~~
??? 54.05
??????????????? ?????????????????????
???????????????? ??????????
?????? ???????? ? ??????? ? ????? ????????
?.?. ??????????,?, ?.?. ???????????, ?.?. ??????????,
?. ?????????, ?. ???????, ?.?. ?????????,?*
?
???????? ????? ? ?????????? ?????????? ?? ???,
?????? 660049, ??????????, ??. ?. ??????, 42
?
????????? ??????????? ???????????,
?????? 660041 ??????????, ??. ?????????, 79
?
IRCELYON,
2 Albert Einstein av., F-69626 Villeurbanne Cedex, Lyon, France
Received 10.12.2012, received in revised form 30.01.2013, accepted 07.02.2013
??????? ??????????????? ????????????????????? ???????????????? ?????????? ??????
???????? ? ??????? ??? ??????????? 20-90 °C ? ????? ????????. ???????????, ???
??????????????? ??????????????? ???????????????? (??) ? ??????????? ???????? ???-2
????????? ??????? ??????????? ? ????????????????? ???????? ??????????????? ?? ?
???????? ??????? ????????????????? ????????. ? ?????? ??????????? ???????????????
?? 55 ?? 90 °C ????????????? ??????? ??????????????? ?? ? ?????????? ?????????????????
??????? ? ???????????????? ????????. ???????? ?????? ??? 13C ????????????? ?
???????????????? ?? ?????????? ?????? ????????? ??? C2 ? C4 ?????????? ?????? ????????
???????????? ???? ? ??? C6 ?????????? ?????? ???????? ??????? ????????? ???????? ? ???????
????? ????????????????.
???????? ?????: ???????????????, ???????????????, ???????????????, ?????? ????????,
???????, ???????????????? ???????????????, ????????.
????????
???????????? ???????? ? ????????? ?????????????? ? ??????????? ????????????? ?????
??? ??????? ????????????? ???????????? ?????????. ??????? ????????????? ????????????
?? ??????????? ???????? ????????? ???????????? ???????? ??????? (???), ????????????? ??-
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 158 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
????? ? ???????????? ? ???????? ????????? ???????????. ? ????????? ????? ?????? ??????? ?
???????????????, ?????????? ?? ?????? ???????????????? ??????????? ????????????? ????????????? ?????????????, ??????? ????? ????????? ???????????? ????????. ????????????
? ??????????? ???????? ? ???????? ?????????????? ??????? ? ?????????????? ?????????????????, ??????? ???????? ?? ????? ????????? ?????????????, ???????? ???????? ??????????
???????? ???????? ?? ???????? ???????? ? ???? ?????????? ?????????? ??????????. ?????
????, ??????? ????????????? ???????????? ???????? (??? ????????? 1 ?? ???????? ??????????
???????????? ?? 10 ? ?????? ???????? ???????? ?????) ??????? ? ?????? ??? ????????????? ?
????????? ????????. ? ????????? ????? ????????, ??? ???????????????? ??????????? ???????? ????????? ???????????????? ????????????. ??? ???????? ? ????? ???????, ??????? ????????, ?????????? ??????, ????????????? ?? ?????????? ???????????????? ?????????? [1, 2].
???????????????? ??????????? ???????????????? (??) ????????? ??????????? ???????????, ????????????????? ? ????????????????? ????????? ?? [3], ? ????? ????????? ??????? ???????????????? ? ?????????????????? ??????????, ??? ?????? ????????????? ??
?????????? ??? ???????????? ? ??????? ????????-?????????? ??????????? [4].
??? ??????????????? ????????????? ? ???????? ?????????????? ??????? ????? ??????? ?????????? ????????? ??????? ????????? ? ?????????? ????????? ??????????, ?????
??????? ???????????? ??????? ???????????? ????????? ? ?????????, ?????????, ????????????????? ? ??????????. ??? ?????? ???????????? ??? ??????????????? ?????? ????????? ? ??????????? ?? ?????????? [5-7].
??????? ??????? ????????? ?????????? ??????? ????????? ? ??????????? ???????? ????????????? ? ???????? ????????? ??????? ????????? ??????????????? ???????. ??? ?????????????? ??????????????? ??????? ? ????????? ??? ??????????? 0 °C ?????????? ????????
SO3 ? ??????? ? ????????? ?????? [5, 8]
ClSO3H + 2C5H5N ? SO3?C5H5N + C5H5N?HCl.
????????? ??????? ????????? ???????????????? ??????????? ???????????????? ??????????? ? ??? ??????????????? ?????????? SO3-??????? ? ???????? ??? ? ???????????????? [6, 9, 10]. ??????? ??? ?????????????? ????? ????? ????????? SO3-??????????? [10]. ???
????????? ????????? «???????®», ??????????? ?????????????????? ? ????????????????
???????????, ??????????? ????? ??????????????? ?? ?????????? SO3-??????????????? ?
?????????????????? [7]. ?????????? ????? ??????? ? ????????????? ????????????? ???????
??? ??????? ????????????????? ??, ??? ??????????? ??????????? ????????????????? ????????? ???????? ????????.
??????????????? ????? ???????????? ??????????? ?? ???? ?????????????, ? ??????? ???????? ??? ???????????????. ??????? ??????? ??????????????? ????????? ? ????????????
???????? ? ???????????? ????????? ???????? ?????????. ????????, ??? ???????? ??????????? ??????????? ??????? ??? ????? ????? ?? ???????????????? ?????????, ????????? ????????? ? ?? ?????????. ? ?????????? ?????????? ????????????? ???????? ???????? ? ?????????? ??? ?????????? ???????????. ???????????????? ????????? ????? ?????????????? ???
????????? ??????????? ??????????? ???????? ????????????? ????? ?????????? ????????????? [11].
# 159 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
??????????? ???????? ?????? [12] ???????????? ???????? ? ???????????? ????? ??????????????????? ????????????????, ??????????? ?? ????????? ??????????? ?????????, ????????, ??? ?????????? ???????????? ?? ??? ???????????? ????????? ?? ??????????????
?????????????? ?????????? ? ?????????? ?????? ???????? ??????? ???????????? ?????
??. ????? ??????????? ???????? ??????????? ? ????????? ?????????????? ????????? ????????????? ??????? ??? ?????????? ???????????????? ????????? ?? ? ??, ??? ????????? ??
??????? ????????? ???????? ???? ???? ?????????? [12].
????? ?????? ?????? ???????? ???????????? ??????????? ?????????????? ????????
??????????????? ???????????????? ?????????? ?????? ???????? ? ??????? ????? ????????????? ??????????????? ??????????????? ????????????????.
????????????????? ?????
? ???????? ????????? ????? ???? ??????????????? (??) ????????? ??????????? ????????? (Larix sibirica Ledeb.) ???????????? ??? «????? ?????????» (???????, ??????) ??? ????????????? ????????? «?????????».
??????????????? ????????? ? ????????????????????? ???????????????? ????????????
?????????? ???????? ? ??????? ?????????, ??????????? ??????????????? ???????? ? ??????????????? ??????? [13]. ??? ????? ? ?????????? ?????, ?????????? ???????????, ???????????? ????????, ????????? ???????? ? ??????? ?????, ???????? 30 ?? ???????? ? ???
??????????? ????????????? ? ??????????? ????? 0 °C ????????? ?? ?????? 4 ?? (60,8 ?????)
??????????????? ???????. ?????????????? ???????? ??????? ????????? ? ???????? ????????? ?? 50 °C ? ???????? 2 ? ????????????????. ????? ??????????? ??????????? ????? ????????? ?? 70-90 °C ? ???????????? ? ??????? 3-4 ?. ?? ????????? ???????? ???????????????
???????????? ?????????????. ?????? ??????? ?????????? ? 15 ?? ????, ? ????????????????
??????????????? ? ???? ???????????? ???? ???????? ????? ??????????? ? 150 ?? 96 %-????
???????, ?????????????? ?????? ???????????????. ???????????? ???? ?????????? ? 20 ??
???? ? ?????????????? 1 %-??? ?????? ????????? ?????????? ?????? ?? ?? 9. ?????????????? ????????? ???? ???????? ???????????????? ???????? ????? ??????????? ? 150 ??
96 %-???? ???????, ???????????????, ????????? ?? ??????? 96 %-??? ???????? ? ?????? ?
???????. ? ?????? ????????????? ??????? ???????? ?? ????????? ?????? ????????????????
????.
???????????????? ????????? ?? ????????? ? ??????????? ???????? ???-2 ??? ???????????? ?????????, ??????????? ???????? ?????? ? 60 g. ??????? ????????-?????? ?? ??????
2 ? ?????????????? ? 20 ?? ????????????? ????????. ????????? ???????? ? ??????? ???????? 100 ?? ? ?????????????? ???????? ????? ?????? 75 ? ? ?????????? ?????????????????
??????????? ? ??????? 10 ???. ? ??????????? ???????? ???????????? ??????????????? ? ???
?????????? ????????.
?????????? ???? ? ???????? ???????????????? ?????????? ?? ???????????????? ???????? [14] ????????? ? ???? ????????? ? ??????????? ??????????? ????????? ???????? ?????????? ???????? ? ??????????? ??????? ? ??????????? ?????????? ?????????? ????????.
??-??????? ?? ? ????????? ??? ??????????????? ????? ? ?????????????? ??-?????
???????????? Tensor-27 (Bruker, ????????) ? ??????? ???? ???? 400-4000 ??-1. ????????? ????# 160 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
???????? ?????????? ????????? ?? ????????? OPUS (?????? 5.0). ??????? ??????? ??? ??????? ???????? ? ???? ???????? ? ??????? KBr (2 ?? ??????? / 1000 ?? KBr).
??? 13C-??????? ????????? ? ????????????????? ???????????????? ????? ??? ??????????? 25 °C ????????????? Bruker Avance III 600 M?? ? D2O ? ????????? ? ???????????? ????????? ????????????.
?????????? ? ??????????
??????????????? ?????????
? ????????????????????? ????????????????
??????? ??????????????? ???????????????? ?????????? ??????? ????????? ? ????????
? ??????????? ????????? ???????? ???????????????? ? ???? ????????? ???? ???????????? ??
?????:
O
O
OH
OH
HO
OH
O
SO3 - C 5H 5N
O
O
OR1
O
R 1 = H, SO3H - C 5H 5N
R 2 = H, SO3Na
O
OR 2
O
O
OH
OR2
HO
NaOH
O
O
OH
OR 1
HO
O
O
OH
O
O
O
OR 1
O
O
OR 2
???????? ??????? ????????? ? ????????, ?????????? ?? ??????????????? ??????? ? ????????, ???????? ????? ?????? ?????????????? ?????????, ??? ???? ??????????????? ???????, ????? ?????? ????????????? ? ???????? ? ?????????????? ??????????? ???????????
??? ??????????? ????? 55 °C. ?????? ?? ??????? ??????? ??????????????? ?? ?? ??????????
???? ? ????????????????? ??????? (???) ? ???????????????? ???????? ????????? ? ????. 1.
??? ???????? ??????? ??????????????? ?? ??????????? ??????????? ? ?????????????????
???????? ??? ?????????? ??????????? ?????????? ?? ? ??????????????? ???????, ??????
1:30 ?/?????.
?? ??????????? ? ????. 1 ?????? ???????, ??? ?????????? ????????????????? ????????
??????????????? ?? ??? ??????????? 70 °C ?? ?????? ?? ???? ????? ???????? ?????????? ????
? ???????????????? ???????? ? 5,4 ?? 11,5 % ???. ?????????? ???? ????????????????? ??????????????? ??? ???? ??????????? ??????????? ?? ??????????? ?????????? ???? ? ????????
??. ???????? ??????? ?????????? ???? ? ?? (13,5 % ???.) ??????????? ??? ??????????? ???????
90 °C, ?????? ??? ???? ?????????? ???????????? ?????????? ???? ????????????????? ???????
? ???????????????? ???????? ?? ????????? ? ???????? ??. ??????? ??????? ?? ?????????
???????, ??? ? ???????? ???????????????? ?????????? ??????? ? ???????????? ?????? ?????
7-10 ??? ?????????? ????? 7 %. ??? ?????? ??????????? ? ????????????? ??????? ? ???, ???
??????????????? ??????????? ????????? ???????? ????????? ???????????? ?????? (?????????????? ?.?. 9000-20 000) ? ????????? ???????? ???????????????? [15]. ? ???????????????? ????????????????, ?????????? ??? ??????????? ??????? 90 °C, ?????????? ????????????????? ??????? ??????????? ?????? ? ????? ????????? 27,5 %. ????? ???????, ?????????
# 161 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
??????? 1. ??????? ??????? ??????????????? ???????????????? ?????????? SO3 ? ??????? ??
?????????? ???? ? ????????????????? ??????? ? ???????????????? ????????
? ???????
T ???????, °C
?????????????????
???????, ?
?????????? S, %
????.
?????????? ???, %
1
70
2
70
1
5,4
11,5
2
8,0
11,5
3
70
3
11,5
13,0
4
70
4
11,8
14,0
5
80
2
12,1
15,5
6
80
3
12,4
19,0
7
90
2
12,8
25,0
8
90
3
13,5
27,5
??????????? ??????????????? ?? ?????????????? ?????????????? ?????????? ?????????
?????????? ???????????? ??? ?????????, ??? ? ????????????????? ????????????.
???????????, ??? ??????????????? ??????????????? ???????????????? ? ????? ????????
? ??????????? ???????? ???-2 ???????? ??? ??????????? ??????????? ? ??????? ??????????????? ?????????? ??????? ????????? ? ????????. ?????? ?? ??????? ??????? ??????????????? ????????????????????? ?? (???????????, ????????? ??/?????????????? ????????,
?????????????????) ?? ?????????? ???? ? ???????????????? ???????? ????????? ? ????. 2.
?????????? ?? ??????????? ??????? ??????? ?????????? ???? ? ???????? ?? (?????
12 % ???.) ??????????? ??? ????????????????? ??????????????? 1 ?. ??? ????? ????????????????? ???????? (0,5 ?) ?????????? ???? ? ???????? ????????????? ? ?????? ?????????
?????????????? ????????/??. ??? ????????? ??????????? ???????, ??? ? ?????????? ?????????? ??????????????? ????????? ? ??????????? ????? ???????????? ???????? ?????????
?????????? ????????????????????? ??, ? ?????????? ???? ??? ???????????????? ???????????
??????????? ?????? ???????.
??????????????? ???????????? ????????? ???????????????? ??? ????????????? ???????????? ???? ?????? ?? ??? ??????????? ??????????? ? ??????? ??????????????? (????. 2).
?????? ???????????????? ????????? ???????????????? ? ????? ???????? ????????? ???????
???????????? ?????????????? ???????? ??? ??????????????? ?????????? ??????? ?????????
? ????????. ??? ???? ??????? ??????? ?? 15 °C ??????????? ???????? ? ?? ???? ??? ?????????
??? ?????????????????.
??? ????????? ????????? ?? ? ??????? ??????????? ???? (11,8 % ???.) ? ????? ??????????? ????????????????? ????????? ?????????? ???????????? ????????????? ?????????
??????? ??????????????? ????????????????????? ???????????????? ?????????? ?????? ???????? ? ??????? ??? ??????????? 55 °C ? ??????? 1 ?.
???????? ????????? ??????????????? ????????????????.
? ??-???????? ????????????????? ????????????????, ? ??????? ?? ????????? ??, ???????????? ?????? ??????? ????????????? ??? 1254-1260 ??-1, ????????????? ????????????? ??# 162 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
??????? 2. ??????? ??????? ??????????????? ????????????????????? ???????????????? ??????????
??????? ????????? ? ???????? ?? ?????????? ???? ? ???????????????? ????????
? ?????
1
2
3
4
5
6
7
8
9
10
11
12
13*
14**
15**
16**
???????????
???????, °C
55
55
55
70
70
70
70
70
70
70
70
70
55
55
70
70
????????? ??/??????????????
????????, ?/?????
1:30
1:30
1:40
1:23
1:23
1:23
1:30
1:30
1:30
1:40
1:40
1:40
1:30
1:30
1:30
1:40
?????
???????, ?
1
3
3
0,5
1
3
0,5
1
3
0,5
1
3
3
3
3
3
??????????
S, % ????.
11,8
11,9
12,0
4,9
7,2
8,9
8,2
11,9
12,0
8,8
12,1
12,3
5,8
5,1
10,8
11,9
* ? ?????????????? ??? ????????????; ** ? ???????????????? ??.
??????? ?????????? ?as(O=S=O) (???. 1). ??????? ????? ?????????? ??? 812-814 ? 861-862 ??-1,
????????????? ? ??-??????? ????????? ????????????????, ??????????????? ? ???????????
????????? ? ????????? ????????? ????????? ???? ????????????????. ? ??-???????? ???????????????? ???????? ?? ????????? ? ???????? ?? ??????????? ?????????? ?????????????
?????? ?????????? ????????? ????????? ????????????????? ??-????? ? ??????? 3423 ??-1 ?
?????? ?????????? ??????????? ?????????????? ????????? ??-????? ? ??????? 1376 ??-1,
??? ??????????????? ?? ?????????? ????? OH-????? ? ???????????????? ???????? ??????????
?? ????????? ?? SO3-??????.
???????????? ??-???????? ????????? ? ????????????????????? ???????????????? ????????? ?? ??, ??? ??? ??????????????? ?? ?????????? ???????????? ????????? ? ??????? ? ?
????????? ????????????????.
??-?????? ????????????? ???????????? ????????????????? ???????????????? (???. 2)
???????? ????? ??????? ?? ????????? ?? ???????? Na-???? ????????????????? ????????????????. ?????? ????? ????? ?????????? ? ??????? ????????????? ???????????? ????????????
?????? ?????????? ??????? ????????????? ??? 3077 ??-1, ????????????? ????????? ?????????? ????? C?H. ????? ? ??????? ???????????? ?????? ????????? ????????? C=C ? C=N ?????? ???????? ??? 1545 ? 1490 ??-1 ?????????????? ? ?????? ?????????????? ????????? ?????
C?H ????????????? ?????? (1042 ??-1).
??? ??????? ?? ??????????? ???????? ?? (???. 3), ??????? ??????????????? ????? ????????? ?? ?????????? ????????????? ???????, ????????????? ???????? ??????????? ?????????? ???????????? ?? (???. 4).
# 163 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
???. 1. ??-??????? ???????????????? (?) ? ????????? ????? ????????? ???????????????? (??????? 1-4
?? ????. 2)
???. 2. ??-?????? ???????????? ???? ????????????????? ????????????????
? ?????? [16] ???????????, ??? ??????????????? ?????????????? ????????????? ??????
??, ??????????? ??? C2 ? C4 ?????????? ?????? ???????? ???????????? ????, ? ????????? ????????????? ??????, ??????????? ??? C6-????? ???????? ???????? ??????? ????????? ???????? ? ??????? ????.
???????? [17], ??? ??????????? ???? ?????????? ????? ???????? ???????????? ???????? ? ??????? ??? 13? ???????? ????????? ?????? ???????? (??? ???????, ?? 6-10 ?.?. ? ?????? ???? ??? ?????, ???????? ???????????, ? ?? 2-4 ?.?. ? ??????? ???? ??? ???? ????????
??????). ??? ???? ??????????? ?????????? ????? ??????????? ????? ???????????? ?? ????????
??? 13?.
# 164 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
HO
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OH
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OH
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O
O
O
OH
O
HO
O
OH
OH
O
O
OH
OH
O
HO
OH
HO
OH
OH
OH
O
OH
???. 3. ????? ???? ????????????? ?? ????????? ???????????
OH
O
4
O 3
OH
6
5
O
4
2
1
OH
HO 3
?3,6)-?-D-???????????????-(1?
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3
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6
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6
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?-D-???????????????-(1?
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3
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?-L-???????????????-(1?
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5
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?-L-???????????????-(1?
???. 4. ???????? ??????????? ????????? ???????????? ??
????????? ?????????? ??????????? ? ?????????? ???? ???????? ?????????????????
???????????????? ??????????? ? ?????????????? ??? 13C-????????????? ?? ?????? ?????????????? ??????? ???????? ????????? ? ????????????????? ??.
?? ???. 5 ????????? ??? 13C-??????? ????????? ? ???????????????? ???????? ?? ??
????????? ???????????, ? ? ????. 3 ???? ????????? ???????? ? ??????????????? ?????? ???????? ? ??????? ????????????.
??? ??????? ?? ??????????? ? ????. 3 ??????, ? ??? 13C-??????? ???????? ?? ??????
?????? ???????????????? ???????? ?????? ???????? ?-D-????????????????? ??????????
???????? ????????????? ?? ?????????? ?????????????? ??????? ?????????? ??????, ???
??????????????? ? ???????????? ? ????????????? ???????????? ?????????? ? ???????? ???????????????.
???, ?????? ? ??????? 67,24 ?.?., ????????????? ? ??????? ????????? ??, ????? ???? ??????? ? C6-?????? ???????? ?-D-????????????????? ??????????, ????????? ? ????????????????? ?????????? ?????????? ????????. ?????????????? ????? ????????????? ??????
# 165 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
???. 5. ??? 13C-??????? ???????? ????????? (1) ? ????????????????? (2) ?? ?? ????????? ???????????
??????? 3. ????????? ???????? ? ??? 13C ???????? ?? ? ???????? ?? ? ??????????????? ?-??????
?
???????
1
??
2
???????????????? ??
C1
C2
C3
C4
C5
C6
103,39
70,78
72,76
68,68
75,18
61,09
103,44
70,82
72,81
68,72
75,22
61,13
101,74
75,58
72,01
74,99
73,69
67,24
???????????? ?????????? ????????????? ??????? C6-????? ??? 61,13 ?.?., ?????????? ?? ?????????? ?????????? ?????????? ????????.
?????? ?????????? ????????????? ??????? ????? ???????? C5 ??????????? ??????????
? ??????? 75,22 ?.?., ???????????????? ?????????? ??????? ????? ????????????? ? ???????
73,69 ?.?., ????? ???? ????????? ???????????????? ???????? ????????????? ?????, ????????????? C4 ? C6 ?????????? ??????. ? ???? ?????? ?????? C5-????? ???????????? ????? ?
??????? ???? ?? 2-4 ?.?. (?-?????? ??????????????? ??????????? C4- ? C6-??????), ?????????????, ? ???? ????? ???? ??????? ?????? ? ??????? 73,69 ?.?.
?????? C4-????? ?????????? ? ?????? ???? ???????? ?? 6 ?.?. ? ???????????????? ? ??????? ???????? ?? ? ??????? 74,99 ?.?.
??????????? ????????? ?????????? ???????, ????????? ? ???????????????? ????????? ?????? ????????, ??????????? ??? C2-????? (????? ? ?????? ???? ? 70,82 ?? 75,58 ?.?.) ?
C3-????? (????? ? ??????? ???? ? 72,81 ?? 72,01 ?.?.) ?-D-????????????????? ?????????? ???
?? ????????? ? ???????????????? ????????? ? 13C ???-??????? ??.
??????? ?????????? ????? ??? C2-????? ? ?????? ???? ?-D-????????????????? ?????????? ???????? ?? ?????????????? ?????????? ??????????????? ???????? ??????? ??????????? ????? C1 ??? 101,74 ?.?., ?????????????? ? ??????? ????????? ??. ??????????
# 166 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
????? C1-????? ?-D-????????????????? ?????????? ???????? ????????????? ?? ?????????? 103,39 ?.?.
????? ???????, ? ???????????????? ???????????????? ?????????? ?????? ????????? ???
C2 ? C4 ?????????? ?????? ???????? ???????????? ???? ? ??? C6 ?????????? ????? ????????
??????? ????????? ???????? ? ??????? ????? ??.
??????
??????????? ??????????? ???????????? ?????????????? ???????? ??????????????? ???????????????? ?????????? ??????? ????????? ? ???????? ??? ????????????? ???????????????? ??????????????????? ???????????????? ? ????? ????????. ??? ???? ??????? ??????? ??
15 °C ??????????? ???????? ? ? ??? ???? ????????? ??? ?????????????????.
????????, ??? ? ?????? ??????????? ??????????????? ???????????? ? ??????????? ?????????? ???? ?????????? ???? ????????????????? ??????? ? ???????????????? ????????
?????????? ?????????? ????????? ?????????? ????????? ?? ? ??? ???????????????? ???????????.
??? ????????? ????????? ?? ? ??????? ??????????? ???? (11,8 % ???.) ? ????? ??????????? ????????????????? ????????? ?????????? ???????????? ????????????? ?????????
??????? ??????????????? ????????????????????? ?? ??? ??????????? 55 °C ? ??????? 1 ?.
???????? ?????????????????? ???????????????? ???????????? ???????? ??- ?
??? 13C-?????????????. ???????????????? ??????????????? ???????????? ????? ????????????????????? ???????, ? ??????? ?????????? ?????? ????????? ??? C2 ? C4 ??????????
?????? ???????? ???????????? ???? ? ??? C6 ?????????? ?????? ???????? ??????? ?????????
???????? ? ??????? ????? ??.
?????? ????????? ??? ????????? ?????????? ????????? ???? (??????? ? 12-0393117 ? ? 12-03-31433) ? ?????? ??? «?????????????? ??????????? ????????» ?????
???????? ? ???????.
?????? ??????????
1. ?????? ?.?., ?????? ?.?., ?????? B.C., ???? ?.?. ???????????????? ? ????????????? ??????? ?????????? ????????????? ?? ????? ??????? ?????????? // ????????. ? ????????.
1991. ?.54, ?5. ?. 40-42.
2. Bengtsson G., Olivecrona T., Hццk M., Riesenfeld J., Lindahl U. Interaction of lipoprotein
lipase with native and modified heparin-like polysaccharides // Biochem. J. 1980. V. 189, ? 3.
P. 625-633.
3. Patent US ? 5478576. Arabinogalactan derivatives and uses thereof / C. Jung, P. Enriquez,
S. Palmacci, L. Josephson, J.M. Lewis // Publ. 26.12.1995.
4. ????? ?.?., ????????? ?.?., ????????? ?.?., ??????? ?.?., ????????? ?.?., ??????????
?.?., ????????? ?.?. ???????????????? ?????????? ?????????? ???? ?????, ???????? ????
???, ?????? ? ?????????, ?????????? ?? ????????? ?????, ????? ? ?????? ??????? // ????????????????? ? ??????????? ????????????. 2010. ?.73, ?6. ?. 5-9.
5. ????????? ?.?. ????????????? ???????????? ??????????. ?.: ?????, 1969. 416 ?.
# 167 #
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?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
6. Kamitakahara H., Mikawa Y., Hori M., Tsujihata S., Minato K., Nakatsubo F. Syntheses,
characterization, and biological activities of sulfated polysaccharides // 10th Int. Symp. on Wood Pulp
Chem. Yokohama, Japan. 1999. V. 2. P. 238-241.
7. ?????? ?? ? 2319707. ?????? ????????? ???????????????? ??????????? ????????????????, ?????????? ???????????????? ? ?????????????????? ??????????? / ??????? ?.?.,
??????? ?.?., ????????? ?.?., ????? ?.?., ???????? ?.?. // ?????. 20.03.2008.
8. ???????? ?.?., ??????? ?.?. ????????? ?????????? ?????????? ??????????? ????????? ????????? ?????? ? ?? ??????????? II. ??????????????? ?????????? ??????????,
?????????? ??????????? ????????? ????????? ?????? // ????? ????????????? ?????. 2007.
? 3. ?. 63-67.
9. Patent CN ? 101054420. Preparation of arabinogalactan sulfate from arabinogalactan / Guizhen
Fang, Yanli Ma // Publ. 17.10.2007.
10. Patent FR ? 4874. Nouvelles compositions medicamenteuses a activite anti-coagulante et
clarifiante / J.-R. Bossard // Publ. 03.04.1967.
11. ????????? ?.?. ??????????? ???????????? ??????? ??? ????????? ???????????? ?????????? // ?????? ?????. 1999. ? 68. ?. 708-724.
12. ????????? ?.?., ???????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?., ??????
?.?. C?????????? ??????????? ???????????????? ?? ??????????? ????????? ??? ???????????????? ????????? ? ????????????? ???????? ????????? // ????? ????????????? ?????. 2009.
? 3. ?. 49-56.
13. ?????? ?? ? 2466143. ?????? ????????? ???????????????? ??????????? ???????????????? / ????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?. // ?????. 10.11.2012.
14. ??????? ?.?., ?? ?.?. ?????- ? ??????????????? ????????????? ???????????????
???????. ?.: ?????, 1973. 576 ?.
15. ????????? ?.?., ???????????? ?.?., ???????? ?.?. ??????????????? ?????????????
???????????????? // ???. ?????. ?????? ??????. 2002. ? 6. ?. 108-114.
16. ??????? ?.?., ????????? ?.?., ????? ?.?. ?????? ???????????????? ??????????? ???????????????? // ??????? ??????????????. 2004. ? 3. ?. 10-12.
17. ???? ?.?. ???????? ? ?????????? ? ??????????? ??????? ???????????????? ????????????? ??????? ?????????? // ????? ????????????? ?????. 2001. ? 2. ?. 7-20.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ??????????? ??????????????? ????????????????????? ???????????????? ???????????
Sulfation of Mechanically Activated Arabinogalactan
by Complex Sulfuric Anhydride ?
Pyridine in Pyridine Medium
Natalia Y. Vasilyevaa,b, Alexandr V. Levdanskya,
Alexandr S. Kazachenkoa, Laurent Djakovitchc,
Catherine Pinelc and Boris N. Kuznetsova,b*
a
Institute of Chemistry and Chemical Technology SB RAS
42 K. Marx Str., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
c
IRCELYON,
2 Albert Einstein av., F-69626 Villeurbanne Cedex, Lyon, France
Sulfation of mechanically activated arabinogalactan (AG) by complex of sulfuric anhydride ? pyridine
at temperatures 70-90 °C in pyridine medium was studed. It was found that the preliminarily mechanical
treatment of arabinogalactan in planetary mill AGO-2 allows to reduce the temperature and time of
AG sulfation and to increase the purity of sulfated product. The growth of sulfation temperature from
55 to 90 °C results in the increase both a degree of AG sulfation and a content of low-molecular
fractions in sulfated product. According to NMR 13C spectroscopy data sulfate groups are fi xed at
?2 and C4 positions of galactose unit of basic chain and at C6 position of terminal galactose units of
basic and side chains of arabinogalactan.
Keywords: arabinogalactan, mechanical activation, sulfation, sulfuric anhydride, pyridine, sulfated
arabinogalactan, structure.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 170-179
~~~
??? 544.723 : 547.022
????????-?????????? ????????
???????? ??????? ? ???????? ????? ????????
?? ??????????? ??????? ? ?????????
?.?. ???????*?, ?.?. ?????????,
?.?. ?????????, ?.?. ????????,?, ?.?. ??????
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79
?
???????? ?????? ??. ?.?. ?????????? ?? ???,
?????? 660036, ??????????, ?????????????
Received 12.07.2012, received in revised form 22.01.2013, accepted 11.02.2013
? ??????? ????????-?????????? ???????? ??????????? ??????? ?????????????? ???????
???????? ? ???????????? ??????? ? ????????? ? ????????? ??????????, ? ????? ???????
?????????????? ?????????? ????????? AA ? AB ????. ?????????? ???????? ??????????????
???????? ????????? ? ??????? ? ?????????. ????????, ??? ???????? ?????????????? ????????
????????? ? ????????? ??????, ??? ???????? ??????????????? ??????? ???????? ? ???????
?????????? ??????? ?????????????? ?????????????? ??????? ?? ?????? ?????.
???????? ?????: ????????? ?????, ??????, ??????, ????????.
????????
????????? ?????????? ????????? ???????? ??????? ?????????????? ? ????? ? ???, ???
???????? ?????? ?????????????? ??????????? ??? ????????????????, ???????? ????? ?????????? ???????, ??????????? ?????????. ? ?????????, ???????? ??????? ???????? ????????
???????????????????, ??????????? ? ?????. ??? ???????? ????????? ?? ?????? ??????? ?????
????? ??????????? ?????????????? ??? ????????? ???????. ????? ?? ????? ???????? ???????? ????????? ????????? ????????, ? ????????? ????????.
????????????? ?????? ????????? ??????????? ????? ???????? ???????, ??????????? ????????? ??????????? ????????? ? ????????? ???????????. ?????? ??? ????????????? ???????? ??????????? ???????, ????? ??? ???????? AB ????, ????? ????? ???????? ???????, ????????? ??????????? ???? ???-???-???????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: dskalyakin@mail.ru
# 170 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
???? ?????? ?????? ? ????????????? ???????????? ????????? ???????? ? ??????? ? ?????????.
????? ????????, ???????? ????? ??????????? ????
???-???-??????? ? ?????????? ??????????
??????? ????????? ? ?????????????? ???????????? ?????? NWChem [1] ? ?????? ?????? ??????????? ????????? (DFT) [2-4] ? ??????????? ???????????? SVWN5, B3LYP, LCBOP, PBE, LC-PBE ? ????????? ? ???????? 6-311++G (3df,3pd); 6-311G**; 6-311G**++, ????????????? ?????????? (DFT-D) [5] ? ?????????? ?????? ???????????? ????????? ??????
(BSSE-?????????) [6].
??? ????????? ???????? ????????? ??????? ???????????? ??????? ?????????????? ????
??????? ???????, ?????????? ?-???????? ????? (???. 1).
?????????? ???????? ??????? ?????????????? ????????? ? ?-???????? ?????? ???????
?????????? ?????????? ???????????? ? ????. 1.
???. 1. ????????? ????????? ?-????????? ?????? ???????
??????? 1. ?????????? ???????? ??????? ?????????????? (E??) ??????? ??????? ? ?-???????? ??????
???????? ???????
LCBOP
6-311++G(3df,3pd)
LCBOP+BSSE
6-311++G(3df,3pd)
SVWN5
6-311++G (3df,3pd)
B3LYP
6-311G**
LCBOP-D
6-311++G(3df,3pd)
LCBOP-D+BSSE
6-311++G(3df,3pd)
E??, ??
0,13
0,11
-0,13
0,04
-0,08
-0,05
???????? ???????
SVWN5-D
6-311++G(3df,3pd)
SVWN5-D+BSSE
6-311++G (3df,3pd)
PBE-D
6-311G**++
PBE-D+BSSE
6-311G**++
LCPBE-D
6-311G**++
LCPBE-D+BSSE
6-311G**++
# 171 #
E??, ??.
-0,35
-0,32
-0,14
-0,13
-0,26
-0,28
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
???. 2. ????????? ????????? ?????? ??????? PD-????
? ???? ???????????? ???? ????????, ??? ???????? ?????? ????????? ???? ???????? PBED+BSSE 6-311G**++, ?????????? ?? ????????????? PBE-???????????, ?????? ???????? ??????? 6-311G**++, ????????????? ????????? ? BSSE-?????????. ???????? ??????? ???????
??????? ?????????????? ????????? ? ?-???????? ?????? ??????? ????? 0,13 ??, ??? ??????????? ? ?????????????????? ??????? (0,10 ± 0,02 ?? [7]) ? ???????????? ???????? ???????
???????????? ????????? CCSD (0,12 ?? [8]).
??? ????????????? ????????????? ????????? ???????? ??? ???????? ?????? ??????
??????? PD-???? (???. 2).
???????????? ??????? ????????? 0,11 ??, ??? ????? ?????? ??????????? ? ?????????????????? (0,10 ± 0,02 ?? [7]) ? CCSD (0,12 ?? [8]) ???????.
???????????? ??????? ?????????????? ??????? ????????
? ???????????? ??????? ? ????????? ? ????????? ??????????
? ??????? ?????????????? ?????????? ????????? AB ? ??-????
???????????? ????????? ??? ? ?????????? ???????????, ??? ? ? ?????????????? ????????????? ????????.
??????? ? ?????? ??????????? ??????????? ????????? ??? ?????? ???????????? ?????? NWChem ? ?????? ?????? ??????????? ????????? (DFT) ? ?????????????? ??????????? ??????-?????-????????? (PBE), ?????? ???????? ??????? 6-311G**++, ?????????????
????????? (DFT-D) ? ????????? ?????? ???????????? ????????? ?????? (BSSE-?????????).
? ???? ?????????????? ??????????? ?????????? ????????????? ??????? ???????? ?????????
??????? ??????? ? ????????? ???????????? ?????????? ?????????. ??? ?????????? ????????? ???????? ?????????? ???? ?????? ? ???????? ??????? ? ???, ??? ????????? ????? ? ????
?????????????? ??????????? ???????? ????????????, ?? ???? ????????? ? ?????????????
?????????. ??? ???? ????? ???? ??????, ??? ???????????? ??????? ???????? ??????????
?????? ????? ???????? ? ????????? ??????? ??????????????, ? ?? ????? ??? ??? ???????????? ??????? ?????? ?????????? ?? ????? ???????? ?????? ??????????? ????????? ?????????.
??????? ????????????? ???????? ???????????? ? ??????? ???????????? ?????? VASP
[9-11] ? ?????? ?????? ??????????? ????????? (DFT) ? ?????????????? ??????????? ???????????-????????? (PBE), ?????? ??????? ????, ???????????? ????????????????? ????????????
# 172 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
???. 3. ???????? ???????? ????????? ??????? ?? ??????????? ??????? (?), ????????? (?) ? ????????????
????????? ?????? ? ????????? ??????? ??????? (?), ????????? (?)
[12] ? ????????????? ????????? (DFT-D). ???????? ???????????? ? ?????? ???? ?????????
????????????? ??????????? ?? ????? ?? ????? ?????????-???? [13], ?????????? k-????? ?????
??????? ?? ??????????? ?????????? 3?3?1. ??? ????????????? ??????? ? ????????? ????????? ????????? ?????????? ????? ??????? ? ???????????. ??? ???????? ??????????? ??????
?? ?????????????, ??? ?? ?????? ?????????? ???????? ??????????? ?? ????? ????????????????? ???? ? ??????. ????? ????, ? ???? ??????????? ????????? ?? ??????????? ???????????? ????????? ????????? ??????, ??? ??? ? ??????? ?? ??????????? ??????????? ??????????
????????????? ????????? ?? ????????? ?????????? ?????????. ??? ??????? ??????? ????????????? ???????? ???????????? ??????????? ???????? 8?8?1, ?.?. 64 ???????????? ??????,
?????????? ? ???? 128 ?????? (129 ??? ??????? ???????) ? ?????? ??????? ? 256 ?????? (257
??? ??????? ???????) ? ?????? ???????.
??? ????????? ????????, ?????????? ? ??????? ?????? ?????????? ????, ?????????????
????????? ?????? ???????? ? ?????? ??????? ????. ? ???? ?????? ???????????? ???????????
????? VASP, ?????? ??????????? ????????? (DFT), ?????????? ??????-?????-?????????
(PBE) ? ????????????? ????????? (DFT-D). ??? ???? ? ???????? ???????????? ?????????????? ???? ?-?????.
?????????? ???????? ????????????? ???????? ????????? ??????? ?? ??????????? ??????? ? ?????????. ??? ??????? ???? ?????????? ?????? ????????? ??? ?????? ??????? ? ???????, ? ?? ????? ??? ??? ????????? ???? ?????????? ???????? ????????? ????? ???????????????, ???????????? ??????? ???????? ????? ????????? ? ?????? C-C ?????? ????????? (???. 3).
??????? ?????????????? ??????? ? ???????????? ??????? ? ????????? ? ???????? ????????????? ???????? ?????????? ???????????? ? ????. 2. ?????? ?????????????? ????????? ???????
?? ??????????? ??????? ? ????????? ????????????? ?????????.
# 173 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
??????? 2. ?????????? ???????? ??????? ?????????????? (E??) ??????? ???????? ? ???????????? ???????
? ?????????
??????? ?????????????? ??????? ???????? ? ???????????? ???????
?????? ???????
PBE-D 6-311G**++ ?????????? ???????????
PBE-D
?????????? ???????????
????? ??????? ????
PBE-D
????????????? ??????
????? ??????? ????
???????????????
E??, ??
1
-1,14
3
-1,05
1
-1,43
3
-1,49
??????? ?????????????? ??????? ???????? ? ???????????? ?????????
?????? ???????
???????????????
PBE-D+BSSE 6-311G**++ ?????????? ???????????
PBE-D
????? ??????? ????
?????????? ???????????
PBE-D
????????????? ?????? ????? ??????? ????
E??, ??
1
-0,14
3
-0,10
1
-0,28
1
-0,61
??????? 3. ?????????? ???????? ??????? ?????????????? ?????????? ????????? ? ???????? ?? ?????????
??????????? ??????? (E???)
?????? ???????
E???, ??
PBE-D+BSSE 6-311G**++
?????????? ???????????
PBE-D
?????????? ??????????? ????? ??????? ????
PBE-D
????????????? ?????? ????? ??????? ????
-0,19
-0,18
-0,30
???? ???????????, ??? ??????? ???????? ?? ????????????? ??????? ???????? ?????????
???????????, ?????????????, ???????? ?????????? ?????????? ???????????? ?????????????
???????, ??? ??? ????????? ????? ????????? ??????? ????????????? ??????????. ?? ?????????
??????? ????? ????? ??????? ?????, ??? ??????? ?????????????? ??????? ? ???????????? ??????? ? ????????? ????? 1,49 ? 0,61 ?? ??????????????.
? ?????? ????? ??????????? ??????? ?????????????? ?????????? ????????? (????. 3).
?? ????????? ???????????, ??????????? ? ????. 3, ????? ??????? ????? ? ???, ??? ???????????? ???????? ? ???????? ??????? ?????????????? ?????????? ?????????, ??? ? ??? ???????
??????? ?????????????? ??????? ? ???????????? ??????? ? ?????????, ???????? ????????????
????? ????????????? ??????????. ?????? ???????, ??? ??????? ?????????????? ??????????
# 174 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
????????? ???????? ????????? ?????????? ? ???? ?????????????? ???????. ???????? ???????
?????????????? ?????????? ????????? ????? 0,30 ?? ? ????????? ?? ????????? ???????????
??????? (??? ??????????????, ???????????? ??????? ???????? ? ????????????????? ?????
?????). ?????????? ???????? ??????????? ? ?????????????????? ??????? [14], ???????? ??????? ??????? ?????????????? ????? ??????? ?????????? 0,27 ??.
????????? ??????? ????????? AA-???? ??? ??????????? ????????? ????????? ? ????????? ??????? ????????? AB-????, ?????????????, ??????????? ????????? AA-???? ????????????? ?????????.
???????????? ?????????? ?????????
? ???????? ??????????????? ??????? ???????? ? ??????? ? ?????????
??????? ????????? ? ?????? ??????????? ??????????? ? ? ?????????????? ????????????? ????????. ??? ???????? ????????? ????????, ????????? ????. ??? ??????? ??????????? ????????? ? ????????????? ?????????? ????? ????? ??????? ????? [15, 16]. ???
????????????? ????????? ??????? ? ????????????? ?????????? ???? ??????? ????????? ??
10 ?????.
???? ???? ???????????, ??? ??? ??????? ???????? ???? ?????????? ?????????, ? ?? ????? ??? ???????? ???????? ????? ???????????????? ??????????? ??????????? (??????????
????????? I ????????????? ????????? ??????? ?? ?????? ???? ??? ?????? ?-? ??????? ????;
?????????? ????????? II ????????????? ???????????? ??????? ??? ??????? ??????????????)
(???. 4).
???????? ??????????????? ??????? ???????? ? ??????? ? ????????? ???????????? ? ????. 4
? 5 ??????????????.
?? ??????????? ????????, ?????????? ? ????. 4 ? 5, ????? ??????? ????? ? ???, ??? ???????? ?????? ???????? ??? ??????? ???????? ??????????????? ??????? ???????? ? ??????? ?
?????????, ??? ? ??? ??????? ???????? ??????? ??????????????, ???????? ?????????? ???????? ????????????? ??????????. ?????????????, ???????? ?????????????? ???????? ????????
? ??????? ? ????????? ???????? ????????? ??????? ? ???? ????????????? ???????? ? ?????????? 0,45 ?? ??? ???????, 0,33 ?? ??? ????????? ??? ?????????? ????????? I ? 0,38 ?? ???
?????????? ????????? II.
???????? ?????? [17] ???????? ??????????????? ??????? ???????? ? ??????? ?????? 0,33 ??,
??? ??????????? ? ??????????? ???? ???????.
??????? 4. ???????? ??????????????? ??????? ???????? ? ???????
?????? ???????
E??, ??
PBE-D 6-311G**++
?????????? ???????????
PBE-D
?????????? ??????????? ????? ??????? ????
PBE-D
????????????? ?????? ????? ??????? ????
0,55
0,57
0,45
# 175 #
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???. 4. ?????????? ????????? ? ??????? (?), ?????????? ????????? I (?), II (?) ? ????????? ? ????????????
????????? ?????? ? ????????? ??????? ??????? (?) ? ????????? ??? ???????????? ??????????? ?????????
I (?) ? II (?)
??????? 5. ???????? ?????????????? ???????? ???????? ? ?????????
?????????? ????????? I
?????? ???????
PBE-D+BSSE 6-311G**++
?????????? ???????????
PBE-D
?????????? ??????????? ????? ??????? ????
PBE-D
????????????? ?????? ? ??????? ??????
E??, ??
0,60
0,55
0,33
?????????? ????????? II
?????? ???????
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?????????? ???????????
PBE-D
?????????? ??????????? ????? ??????? ????
PBE-D
????????????? ?????? ? ??????? ??????
E??, ??
0,67
0,70
0,38
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?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
???????? ?????????????? ???????? ????????? ? ??????? ? ????????? ????????? ?? ??,
??? ???????? ??????? ???????? ? ????????? ????????? ? ??????? ?????????, ??? ???????? ??
??????????? ???????.
??????????
???????????, ??? ???????? ?????????? ???? ???-???-??????? ? ?????????? ?????????? ?
?????? ??????????? ??????????? ????????? ???????? PBE-D+BSSE 6-311G**++, ??????????
?? ????????????? PBE-???????????, ?????? ???????? ??????? 6-311G**++, ?????????????
????????? ? BSSE-?????????. ????????, ??? ????????????? ??????????? ??????????? ???????? ??????? ???????? ?? ????????????? ???????? ? ?????????? ??????? ? ?????????, ???
????????????? ?????? ???????? ??????? ????????? ????.
???????? ????????????? ???????? ?????????? ??????? ?? ??????????? ??????? ???????? ????????? ??? ?????? ???????-???????, ? ????????? ???? ?????????? ???????? ?????????
????? ???????????????, ???????????? ??????? ???????? ????? ????????? ? ?????? C-C ?????? ?????????. ??????? ?????????????? ??????? ? ???????????? ??????? ? ????????? ?????
1,49 ? 0,61 ?? ??????????????.
??????? ?????????????? ?????????? ???????????? ??????? AB-???? ???????? ????????????? ???????? ?? ???????? PBE-D ?????????? 0,30 ??. ? ???????????? ? ??????????????
????????? ???????? AA ???? ????????????? ?????????. ??? ?????????? ???????? ????????
AA ???? ????????? ? ??????????? ???????? AB ????.
????????? ??????? ??? ?? ??????????? ???????, ??? ? ? ????????, ???????? ?????????
????????? ?????????.
???????? ?????????????? ???????? ????????? ??????????: ??? ??????? 0,45 ?? ??? ????????? 0,33 ?? ? 0,38 ?? ??? ?????????? ????????? I ? II ??????????????.
?? ????????? ??????? ?????????????? ???????? ???????????, ??? ???????? ??????? ???????? ? ????????? ????????? ? ??????? ?????????, ??? ???????? ?? ??????????? ???????.
?????? ??????????
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Nieplocha J., Apra E., Windus T.L., de Jong W.A. NWChem: a comprehensive and scalable opensource solution for large scale molecular simulations // Comput. Phys. Commun. 2010. V. 181. P. 1477.
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International Journal of Quantum Chemistry. 2004. V. 100. P. 559.
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?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ????????-?????????? ???????? ???????? ??????? ? ???????? ????? ?????????
Quantum-Chemical Study of the Sorption
and Migration of Carbon Atom on the Surface
of Graphene and Bigraphene
Danil S. Kaliakina,
Nataliya S. Eliseeva , Yulia E. Ananevaa,
Alexander A. Kuzubova, b and Alexander O. Lykhina
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Institute of Physics, SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
a
With using of quantum-chemical calculations the binding energies of adatom on graphene and
bigraphene in different positions, as well as the binding energies between layers in AA and AB type
bigraphene were investigated. The values of energy barriers of transitions in graphene and bigraphene
were calculated. It was shown that values of energy barriers of transitions in bigraphene is less than
value of energy barrier of transition in graphene, because of weak dispersive interaction of the adatom
with the second layer.
Keywords: quantum chemistry, adatom, graphene, bigraphene.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 180-191
~~~
??? 539.26:519.65:519.68
???????????? ????? ?????????????
??????????????? ????????? ????????
?? ?????? ?????????? ?????????
?.?. ???????, ?.?. ??????,
?.?. ?????????, ?.?. ?????????, ?.?. ???????*
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79
?
???????? ????? ? ?????????? ?????????? ?? ???
?????? 660049, ??????????, ?. ??????, 42
Received 23.09.2012, received in revised form 24.12.2012, accepted 18.01.2013
????????? ???????????? ????? ????????????? ??????? ??????????????? ?????????
?????????? ?????????? ?? ?????? ?????????? ?????????, ????????????? ?????
???????????????? ???????????? ??????? ? ???????????? ???????? ?????????? ???????????.
????????? ????????????????? ???????????? ????????????? ?????????, ???????????????
?????????? ?????? ?????????? ????????????? ?????? ???????????? ??????? ??? ab initio
??????????? ??????????????? ????????? ???? ?????????? ??????????.
???????? ?????: ??????????????? ????????? ????????, ?????? ?????????? ???????????,
???????????? ? ???????????? ?????????, ?????????? ?????????, ???????????????????
?????? ??????????????, ??????????????? ????? ?????????.
????????
?????????? ?? ??????-??????????????? ???????? ?????????? ??? ?????????? ? ??????????????? ?????????? ? ?????????? ??????? ??????? ? ??????????. ?????? ??????????
????????????? ? ????? ?????????-??????????? ?????? (??) [1, 2] ? ???????? ?????????? ?
????????? ???????? ????????? ?????? ? ????????????? ??????????? ????? ????????????
?????? ???????????????? ????????. ???????? ??????? ??? ???????? ????????? ?????? ????????????? ?????? ??????????????, ?????? ? ???????????? ????? ???????, ?????????? ?
????? ??????????????, ????????? ????????? ???????? ?????????? ?????????. ???????????
???????????? ???????? ????? ??????????? ?????????? ???????????? ?????? ? ?????????????-
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: i-s-jakimov@yandex.ru
# 180 #
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?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
??? ?????? ?????????, ??????????? ?????? ??????? ??????????????? ????????? ? ?? ???????????. ??????????? ??????????? ????? ??????? ?????? ?????? ????????????? ?????????????????? ?????????????? ??????? (??????????????) ???????? ??? ????????? ????????,
??????????? ?? ?????????? ????????? ? ?????????? ??????? ??????????????. ??? ???????, ??? ????? ???????????? ???????????????? ????? ???????????????? ????????? ????????????? (????? ?????????) [3], ?????????? ?? ?????????? ???.
????????? ???????? ?????????? ??????????? ??????. ??????????? ?????????? ?????? ??????? ????????? ?? ?????????? ?????????????? ???????????? ???????? ?????? ?????????????, ????? ???????? ????????? ????????? ??????? ? ???? ??????? ??????????
?????? ?? ?????? ?????????????? ? ?????????????? ?????? ? ????????. ?????????????
???????????? ?? ??????? ?????? ?????????? ????????? ?????????????? ??????? ?????????? ???????????, ?????????????? «??????» ????????? ???????? ?? ?????? ? ??????? ?
??????????????? ?????? ???????? ?? ???????? ???????????? ????????? ?????????????? ?
?????????????????. ? ????????? ???? ??????????? ?????????? ???? ????? ?????????????? ????????, ???????? ???????? ?????????? ??????????? [4]. ???????? ??????? ??????
???????? ??????, ?????????????, ????????, ? ?????? ????????? ??????????? ??????????
Fox [5] ? DASH [6].
???????????? ???????????? ???????? (??) [7] ? ?????????????? ????? ?????????? ???????????, ?? ?????????? ???????? ?????????????? ????????????? ??????, ???????????? ???
?????????? (??????????) ????? ?? ???????????? ?????????? ???????? ?????????? ?????????????? ???????, ??????? ?? ???????????? ???????????, ????????????? ??????? ? ????????
????? ????????? ????????? ?? ??????? ???????.
???????? ?? ?? ??? ??? ?????? ?????? ?????????????? ??? ???????????? ??????? ??????????? ???????????? [8, 9] ? ? ??????? ?? ?????? ??? ???????? ????? ??????? [10], ???? ?????
??? ???????????? ?????? ??? ???????? ??????????. ? [11] ????????, ??? ? ????????? ???????
??? ?? ????? ??????????? ????????? ??, ???? ????????? ???????????? ??????? ??? ??????
???????????, ? ????????? ??????? ???????????. ???????? ?????? ????????????? ?????????
????????????? ????????? ?? ??? ?????? ?????????, ? ?? ? ???????????? ??????? ???????????? ?? ???????? «??????? ?????».
????? ????????????? ???????????? ?????????????
? ?????? ?????? ??????????? ????? ????????????? ???????????? ????????????? (???),
?????????????? ???????? ????????????? ???? ????? ????????????? ?????? ?????? ??????????? ??????? [12]. ???????????? ??? ???????????? ?????? ?????????? ?? ? ??????????? ??????? ???????? ??? ????????????? ???????????, ?????????????? ???????????? ?? ? ???????
???????????????? ????????? ??????????? ???????. ??????? ?????????? ????????? ???,
?????????? ??? ??????????? «? ????» 21 ??????????????? ????????? ??????? ?????? ?????????, ????????? ? ????. 1. ???????? ??????? ?? ??? ????? ????????? ?????????? Er10W2O21 ?
16 ??????? ? ????? ???????? ??????????? ????? ?????? (48 ??????? ?????????).
????? ???????, ??? ?????? ????????? ?? 6-7 ??????, ????????????? ? ?????, ????????????? ??????????? ???????? ??????, ? ??????? ??????????? ????? ????? 3000 ???????????
???????. ????????, ??? ????? ???? ??? ??????????? 19 ?????????? ????? ???????. ???????,
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????? ????? ? ?????? ??????????? ???????????? ????????, ?????????????? ?????????? ???
??? ??????? ???????? ?????? ????????????? ??????? ??????????????? ????????? ????????
?? ????????????????? ?????? ?????????? ?????????.
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????????? ?? ?????? ?????????? ????????? PS,? ???? ?. ? ???????? ?????????? ????????? ????? ?????????????? ?????????? ????????? ?????? ? ?????? ????????? ????? ?????? (???????
? ??????????? ??????????) ? ????????? ???????? ????????? ??????. ? ? ??????? ????, ????????? ?? ?????????? ?????????? ???? PB, P = ?L,?ЧPS,?ЧPB ? D. ???????????? ?????????
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?????? ???????????? ??????????? ??????? ?????? ???? ?, ??? ?????? ?????? ??? ??????????
?????? ?????????? ?? ??? ?? ?????? ????????? ?????????? ?/??? ??????????? ?????????? ?? Pi. B-???????? ???????????? ???????????? ????????? ???????????, ??????? ? ??.,
??????? ??????? ????????? ?????????? ???:
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??? ?????? ??? ???????? ?????????? ?? ?????????? ????? ?? ???????? ? ???????? ???????? R (??? ?? ????? ??????????????? ???????). ????????? ???????? ?????????? ? ????????? ????????????? ??????????????? ?????????, ?????????????? ??? ??????????????????
???????????? ????????? ?????????? ?????????? ?????? ???.
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?? 1-? ?????? ???. ?????????? ?????????? ?????????????? ??? ??? ????????????? ????
???????? ? ??????????? ????????? ?????? ?? ?????? ?????? ????????? ?????? ????????, ???
??? ???????? ???? ?????? ?? 10?15 ???????? (??????????? ?????????????? ??????????) ??????????? ???????? 5-?????? ?????. ? ???????? ??????? ? ????. 2 ???????????? ?????????? ????????????? ????????? ????????? Ba2CrO4 (????????? ???????: a=7.67Е, b=5.89Е, c=10.39Е,
?=?=?=90?, ???????????????? ?????? ????????? Pn21a), ? ??????? ??????????? ?????????? 21
?????????? 7 ?????? ? ??????????? ????? ??????. ??? ?????????? ??????? ???????????????? ???????????? (????????, ??????? ???????????? ? ?.?.) ? ???????????? ??????? ????????
???????? R-??????? ???????????? ????????? ??????????? ?????????????? (??????????????
?????? ??????? ?????????????????). ????????? ???-?????????????? ?????, ??? ?????????
?????????? ???????????? ?????????? ???????????? ?? ?????? ??????????? ???????? ????????? ??? ??? ??????? ??????? ?????.
??? ???????? ??????????? ????????????? ??????????? ????????? ?? ????????? ? ????????????? ????????? ?????? ?????????? ?? ?????????????? ??? ???????????? ??? 1-??
??????. ? ????? ??????? ???????????? ?????????? ??????????? ????????? ??????, ? ????????? ?????? ????????? ?? 100 ????????. ??? ?????????????? ??????????? ? ????? ?????? ???
1-?? ?????? ??????????? ????????? ????????? ?????? ?????? ????????? ?? ???. ? ????. 3
???????????? ?????????? ?????????? ??? ?????? ??????????? ???????? ????????? ??? ?
?????? ?? ???? ??????? ??? ????????????? ????????? Ba2CrO4.
?? ???. 1 ???????? ???????? ??????? ??????????. ??? ????????????? ?????? ??? 1-?? ?????? (?????) ??????? R-?????? (1,4 %) ????????? ? ????????? ??????? ?? 102-?, ? ? ?????????????
??? (??????) ? ?? 39-? ????????? ????????. ?? ?????? ??????? ???. 1 ?????????? ????????
????????? ???????????? ????? ???1 ? ???2, ?????? ????? R-??????? ?????? ????????? ??
???????? ???2 ???????????? ???????? ???????????? ????????? ??????????? ?? ???. ?????
???????, ?????? ?????????? ?????????????? ????????? ???????????? ????????????? ???.
??????? 2. ?????????? ????????????? ????????? Ba2CrO4 ? ??????? ????????? ?????
????? 4 ???
??????????
????????
?????? ( %)
20
????? 5 ???
??????? ?????
(???)
??????????
????????
?????? ( %)
40
70
????? 6 ???
??????? ?????
(???)
??????????
????????
?????? ( %)
??????? ?????
(???)
30
40
35
# 184 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
??????? 3. ?????????????? ?????????? ??? 1-?? ?????? ? ?????????????? ???
???????? ?????????????
??? 1-?? ??????
2-????????? ???
?????????? ???????? ?????? ( %)
10
60
??????? ????? (???)
23
30
???. 1. ??????? ?????????? ????????? Ba2CrO4: ????? ? ????????????? ???, ?????? ? ?????????????
(????????? ?????? ? ????? ???1 ? ???2); ??? ??????? ? ????? ?????????, ??? ??????? ? R-??????
???; ??????? ????? ? R-?????? ?????? ?????????, ??????? ?????? ? ???????, ????? ???????? ?
?????? ?? ????????? ?????????
??????? 4. ????????? ????????? ?? ??? ????????? Ba2CrO4 ? ?????????*
????
X*
X???
|?|
Y*
Y???
|?|
Z*
Z???
|?|
Ba1
0,0047
0,0047
0,0000
0,2432
0,2427
0,0005
0,1893
0,1893
0,0000
Ba2
0,8519
0,8519
0,0000
0,2500
0,2500
0,0000
0,5838
0,5839
0,0001
Cr1
0,2770
0,2771
0,0001
0,2420
0,2408
0,0012
0,5800
0,5798
0,0002
O1
0,5230
0,5231
0,0001
0,1900
0,1906
0,0006
0,5770
0,5771
0,0001
O2
0,1650
0,1647
0,0003
0,2330
0,2313
0,0017
0,4260
0,4258
0,0002
O3
0,3250
0,3253
0,0003
0,9930
0,9909
0,0021
0,1570
0,1573
0,0003
O4
0,6950
0,6954
0,0004
0,0050
0,0035
0,0015
0,8500
0,8502
0,0002
?????????? ?????????? ?????? ? ??????? ????????? ??????? ? ?????????: ??????? ?????????? ?????????? |?|??.=0,00047 (????. 4).
?? ???. 2 ?? ??????? ????? ??1 ????????, ??? ?????????? ?????????? ?????? ? ?? ???????? ??????? (x, y, z) ??? ????????????? ????????? Ba2CrO4 ?? ?????????????? ???. ?? ???
??????? ???????? ?????? ?????????, ?? ??? ??????? ? ????????? ????? ?? ????? ?? ????????? X,Y ??? Z ? ??????????? ????? ??????; ???????? ???????? ?????????? ??????? ???????# 185 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
X
Y
Z
???. 2. ??????? ?????????????? ?????????? ????? ??1 ? ???????? ????????? ????????? ? ?????????
???????? Ba2CrO4 (??? ??????? ? ????? ?????????, ??? ??????? ? ?????????? X, Y ??? Z ?????).
???????????? ????????? ????????? ?????? ??????? ??? 1-?? ? 2-?? ???????
??????? ??????? ??????, ???????????? ???????????? ?????? ???????? ??????????? 1-?? ?
2-?? ??????? ???. ? ???????? ?????????? ?????????? ???????????? ? ??????? ????????
(10-??????? ???????? ??? ??????????? ???????? ???????) ? ??????????? ???????? ????????,
????? ??????? ???????? ????????????? ????????? ?????????.
? ??????????? ????????????? ? ??????? ?????????? ??????????, ??? ? ??????????
??????????? ??????? ??????? ??????????? ???????? ????????? ??????? ??????, ? ????? ????? ??????. ??? ? ???????????? ? (1)-(3) ??????????? ??????? ??????? ? ?????????????? ????????? ?? ??????? ??????, ????? ?? ?? ??????????? ? ???????? ??????? ?? ?????? ?????????
?????????????? ?????? ?????? ???????????? ?????? ??????.
????????? ?????????? ??? ????????????? ??????????? ????????? ??? ?????????????? ????????? ???????????? ??????????? ??????? ?? 2-? ??????. ??? ???????? ??????????? ????????????? ?????????? ????????? ??????????? ???????? ?? 2-? ?????? ???
???????????? ???????????? ????????? ???????????? ???? ??????????? ?????????? ?? ??????????????? ?????? ??? ??????????? ????????? ???????? ? ?????????? ??????????.
??? ??????? ?????????? ????????? ?? ???????? ???????? ?? ????????, ??????????? ??????????? ????????? ????? ? ?????????? ??????? ????????????? ??? ???????? ??????????? ??????????. ? ????. 5 ????????? ?????????? ????????? ?? ????? ???????? ?????? ?????????? ?????????? ????? ??????? ???????? ?????????? K4SnO4 (27 ??????? ?????????)
? Pd(NH3)2(NO2)2 (12 ????????? ???????????? ??????). ??? ??????????, ??? ????????? ???
??????????? ??? 2-?? ?????? ???????????? ?????? ?????????? ??? ?????? ????????
???????????? ?? ????????? ? ???.
????????? ???????? ?????????? ??? ????????????? ???????????? ??????? ??????????
??????????? ???????? ???????????????? ??????? ??????? ? ?????????? ????????? ????????? ?? ???? ????????? ??????????? ????????. ???????????????? R-??????? ??? ????????? ??
?????? ?????????? ????????????, ?????????????? ? ???????????????? ?????? ???????? ????????? X, Y ? Z ??????? ????? ? ???????? ??????????????? ?????????? ??????????? ???????
?? ?? ???????? ????????, ?????? ?? ?? ICSD [1]. ????? ??????????? ?? ???????? ???????
?????. ????? ????????? ?????? Z ?????? ???? ???????? ? ???????? ??????? ? ?????????.
?? ???. 3 ???????? ???????? ????????????? R-???????, ?????????? ????? ?????? ????????# 186 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
??????? 5. ?????????? ????????? ?? ??????? ???2 ? ??? ?????? ???????? ?????????? K4SnO4 ?
Pd(NH3)2(NO2)2 ? ????????? ????????? ?????????? ????????? ??????
?????????? ?????????
???
???2
???
???2
K4SnO4
?????????? ???????? ?????? ( %)
??? ????????? 5 %
80
100
??? ????????? 10 %
80
20
Pd(NH3)2(NO2)2
?????????? ???????? ?????? ( %)
??? ????????? 10 %
80
100
??? ????????? 15 %
80
20
350
R s ta rt
Sn1z
K1z
K2z
K3z
K4z
O 1z
O 3z
O 4z
300
250
R
200
150
100
50
0
0
20
40
60
80
100
???. 3. ?????? ????????????? R-??????? ? ????????? ???????? K4SnO4 ??? ?????? ????????? ???????
??????? (x,y,z) ?? ???????? (Rstart ? ????????? ?????????, Sn1z ? ????? ?????? ??????? ????? Sn,
?1z ? ????? ?????? ??????? 1-?? ????? ? ? ?.?.)
?? Z ? ????????? ?? 100 ??????????? ??????? K4SnO4, ????????????? ? ??????? ????????
R-???????.
?????? R-??????? ????????? ????????? ??????????, ??? ??? ? ????????? ???????? ?????????????? ???????? ??????? ????????? ?? ????? ? ???????????? ????????? R-????????. ??
???? ??????????? ?????? ? ???????? ??????? ?????? ????????????? ?????????????? ??? ????
? ????. ??? ???? R-?????? ? ?????? ?????? ????????????? ???????? ????????????? ? ???????? ??????????????. ???????, ??? ????????????? ????????????? ????????? ?, ?????????????,
R-?????? ??????? ?? ?????????? ??????????, ??????? ??? ??????, ????????????? ?????? ??
???????? ???????, ?????? ? ???????????. ? ?? ?? ????? ?????????? ????? ? R-?????? ??
?????????? ?????????? ??? ?????? ? ????????? ???????? ????? ??????? ??????????????, ?
??? ??????????????? ????? ????????????? R-??????? ? ?????? ????? ???. 1.
???. 3 ?????????? ??????? ???????????????? R-??????? ? ????????? ?????? ? ????????
???????. ??????? ? ???????? ???? ???????????????? ???? ????????????? ???????? ????????
?? ????????? ????????? R-??????? ??? ?????? ?????????? (X, Y ??? Z):
NX
n X {[ 'Ri
cp .
m
¦ 'R
j 1
ij
/ m ] ! 0} / n
# 187 #
(6)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
??????? 6. ?????????????? ???????? R-??????? ??? ???????????????? ?????? ????????? ?????????
?????? ?? ?? ???????? ???????? ? ?????????? ????????? ????????
??????? {NX + N Y}
??????? {NZ}
??????? {?R/R)i??.}
??? ????????? X ? Y
??????? {?R/R)i??.}
??? ????????? Z
69,3 %
94,6 %
2,3 %
14,8 %
K4x
K4y
K4z
40
27,0
O1x
O1y
O1z
25,5
35
24,0
R
R
30
22,5
25
21,0
20
19,5
50
60
70
80
90
100
50
60
70
80
N t
90
100
t
???. 4. ??????? ????????????? R-??????? ? ????????? ???????? K4SnO4, ????? ??? ????? ?4, ?????? ?
??? ?1; ?? ??? ??????? ? ?????????? ????? ?????????; ? ?????? ? ?????? ??????????????? ??????????
????????? ??????
??? ?Rij ? ????????? R-??????? ??? ?????? ?????????? ???????? ?????????? ????? i ?? ???????? ? ????????? j ?? n ?????? ? ????????? ?? m ????????. ???????, ??? ??? ?????????? ???????????????? R-??????? ? ??????????, ???????? ? X, ???????? NX ~50 %, ? ???????? ?Ri??. ~ 0,
? ????????? ?????? NX >>50 % ? ?Ri??.>>0. ??????? ?????????????? ???????? R-??????? ???
?????? ????????? ????????? ?????? ?? ???????? ???????? ??? 10 ?????????? ??????????????? ????????? ???????? ?????????? K4SnO4, As2O3 ? CaC4H4O6·4H2O ?????? ??????? ????????? ??????? ? ????. 6.
? ???????? ??????????? ?? ???. 4 ???????????? ?????? ????? ???????? ???????? ???????? R-??????? ??? ?????? ????????? ?????? ?? ?? ???????? ???????? ? ????????????? ????????? ?? 100 ??????????? ??????? ?????????? K4SnO4, ??????????? ??? ???????? ? ???????
??????: 4-?? ????? (?????) ? 1-?? ????????? (??????). ??????? ??????? ????????????? ??????
????????? ????????? X ? Y, ? ?????? ? ?????? ??????? ??????? (X, Y, Z).
?? ???. 4 ?????, ??? R-?????? ???????????? ? ????????? ? ???????? ??????? ?? ??????
????? ?????, ?? ? ????????? ??? ?????????, ?????? ?? ?????? ??????? (?????), ?? ? ??????
(????????), ???? ? ? ??????? ???????.
?????????? ????????? ?????????? ?????????? ???
??????? 1 ??????????, ??? ????? ??? ????? ???????????? ?????????? ?????????? ????????? ????????? (~100) ??????????? ??????? ?? ????????? ????? ????????? (~26), ???????? ?? ???????? ????? ????????? ????????? ?????????. ????????, ??? ????????? Ba2CrO4
(21 ??????? ??????????) ??? ?????????? 2105 ??? ??????????? ?? 5-?????? ?????. ? ????????????
? (1)-(4) ???????? R-??????? ?????? ??????????? ?? ???? ?????????? ?????? ? ?? ???????? ??# 188 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
???. 5. ????????? ??????? ???????????????? R-??????? ? ?????????? X0Y ??? ????????? K4SnO4:
????? ? ??? ????? ?????, ?????? ? ??? ?????? ?? ??????????
??????. ??????????? ?????????? ????????? ??????? ????? ? ???????? ??????? (x,y,z) ?????????? ?1=1/215, ?.?. ? ??????? ? ???? ??????????? ?????? ????????? ?? ~ 320 ?????????. ????????, ??? ?????????? ???? ?????? ? ???????? ???????? ? ????? ?? ???????? ????????? ???????
???????? ?????? ???????? ? ??????? ??? ??????? ????? ?????????, ??? ?????????? ? ???.
???? ?????????? ?????????? ? ???????????? ?????????????? ???????????????? R-??????? ?
????????? ????????? ?????? ? ?? ???????? ??????? ? ????????? ????????? ????????????,
??? ????????????? ??????? ????????? ? ??? ?????? ? ????????? ?????? ?????? ???? ? ????????? ??????? ??????????. ????????, ??? ??????? ?? ????????????? ?????? ???????????????? R-???????. ?? ???. 5 ???????????? ??????? ???? ???????????? R-??????? ?????????
K4SnO4 ??? ??????? ????????? X ? Y ??? ???????? ????? ????? (?????) ? ??????? ????? ????????? (????????? ??????? ?????????? ??????????? ? ???????? ???????? ?????????). ?????
???????? ??????? ??????? ??????? ????? «???????» ?????? ??????????? ????????. ?????? ?
???????????? ????? (X, Y) ????? ?? ????????? ?? ???????? ???????? ??? ????????? ????????
?????? ?????????? ???????? ? ?????????? ??????? ??????????? ????????? ???? ????? ?? ????
??????? ? ????? ?????? ????????? R-???????, ??????? ????? ??? ????????? ??? ?????????
???? ??????????? ?????? ?? ???.
????????? ?????? ????? 1/24 ??? ???????????? (????. 2), ????? ????????????, ??? ???????? R-??????? ? ??????? ???????????? ?2 ??????? ????????? ????? ????????? ????? ?? ????????? ????? ? ???????? ????????, ???? ??? ???? ????????? ???????? ???? ?????? ?????????
????? ?????????? ? ??????????? ???????? ??????? ????? ? ???????? ????? 1/23. ???????????
????????? ?????????? ????? ? ???????? ???????? 1/25 (? ??????? ? ???? ??????????? ???????
????????? ??????? 100), ????? ??????????? ???????? R-??????? ???????? ?3 =1/211?2. ??? ?2 ~0,5
???????? ?3 =1/212 ? 8 ??? ???? ?1. ???????? R-??????? ???????????? ????????????? ???????????????? ?????????? ????? ??????????? ??????? ? ?????????. ???????? ???????? ????????? ??????, ?????????? ? ????????? ??????????? ??????? ?? ???? ??????????? ? ???????
???????, ???????????? ?????????? ???????? R-??????? ? ???????????????? ?? ?????????
?? ???? ????? ??????????? ? ????????. ????????? ??????????? ?????? ?? ???? ???????????
# 189 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
??????? ?? 2-? ?????? ??? ???????????? ?????? ????????? ????????? (???. 2), ? ?????????
?????? ? ???????? ??????? ??? ????? ??????? R-?????? (???. 4). ?? ???? ?????????? ??????
? ???????? ???????? ??? ???????? ? ?????????? ????? ?? ??????????? ??????? ? ????????
?????????.
??????????
?????????????? ?????? ???????? ?????? ? ???????????? ????????? ???????????? ab
initio ????? ??????? ??????????????? ????????? ?????????? ?????????? ?? ?????????? ??????????????, ?????? ???????????????? ? ?? ??????? ??????? ???????????? ????????????? ?
??????? ???????????? ???????. ??? ??????? ??????????? ?????????? ??????????? ???????????? ??????????????? ? ??? ?? ???????????? ? ?????????????????? ???????, ??? ????? ?????????? ?????????? ? ??????????? ?? ?? ?????? ????????? ??????????? ? ?????????, ???? ?
????, ??? ?????? ?? ??? ???????? ???????????? ?????????? ??????????? ???????????????.
?????? ????????? ??????????????? ????????, ???????????? ????? ????????, ???? ?? ????????? ~ 40 ???????? ??????? ??????????? ?????????? [4, 15]. ??????????? ? ??????????
??????? ??????? ?????????? ?????? ????????????? ?????? ??? ????????? ??????????????
??????????? ??? ???????? ??? ??????????? ????? ??????? ??????????????? ????????. ????? ?? ???????? ????????????? ??????????? ???????? ???????? ?? ?????? ??? ????????????
??????????????????? ?????????? ??????????? ??????? ?? ???? ????????????????? ??????????.
?????? ??????????
1. Inorganic Crystal Structure Database. FIZ Karlsruhe // http://www.fiz-karlsruhe.de/icsd.html.
2. Cambridge Structural Database. Cambridge Crystallographic Data Centre // http://www.ccdc.
cam.ac.uk/products/csd/
3. Young R.A. The Rietveld Method // Oxford University Press. 1995. 298 p.
4. David W. I. F., Shankland K. Structure determination from powder diffraction data // Acta
Cryst. (2008). A64. P. 52?64.
5. Favre-Nicolin V. and Cerny R. FOX, `free objects for crystallography?: a modular approach to
ab initio structure determination from powder diffraction // J. Appl. Cryst. (2002). 35. P. 734?743.
6. Thomas A. N. Griffin, Kenneth Shankland, Jacco van de Streek and Jason Cole. GDASH: a
grid-enabled program for structure solution from powder diffraction data // J. Appl. Cryst. (2009). 42.
P. 356?359.
7. Goldberg D. E. Genetic Algorithms in Search, Optimization and Machine Learning. Addison.
Wesley Publishing Co. Inc., 1989. ISBN 0-201-15767-5.
8. Solovyov L. A., Kirik S. D. Application of a Simulated Annealing Approach in Powder Crystal
Structure Analysis. Materials Science Forum 133-136 (1993). P. 195-200.
9. Kariuki B. M., Serrano-Gonzalez H., Johnston R. L. and Harris K. D. M.. The application of
a genetic algorithm for solving crystal structures from powder diffraction data. Chem. Phys. Letters,
280:189.195, 1997.
10. Kenneth D.M. Harris. Fundamentals and applications of genetic algorithms for structure solution
from powder X-ray diffraction data // Computational Materials Science. V. 45. Issue 1. 2009. P. 16?20.
# 190 #
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?.?. ??????, ?.?. ?????? ???????????? ????? ????????????? ??????????????? ????????? ?????????
11. Cerny R. and Favre-Nicolin V. Direct space methods of structure determination from powder
diffraction: principles, guidelines, perspectives // Z. Kristallogr. 222 (2007) P. 105-113.
12. Yakimov Y. I., Semenkin E. S., Yakimov I. S. Two-level genetic algorithm for a fullprofile
fitting of X-ray powder patterns. // Z. Kristallogr. Suppl. 30 (2009) P. 21-26.
13. Powder Diffraction Theory and Practice, ed. R.E. Dinnebier and S.J.L. Billinge // Royal
Society of Chemistry, 2008. 507 P.
14. Solovyov, L.A. Full-profile refinement by derivative difference minimization / L.A. Solovyov
// J. Appl. Cryst. 2004. Vol. 37. P. 743-749.
15. Bail A. Le, Cranswick L. M. D. Third structure determination by powder diffractometry
round robin (SDPDRR-3) // Powder Diffr. Volume 24, Issue 3, pp. 254-262 (September 2009).
The Evolutionary Method of Modeling
a Crystal Structure
by Powder Diffraction Data
Yaroslav I. Yakimova,
Sergei D. Kirik , Evgeny S. Semenkina,
Leonid A. Solovyovb and Igor S. Yakimova
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx, Krasnoyarsk, 660049 Russia
a
The evolutionary method for modeling of crystal structure from powder diffraction integrated with full
profile analysis method and genetic algorithm is proposed. An evolutionary mechanism of new hybrid
method is studies on ab initio determination a number of known structures.
Keywords: X-ray powder diffraction, crystal structure analysis, genetics algorithm.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 192-202
~~~
??? 547.914.4+539.2:54+615.7
?????????????? ????????? ????????
? ??? ????????????????? ??????????
?.?. ??????????,?,
?.?. ??????????? , ?.A. ???????????,?*,
?.?. ??????, ?.?. ??????,?, ?.?. ?????????,?
?
???????? ????? ? ?????????? ?????????? ?? ???,
?????? 660049 ??????????, ??. ?. ??????, 42
?
????????? ??????????? ???????????,
?????? 660041, ??????????, ??. ?????????, 79
?
???????? ????? ???????? ???? ? ??????????? ?? ???,
?????? 630128, ???????????, ??. ???????????, 18
?
??????-??????????????? ????? «???????????? ??????
? ???????????? ?????????? ??????????» ??? ???,
?????? 630090, ???????????, ??. ????????, 2-125
?
???????????? ??????????????? ??????????? ???????????
??. ????. ?.?. ?????-??????????,
?????? 660022, ??????????, ??. ????????? ?????????, 1
?,?
Received 24.11.2012, received in revised form 04.02.2013, accepted 19.02.2013
? ?????????????? ??????????????? ????????????? ????????, ??? ????????????????
????????? ???????????????? (??) ? ????? ? ?????????? ???????? (???) ? ??????? ????????
???????? ? ????????? ???????????-????????? ????????????? (???) ??. ????? ???????????
???????????????????? (??) ????? ? ???? ? ????????? ???????????? ??????????? ???
???????????? ?????????????? ???. ???????????? ??????????? ????????????????
????????? ??? ? ?? ??? ??????????? ???????? ? ?? ?????? ? ????. ????????, ???
??????????????? ??? ? ?? ???????? ???????????? ???????????? ? ???????? ???????
????????? ?????? ???????? ????????? ??????????, ?????????????? ?????????? ???????
??????????.
???????? ?????: ???????? ????????, ???????????????, ???????????????? ?????????,
???????????, ????-??????????? ?????????????, ????????????????? ????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: ksa@icct.ru
# 192 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
CH 3
C
H 2C
CH3
CH 3
CH2OCOCH3
CH3
CH3?OO
CH 3 CH3
???. 1. ??????????? ??????? ????????? ????????
??????? ???? ???????? ??????? ? ???????? ? ???????? ???????? (?34?54?4, 3?,28?
??????????-??? 20(29)-??) ? ???????? ?? ??????? ??????. ?? ????????? ??????????????????,
??????????????????, ???????????, ??????????????? ???????? ? ???????????? ??? ????????
[1-5]. ????? ?? ??????, ?????????????? ??? ?????????????, ????????? ?????? ?????????????
? ???? ? ??????????????? ????????? (???. 1).
???????????? ????????? ????????????? ?????????? ? ??????????? ??????????????? ??????? ?????? ????? ?? ???????? ?????????? ???????? ??????????? ? ????????????? ????????????? ?????????? ? ????? ????????? ?? ?????????????? [6, 7]. ? ?????????? ????????????
????????? ?????????? ??????????????? ??????????????? ????????? ????????????? ???????
? ?? ??????????????? ? ??????? ???????? ? ???????????? ?????????????? ??????????, ???
???????????? ?????????? ???????? ??????????? ? ????????????? ??????????.
????? ???? ???? ???????? [8, 9], ??? ???????????? ????????? ???????? ? ?????? ? ???????????????? ?????????? ? ????????????????????? (???) ? ?????????????????? (???) ?
???????? ? ??????????? ??????????, ??? ??????? ?????????? ??????????????? ?????????
???????? ? ?????????????? ??? ? ??????????. ??? ??????????? ???????????????? ? ???? ???????????? ???????? ? ???????? ????, ??? ??? ??????????? ????????? ????????. ?????? ???????????? ????????? ??? ? ??? ? ??? ?? ??????? ? ????????? ??? ?????????????, ???,
????????, ??????? ? ???, ??? ??? ???????????? ????????? c ?????????? ??? ?? ?????????
? ???????????????? ????????? ? ?? ???????? ???????????? ?????????? ? ??? ? ??? [8]. ?
????? ? ???? ???????????? ??????? ??????????? ??????? ?????? ????????? ?? ???????? ??? ?
???????????????????? ??????.
??????????????? (??) ? ??????????????? ????????? ???????????, ?????????? ?? ????????? ???????????, ?????????? ?????????? ?????????? ??????? [10]. ?????????????
?? ????? ????????????? ????????: ??????? ???? ??????? ?? ??????? ?????????, ???????????
???????????? ??????? ?-(1?3), ? ??????? ???? ?? ??????? ?-(1?6) ? ?? ??????? ????????? ?
?????????, ?? ????????? ??????? ?????????, ? ????? ???????? ??????, ? ???????? ???????????? (???. 2). ??????????? ???????????? ????? ?? ?????????? ???????? ???? ??????????,
???????????? ? ??? ? ????? ????. ????? ???????????? ???????? ????????? ????????????,
??? ????????????? ?? ?????????? ? ??????????, ????????, ??????????? ?????. ?? ?????
# 193 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
???. 2. ???????? ????????? ????????????????
?????????????? ? ???????? ?????????????, ???????????, ???????? ??? ????????????? ??????????. ??? ???? ??????? ??????? ?? ???????? ? ???????? ????? ???????? ????????? ??? ???????????? ?????.
? ??????? [11-13] ???????? ??????????????? ????????????? ? ???-????????????? ????????, ??? ???????????????? ????????? ?? ? ??????????? ???????? ???-2 ? ???????? ???????? ??-1 ???????? ? ????????? ???????????-????????? ????????????? ? ??????? ??????????????? ??? ????????????, ??? ?? ??????????? ???????????? ?? ??????????? ????????? ??.
????????? ??????????????? ?????????? ?? ? ?????????? ???????????????? ?????????????? ?????????? ????????? ???????? ?? ????????????????? ??????????????. ????????, ???
? ?????? ????????????????? ??????? ?????????? ????? ?????????? ????????? ?? ?????????
? ??????????? ????????.
????? ?????? ?????? ???????? ???????????? ??????? ???????????????? ????????? ??
??????-?????????? ???????? ?????? ????????? ???????? ? ????????????????? ? ???????? ??
????????????????? ???????.
????????????????? ?????
? ?????? ???????????? ??? ? ??, ?????????? ?? ????????????? ???????????? ????????? [14, 15].
???????????????? ????????? ????????? ? ???????? SPEX 8000 (CertiPrep Corp., ???)
? ???????? ????????? ??????? 40 ??. ????? ?????????: ??????? ???? ? ???????? ???? ????????? 6 ??, ????????? ??????? ??? 8-10 g, ???????? 30 ?, ????? ?????????????? ????? 1 ?,
???????????? ????? ????????? 30 ???. ??????????? ??? : ?? ?????????? 1 : 9 (?? ?????).
??????????? ?? ? ??? ?????? ? ??? ? ???? ????????? ? ??????? ????????????? Varian
705 DS. ? ????? ? ????? ???????? 200 ?? ?? ??? 180 ?? ?? ? 20 ?? ??? ? ??????????? ???
?????????? ????????????? ??? 37 °? ? ??????? 2 ???. ????? ???? ??????? ???????????????
# 194 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
? ??????? ???????? ? ????????? ??? 0,2 ???. ????????? ?????????? ??????????? ??? ?????????? ???????? ? ??????????? 35-40 °? (??????????? ?????????? ??-1?, ??????).
??????????????? ?????? (???) ????????? ? ?????????????? ????????????? D8 DISCOVER
? ???????????????? ?????????? (Bruker), CuK?-?????????, 2?=5ч40.
??-??????? ???????? ??????? ??????????? ??????? ??????????? ????????? (????) ?
????????? ?????? 4000-500 ??-1 ?? ????? ??-???????????? Digilab Excalibur 3100 (Varian) ???
??????????? ????????.
??????????? ??????????????? ???????? ?? ????????? ??????????? ?????????? ??1000 HITACHI (??????).
???????????-???????? ????????????? ???????? ??????????? ??????? ???????????????
????????????? ?? ???????????? Agilent 1200 ? ??????????????????? ?????????? 1260 Infinity
(30 °?, PL aquagel-OH 40 300*7,5 ??, 0,1 ? LiNO3, 1 ??/???). ?????????? ??????? ?????????????? ? ??????? ??????????? ???????? ?????????? (Sigma-Aldrich) ? ????????????? ???????
10 600, 20 000, 41 272, 70 000. ????????????? ??????????? ?? ???????? ?????????? ???????????????????? ?????????.
??? ??????????? ?????????? ??? ??????? ??????? 9-10 ?? ?????????? ??????????? ?????????? 1 ?? ??????????. ?????????? ???????? ?????????? ? ??????? ??????? ??????????
? 1 ?? ???????. ?????????? ??? ?????????? ????????????????? ? ??????? ????????????
«???????? ?-02» (??? «???????», ??????) (35 °?, ProntoSIL 120-5C18 AQ 2,0*75 ??, ?2? (?) ?
??3?N (?), 80-100-100 % ?, 100 ???/???). ?????????? ??? ?????????? ?? ?????? ???? 200 ?
210 ??.
???????? ??????????? ????????????????? ?????????? ??????????? ??????? ??
??????? ???????? ?????????????? ?????? ? ????????????? in vitro. ?????????????????
?????????? ???, ?? ? ??????????????? ??? ? ?? ?????????????, ???????? ???? ?????????????? ? ????????????? ???????? ?????? ????? 24 ? ????? ??????????? ??????????. ????????
?????????????? ??????? ?????????? ???????????, ????????? ???????????? ????? ??????, ?????, ??????? ????? 3 ? ????? ?????????? ??????????.
???, ?? ? ?????????????? ??? ? ?? ?????????? ? ??????????? ????? ?????? ?? ???????????? ??? ??????????? 40 °? ? ??????? 4 ?. ????? ? ???? ????????? ?????? ??? ? 200 ???
????? ?????? ????????? ?????????????? ???????????? ???????? ? ???????????? 0,5 ??/??.
?????? ????? ??????????? ? ???? ????????????.
??? ??????????? ??????? ??????????????? ??? ? ?? ? ???????? ?????? ??????? ??
????????? ??????? ?????????? ??????? ???????? ?????? ???????????? ? ??????? ????? ???
??????????????? ? ????????????? ??????????? ??????? 0,5 ??/?? ? ??????? 3 ? ??? ??????????? 37 °?, 5 % ??2 ? ????????? 6 %. ??? ??????????? ?????? ???????????????? ???????
???????????? ?????????????? ???? GreenCa2+, ?????? ? SBFI-AM, ????? ? PBFI-AM. ??????? ?????????? ????????? ?????? ?????? ???????????? ? ?????? ? ???????? ????????????
0,05 ??/?? ? ??????? 30 ??? ??? 37 °?, ????? ???? ?? ???????? ?? ??????? ?????????. ????????????? ????????????? ???????? ?? ????????? ????????? Beckman Coulter FC500. ??????????? ????????????? ?????? ??? ????????? ????????? ?? ???????.
????????????? ?????????????? ? ????????????? ?????? ????????? ? ??????????? ?? ??
??????????? ??????????????? ??????????? ? Hoechst 33342 ? Propidium iodide. ???????????# 195 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
??? ??????? ????????? Hoechst 33342 ?????????? ???????????????? ???????? ?????????????? ?????? ????, ??? ???????? ?????. ??????? ?????????????? ????????? Propidium iodide
???????? ????? ???????????? ?????????????? ???????? ????????????? ?????? ? ?????????? ???. ??????? ?????? ?? ????????? ???????????? (?????????? ?????????????? ???? ?
?????????? Propidium iodide) ???????? ? ???????. ??? ??????????? ???? ?????????????? ?
????????????? ?????? ??????? ???????? ?????? ???????????? ? ???????? ??????, ?????????? Hoechst 33342 (1 ??/??) ? Propidium iodide (1 ??/??), 10-15 ??? ??? ????????? ???????????. ?????????? ?????????????? (????-???????), ????????????? (??????? ? ??????-???????)
? ????? ?????????? ??????? ????? ?????? ???????????? ? ?????? ?????????????, ?????
?????????? ?????? ? ? ???????? ?????? ? ??? ?? ???? ??????. ????? ???????????? ??????????
??????????? ???? ???? ??????? ??????.
?????????? ? ??????????
???????????? ??????? ???????????????? ????????? ?? ??????-?????????? ???????? ?????? ????????? ???????? ? ?????????????????. ????-????????????? ?? (???. 3?,
?????? 1) ????? ???????? ???????? ? lg M = 4,2 ? ????????? ??? ? lg M = 2,8 (??????? ??????
8,9 ? 11,3 ??? ??????????????).
???????????? ????????? ? ??????? 10 ??? ???????? ? ??????????? ????????? ????
?????????? ????????? ?????? ????????? ? lg M = 3,9 (????? ?????? 9,35-9,4 ???) ? ????? ????????????? ????????? ????. ??? ???? ????????????? ?????? ????????? ????????? ?????????
?? ?? ??????????? (???. 3?, ?????? 2). ???????????? ????????? ? ??????? 30 ??? ???????? ?
1
2
3
0,8
0,6
0,4
0,2
0,0
5,0
4,8
4,6
4,4
4,2
4,0
3,8
lg M
3,6
3,4
3,2
3,0
2,8
2,6
1
2
0,8
?)
0,6
0,4
0,2
0,0
5,0
4,8
4,6
4,4
4,2
4,0
3,8
lg M
3,6
3,4
3,2
3,0
2,8
2,6
?)
???. 3. ????-????????????? ?? ? ??? ?????? ? ???: ?) 1 ? ????????? ??, 2 ? ?? ????? ?? 10 ???,
3 ? ?? ????? ?? 30 ???; ?) 1 ? ?? ????? ?? 10 ???, ??????????? ? ???? ? ???????????? ?????????
????????????, 2 ? ????? ??? ? ?? ????? ?? 10 ???, ??????????? ? ???? ? ???????????? ?????????
????????????
# 196 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
??????? ?????? ????????? ? lgM = 4,2 ?? lg M = 3,9 (???. 3?, ?????? 3). ??? ??????? ? ???, ???
? ????? ??????? ?? ?????????? ?????????? ???????????? ????? ???????? ? 2 ????: ? ~16000
?? ~8000, ??? ??? ??????????? ? [13] ??? ???????????? ????????? ? ?????? ??????? ?????????. ??????????? ???????? ????? lg M = 3,9 / lg M = 4,2 (? ??????????? ????????????? ? ?????
??????) ????? 10 ? 30 ??? ???????????? ????????? c????????? 1,2 ? 6,3, ??? ?????????????
«??????? ???????????» ?? ? ????????????????? ????????? ~ 55 ? 87 %.
??????????? ???????????????????? ???????? ?? ? ???? ? ??????????? ?????????? ???????????? ???????? ? ?????????? «??????????????» ???????????? ????? (???. 3 ?, ?????? 1).
? ?????? ?????? ?? ? ??? ????????????? ???????????????????? ???????? (???. 3 ?, ??????
2) ????? ??????????? ?? ? ???? ? ??????????? ???????????? ??????????? ??? ????????????
????????? ??.
??????????? ??? ? ????? ???????????? ??????????? ?? ???????????? ??????? ? ???????
???????????? ??????. ???????? ????? ????? ???? ???????????????????? ? ????????. ??????????, ??? ??? ?? ??????????? ?? ??????? ???????? ????? ??? ? ?? ??? ?????????? ????????. ??? ??????? ? ???, ??? ? ?????? ????????, ??-????????, ?????????? ???????????????
???????? ?? ? ???. ????????? ?? ??????????? ????????????? ?????? ????? ? ??-????????,
???????? ???, ????????, ????????? ?????? ?????????????? ???????? ? ??????? ? ??????????
?? ?? ???? ???-???-?????????? ??????????????. ????????, ??? ??? ? ???? ??????????? ???????????, ?? ????????? ???????????????????? ??? ? ?? ???? ???????? ???????? ? ????????????? ??? 0,15 ? 0,18 ??/??.
???????? ??????? ???????? ??? ????????? ???????????? ??????????? ???????????
????????? ? ???????? ?????????? ???????????? ??. ??????????? ???????????? ????? ??? ?
???????????? ?????? ?????????, ????? ????????????, ??? ?? ???? ????????????? ?? ?????????? ????? 1 ???????? ???. ??? ????????????, ??? ??? ????? ????????????????? ? ??????????? ??????????????? ??.
???????????? ????????? ??? ?? ??????????????? ???????????????????? ?????? ???????????? ????????????? ????? ????????????????? ???????? ? ??????? ???????? ? ???????????? ??????????????? [16]. ? ??-???????? ???????????????????? ?????? ?? ???????????
?????? ?????????? ?????, ??????????? ? ?????????? ?(?=O) ? (?-O), ?.?. ?????, ??????? ????? ????????? ??????? ? ??????????? ?????????? ??????, ?? ????????? ? ?????????? ??????
???????????, ??? ????? ????????????????? ? ????????????? ??? ? ??????? ?? ??? ??????????? ??????????????? ?????????? ??????. ???????? ??????????? ????????? ?? ??????? ?????????????? ????????? ???????????????? [12]. ???????? ?????????? ???????????? ?? ???
???????????? ?????????, ??????????? ? [13], ????? ???????????? ????????? ?? ???????????
????? ??, ??? ?????? ?????????????? ??????????? ?????????? ? ???, ?????? ??????????? ??????????? ??? ????????????? ????? ?? ? ???????? ???.
?? ???. 4 ???????????? ??????????-??????????? ??????????? ????????? ????????, ?
????? ??? ????????????????????? ????????? ? ?????????????????. ????????? ????????? ???????? ????? ????????????? ????? ????????? ?? 10 ?? 100 ??? (???. 4?). ? ?????????? ???????????? ????????? ????????? ??? ???????????? ?? ???????? 5-10 ??? ? ????????????
????? ???????? ?????? ???????? 5-30 ??? (???. 4?). ????? ????????????, ??? ????? ???????????????? ? ?????????? ??????????????? ? ????????????? ???????????.
# 197 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
?
?
???. 4. ??????????-??????????? ??????????? ???????? ??????? ???????? (?) ? ???????????????
????????? ???????? ? ????????????????? (?)
???????? ????????? ????????????? ??? ? ???? ????? ????????? ??????????????? ? ??,
????? ???? ??????? ????????? ??? ??????????????, ??????? ???????????? ??????? ???????
????????????????? ???????? ?? ?????????? ? ????????? ? ?????? ???.
????????????????? ????????????. ????????????????? ???????????? ?? ???? ???????????????? ?????????????? ?????? ?. ??????????? ????????, ??? ?????????? ???????????????
??? ? ??, ??? ?? ??? ? ?????????????? ????????, ? ???? 2000 ??/?? ?? ???????? ????????? ?
???????? ????????????? ????????????????? ????????????? ?? ????? ??????? ? 4-?? ??????
????????????? ???????.
???????? ????????????????? ?????????? ????????? ????????? ???????? ? ????????????????? ?? ??????? ???????? ?????????????? ?????? ? ????????????? in vitro. ????????, ??? ??????????????? ??????? ???????? ???????? ?????? ??????????????? ????????????,
??????? ???????? ?????????? ??? ???????? ??????? ????????, ?, ????? ???????, ?? ??????????
?????????????? ????????? ?????? ? ?????????????? ???? ?? ???????? [17-20]. ???????????? ?????????? ??????????????? ???????????? ???????? ??????? ??????????? ????????? ??????? [21].
? ????? ????????????? ????????? ???????? ?????? ? ??????????? ???????? ???????? ??
??? ???????: ? ??????? ? ?????????? ????????????? ???????? ???????. ?????????? ?????? ?
??????? ????????????? ??????? (?????? ????? ????????) ?????????? (42±1,3) %, ? ????? ??????
? ?????????? ????????????? ??????? (???????????? ??? ?????????? ??????) ? (58±2,2) %
(???. 3 ?). ???, ?? ? ?????????????? ??? ? ?? ????????? ???? ?????? ? ??????? ????????????? ???????, ??? ??????? ????????? ?????????????? ?????????? ?????? ????????????
???????? ??????.
??? ????? 3 ? ????? ?????????? ???, ?? ??? ?? ??????????????? ???? ?????? ? ???????
????????????? ??????? ??????????? ?? (22±1,0) % (???. 5 ?), ??? ????????????????? ? ????????
????? ?????? ? ????????? ?????. ?????????????, ???????? ???????? ??? ? ?? ? ?????????????? ??? ? ?? ??????????? ????????? ????????? ????????? ???????????? ?????? ????????
????????? ?????? (???).
?????? ? ????? ? ???????? ??????????????? ???????, ??????????? ? ???????????
????????????? ????????, ????????-????????? ???????, ????????? ??????? ??????, ????????
# 198 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
?
?
?
???. 5. ????????? ???????????? ???????? ??????? (?), ?????? (?) ? ????? (?) ? ??????? ??? ??? ????????
??????????????? ??? ? ?? (2), ??? (3) ? ?? (4) ? ????????? ? ????????? (1)
??????? ? ????????. ?????????? ??? ?????????? ???????????? ????? ?????? ????? ? ????????? ???????? ??????. ??? ????????, ?????????? ???????? ?????? ????? ????????? ????????
????????, ? ?? ?????????? ? ???????? ???????. ??? ??????????? ???????? ??????? ???????????? ???????????????? ????? ? ??????, ?????? ? ??????? ??????? ?????????? ???????? ?????
? ?????? ????????? ??? ???????????? ??????????????? ??? ? ??. ????????????? ????????
?????????? ????? ? ?????? ? ?????? (???. 5?, ?) ??????????????? ? ??????? ???????? ? ???????.
??? ???? ????? ????????????, ??? ???????? ??? ? ?? ??????????? ??????? ?????? ??? ?
??????? ???????, ??? ???????? ???????? ??? ? ??.
????? ???????, ???????????????????? ????????? ??? ? ?? ???????? ?????? ????????? ??????, ?????? ???????????? ???????, ?????? ? ????? ? ??????. ????????? ????????, ???
?????????? ?????????? ?????????? ??????, ????? ? ??????? ???????? ? ???????? ????????,
????? ????????????, ??? ???????? ??? ? ?? ??????????? ??????? ?????????? ????????
??????.
?????? ?? ??????? ??????????????? ??? ? ?? ? ???????? ??????? ?? ??????? ?????????? ???????? ?????? ????????? ?????? ???????????? ? ????. 1.
??? ???????? ???? ??????????? ??????? ??????????? ???? ?????? ??? ? ????????? ????????: ? ??????????? ?? ????? ??? ? 5 ???, ? ??????????? ??? ????? ??? ? 7 ???, ? ? ???????????
??????????????? ??? ? ?? ????? ? 12 ???. ?????????? ?????? ?? ?????? ???????? ? ??????? ?
???????? ??????? ??? ???????? ??????????? ??????? ?????????? ????????? ????????????????? ?????? ????????? ???????? ? ????????????????, ?? ? ??????? ??????? ???????????????
??? ? ??, ??? ????????? ??????????? ? ??????? ??????? ??????????, ??????????????? ??
???. 5.
????? ???????, ? ?????? ?????? ??????? ??????????????? ????????????? ???????????,
??? ???????????????? ????????? ???????????????? ? ??????? ???????? SPEX 8000 ???????? ? ????????? ??? ???????????-????????? ?????????????. ??????????? ????????? ????????
???????????? ?????????????? ??? ????? ??????????? ???????????????????? ????? ? ???? ?
????????? ????????????. ???????????? ?????????? ?????? ????????? ???????? ? ????????????????? ???????? ??????????????? ? ?????????? ????????????? ??? ? ??????? ????????.
# 199 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
??????? 1. ??????? ??????????????? ??? ? ?? ? ???????? ??????? ??? ? ?? ?? ??????? ??????????
???????? ?????? ????????? ??????
?????????? ????????????
?????? ???
???????
??
???
??????????????
???+ ?? (1:9, ????.)
????????
6,6±0,8
5,0±0,6
6,6±0,9
7,3±0,5
???????, %
16,7±1,8*
23±2,5*
36±3,8*
3,1±2,8
????? ????
??????????????? ??????
23,3±2,8
28,0±3,0
42,6±5,8
10,4±1,3
??????, %
??????????: * ? ????????????? ??????? ?? ????????, ?<0,05.
????????, ??? ??? ????????????? ??????????????? ????????? ???????? ? ?????????????????
??????????? ??????? ???????? ?????? ????????? ??????, ?????? ?????????? ?????????????? ?????? ?????????? ????? ? 12 ??? ?? ????????? ? ?????????. ?? ????????? ?????? ??????? ?????????? ????????????, ??? ???????? ???????? ?????????? ?????? ????? ???? ????????
???????????????? ?????????? ???????? ?????? ? ?????, ?????????? ? ?????????? ????????? ???????? ?, ?????????????, ??????? ????????.
?????????????
?????? ????????? ??? ?????????? ????????? ???? (11-03-12114-???-?), ?????? ?? ??????? ??? ?????????? ?? ?? ????????? ??????? ??????? ???? (??-221.2012.3) ? ?????????
?????????? ??? «??????????????? ????? ? ????????». ?????? ?????????? ?.?. ??????? ?
?.?. ????????? ?? ?????? ????-???????????? (????? ?? ???), ?.?. ??????? (????? ????????????? ??????????? ????????????? ???????? ??????) ?? ?????? ??????????-???????????
??????????? ????????) ? ?.?. ????????? ?? ??????????? ??????? (???? ?? ???).
?????? ??????????
1. ?????? ?? ? 2150473. ?????? ????????? ????????? ?????????? / ???????? ?.?., ???????? ?.?., ???????? ?.?., ??????? ?.?. 2000. ???. 16.
2. ???????? ?.?., ???????? ?.?., ??????? ?.?., ?????? ?.?., ????? ?.?. ???????? ???????????????? ???????????? ??????????? // ????? ????????????? ?????. 2001. ?1. ?. 69-73
3. Masayoshi T., Yoshihiro S. and Akio I. Polymer obtained from betulin and its production
method// Patent Japan ?2001-288222. 2001.
4. ????? ?.?., ???????? ?.?., ?????? ?.?. ? ??. ?????? ??????????????? ???????????
??????????? ? ??????????? ?????? ? ?? ????????????????? ?????????? // ???????????????
?????. 2005. ?. 31, ?3. ?. 320?325.
5. Patent US ?20090318719. Method of preparation and isolation of betulin diacetate from birch
bark from paper mills and its optional processing to betulin / Sarek J., Svoboda M., Haiduch M. 2009.
6. Shakhtshneider T.P., Boldyrev V.V. Mechanochemical synthesis and mechanical activation
of drugs. ?Reactivity of Molecular Solids?. Ed. E. Boldyreva, V. Boldyrev. John Wiley & Sons LTD.
England. 1999. P. 271-312.
# 200 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
7. Colombo I., Grassi G., Grassi M. Drug mechanochemical activation // Journal of Pharmaceutical
Sciences. 1998. V. 98. ? 5. P. 3961-3986.
8. ?????????? ?.?., ??????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?.,
???????? ?.?. ??????? ???????????? ????????? ?? ???????? ???????? ? ?? ????? ? ???????????????? ?????????? // ????? ????????? ??????????. 2011. ?2. ?.211-214.
9. ??????????? ?. ?., ????????? ?. ?., ?????????? ?. ?., ????? ?. ?., ????????? ?. ?.,
???????? ?. ?. ????????? ??????????? ?????????? ???????? ? ????????????????????? ?
?????????????????? // ?????? ?????????? ???????????? ????????????. ?????. 2012. ?.5, ? 1.
?. 52-60.
10. ????????? ?. ?., ?????? ?. ?., ?????????? ?.?. ??????????????? ??????????? ?
???????? ? ??????????? ????????????? (?????) // ????? ????????????? ?????. 2003. ? 1.
?. 7-37.
11. ???????? ?.?., ?????? ?.?., ?????????? ?.?., ????????? ?.?., ??????? ?.?., ?????????
?.?., ???????? ?.?., ?????? ?.?. ???????????????? ????????? ? ????????????????? ?????????? ??????????????? ?????????? ???????????????? ? ????????????? ??????? // ????????
???, ????? ??????????. 2008. ?6. ?. 1274?1282.
12. ?????? ?? ? 2337710. ??????????????? ????????????? ?????????? ? ?????? ?? ????????? / ?????? ?.?., ?????????? ?.?., ????????? ?.?., ???????? ?.?. 2008. ???. 31.
13. ????????? ?.?., ???????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?., ??????
?.?., ?????????? ?.?., ??????? ?.?., ?????? ?.?. ??????????? ??????????? ???????????????? ?? ??????????? ????????? ??? ???????????????? ????????? ? ????????????? ????????
????????? // ????? ????????????? ?????. 2009. ?3. ?. 49?56.
14. ?????? ?? ? 2324700. ?????? ????????? ????????? ?????????? / ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?. 2008. ???. ? 14.
15. ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?. ?????? ????????? ????????????????// ?????? ?? ? 2273646. 2006. ???. ? 10.
16. Boldyrev V.V. Mechanochemistry and mechanical activation// Materials Science Forum.1996.
Vols. 225-227. P. 511 520.
17. Zamay A. S., Zamay T. N. Change in Physicochemical Parameters of Membranes of Ehrlich
Ascite Adenocarcinoma in the Course of Tumor Growth // Doklady Biochemistry and Biophysics.
2005. Vol. 402. P. 197?199.
18. Liu Z.M., Chen G.G., Vlantis A.C., Tse G.M., Shum C.K., van Hasselt C.A. Calcium-mediated
activation of PI3K and p53 leads to apoptosis in thyroid carcinoma cells // Cellular and Molecular Life
Sciences. 2007. Vol. 64, ? 11. P. 1428-1426.
19. Clapham D.E. Calcium Signaling // Cell. 2007. Vol. 131, ? 6. P. 1047?1058.
20. Neher E., Sakaba T. Multiple roles of calcium ions in the regulation of neurotransmitter release
// Neuron. 2008. Vol. 59, ? 6. P. 861-872.
21. ????? ?.?., ????? ?.?. ??????? ??? ?? ???????????? ???????? ??????? ? ????????
??????? ????????? ?????? ? ???????? ?? ????? // ????????. 2006. ?. 71, ? 10. ?. 1347-1353.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
The Mechanocomposite of Betulin Diacetate
and its Antitumor Activity
Svetlana A. Kuznetsovaa,b, Tatyana P. Shakhtshneiderc,d,
Mikhail A. Mikhailenkoc,d, Yuriy N. Malyara,
Anna S. Zamaya,e and Vladimir V. Boldyrevc,d
a
Institute of Chemistry and Chemical Technology SB RAS
50/24, Akademgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk,660041 Russia
c
Institute of Solid State Chemistry and Mechanochemistry SB RAS
18 Kutateladze St., Novosibirsk, 630128 Russia
d
Research and Educational Center ?Molecular Design
and Ecologically Safe Technologies?
2 Pirogov St., Ch. Building, 125, Novosibirsk, 630090 Russia
e
Krasnoyarsk State Medical University
named after Professor V.F. Voyno-Yasenetsky,
1 Partizan Jeleznyak St., Krasnoyarsk, 660022 Russia
Using gel-penetrating chromatography, it has been shown that mechanochemical treatment of a
mixture of arabinogalactan (AG) with betulin diacetate (DAB) in a ball mill led to change of the
molecular weight distribution (MWD) of AG. The presence of DAB in the mixture promoted restoration
of MWD after dissolving the mechanically activated mixture in water and solvent evaporation. The
formation of intermolecular complex DAB with AG at dissolution of initial and mechanically activated
mixtures in water was suggested. It was shown that the mechanocomposites DAB with AG had the
ability to induce cells in ascites Ehrlich carcinoma cell elimination processes mediated disturbance
of ion homeostasis.
Keywords: betulin diacetate, arabinogalactan, mechanochemical treatment, dissolution, gelpenetrating chromatography, antitumor properties.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 203-209
~~~
??? 541.49+546.92+539.26
?????? ? ??????-?????????? ????????????
?????????????? ??????????
?????-????????????????????(II)
?.?. ???????*, ?.?. ???????????
???????? ????? ? ?????????? ?????????? ?? ???
?????? 660049, ??????????, ??. ?. ??????, 42
Received 05.12.2012, received in revised form 16.01.2013, accepted 03.02.2013
??????? ????? ??????? ??????? ? ????????? ??????-?????????? ???????? ??????????????
?????????? ?????-?????????????????????(II) ? ???????? ?????-[PtLL`Cl2], ??? L, L` =
?????????, ???????? ? ?????????????. ??? ??????????? 20 °? ? ???????? 0,5 ? KCl ???????
?? ?????????????. ??? ?????????????? ????????????????, ???????? ? ??????????????
??????-?????????? ??????? ?????????????? ?????????? ???????????? ?????? ???????????
???????, ???, ???, ????????????????, ??-?????????????????.
???????? ?????: ??????????? ?????????? ???????, ??????, ??????-?????????? ????????,
?????.
???????? ???-??????? ???-[Pt(NH3)2Cl2] ???????? ????????????? ??????????? [1]. ?? ???????? ? ??????? ?????????? ???????????. ??? ????? ???? ??????? ??????? ????????. ???
?????????? ?????? ???? ?? ????? ?????? ???????????? ? ???????? ?????????????????? ????????? [2]. ????? ?? ?????? ??????? ??? ??????? ????????????????? ?????????? ???- ?
?????-????????????????????(II) ???????? ???????? ? ???????????? ??????????????? ???
????????? ????????? ???? ??????????: ???????? ????????? ???-??????? ??????????? ??????
???????? ????????? ?????-???????, ????????? ???? ???-?????? ???????? ????? ? ??????????
???? ?? ??????? ???, ? ?????-?????? ???????? ? ??????? ? ???????????? ???????????? ???????? ? ??????????????, ?????????? ? ??. ???????? ????????? ????? ???????????? ??????
? ???????, ??????? ???????? ???????????? ??? ??? ???-, ??? ? ??? ?????-???????? ??????????? ?????????? ???????(II) [3,4].
????????????? ??????????????, ??? ????????? ?????-?????? ?????????? ??????? ???[Pt(NH3)2Cl2] ?? ???????, ?? ? ??? ?????????? ????????? ?????-???????????? ????? ?? ???????? ????????????????? ?????????? [5, 6]. ?? ?????? ??????????, ??? ????????? ????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: kaz@icct.ru
# 203 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
NH3 ? ?????-[Pt(NH3)2Cl2] ?? ?????? ????? ???? ?????????? ?????-[PtLL1Cl2], ??????? ?????
???????? ???????????????? ? ????????????? ?????? ???? ?? ???????, ??? ? ???-[Pt(NH3)2Cl2]
[7]. ????????????????? ?????????? ??????????? ?????????? ???????(II) ?????-????????????
????? ?????????? ?? ???? ????????? ???????? ?????????? ??????? ????????, ??????? ?????
????????? ???????? ????????? ????????? ???????? ? ?????????? ???????. ???????? ????????, ???????????????? ? ?????? ???????, ????????? ???????????? ????????? ????????????????? ?????????? ???? ?????????? [8, 9].
?????????? ????????? ?????-???????????? ??-???????? ???????????? ??????? ??????? ? ?????????????? ????????????? ????? ?????????? ?????????????? ??????????,
????????? ?????????? ???????????? ??????????? ??? ???-???????. ??????? ????????
??????-??????????? ???????? ????? ?? ?????????, ??????????????? ?? ????????? ????????
? ?????? ??????????, ????????? ?????? ? ????????????? ?????????????? ?????????? ????????????????? ?? ????? ???????.
????????????????? ?????
??? ????????? ??????????? ?????????? ?????-???????????? ???????? ????????? ???????????????? ????? L ?? ???? ???-[Pt(L)2Cl2] ? ????? L` c ???????????? ??????????? ?????????? ???????(II) ? ??????????? ???????????? ?? ? ??????? ??????? ? ???????? ?????????.
???-[Pt(L)2Cl2] + 2 L` = [Pt(L)2 (L`)2]Cl2
[Pt(L)2 (L`)2]Cl2 + 2HCl = ?????-[PtLL`Cl2] + L·HCl + L`·HCl , ??? L,L` = CH3NH2, ?2H5NH2, i-C3H7NH2.
?????? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2]. ? 1,5 ? ???-[Pt(i-C3H7NH2)2Cl2] (3,9·10 -3 ???) ????????? 0,52 ? CH3NH2·HCl (7,8·10 -3 ???) ? 15 ?? H2O. ????? ? ???????? ???? ????? ??? ?????????
??????????? ?????????? 1,5 ?? CH3NH2 ? ????????? ??? 40 °?, ???? ??????? ?? ????????????.
??????? ????????? ? ???????????????. ????????? 15 ?? ??????? ??????? 12? ? ????????? ?? ?????? ? ???????? ????????? ? ??????? 8 ?. ?????????? ?????? ??????? ?????????,
???????? ?????? ???????????????, ????????? ??????? ? ??????. ?????????? ???????????
????????? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2] ? 1,02 ?, ??? ????????? 82 % ?? ??????????????.
?????????? ??????????? ??????? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2]
?????????, %
Pt
N
C
H
Cl
54,77 7,86
13,49 3,96
19,91
???????, %
54,79 7,75
13,58 3,80
20,06
?????? ?????-[Pt(CH3NH2)(?2H5NH2)Cl2] ? 2 ? ???-[Pt(?2H5NH2)2Cl2] (5,6·10-3 ???) ?????????
0,756 ? CH3NH2·HCl (1,12·10-3 ???) ? 15 ?? H2O. ????? ? ???????? ???? ????? ??? ????????? ??????????? ?????????? 2 ?? CH3NH2 ? ????????? ??? 40 °?, ???? ??????? ?? ????????????. ???????
????????? ? ???????????????. ????????? 15 ?? ????????????????? ??????? ??????? ? ????????? ?? ?????? ? ???????? ????????? ? ??????? 8 ?. ?????????? ?????? ??????? ?????????,
???????? ?????? ???????????????, ????????? ??????? ? ??????. ?????????? ???????????
????????? ?????-[Pt(CH3NH2)(?2H5NH2)Cl2] 1,50 ?, ??? ????????? 78 % ?? ??????????????.
?????????? ??????????? ??????? ?????-[Pt(CH3NH2)(?2H5NH2)Cl2]
?????????, %
Pt
N
C
H
Cl
57,02 8,19
10,53 3,83
20,72
???????, %
57,07 8,30
10,67 4,00
21,00
# 204 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
?????? ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2] ????? ??? ????? ?? ????????, ??? ? ?????? ????
?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2], ?????? ? 1,5 ? ???-[Pt(i-C3H7NH2)2Cl2] (3,9·10 -3 ???) ?????????
0,64 ? C2H5NH2·HCl (7,9·10 -3 ???) ? 15 ?? H2O. ????? ? ???????? ???? ????? ??? ????????? ??????????? ?????????? 2 ?? ???????? ????????? ? ????????? ??? 40 °?, ???? ??????? ?? ????????????. ? ???????????? ???????? ?? ?????? ??????????? ????????? 15 ?? ?????????????????
??????? ???????. ?????? ??????-??????? ?????. ????? 1,15 ?, ??? 80 % ?? ??????????????.
?????????? ??????????? ??????? ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2]
?????????, %
Pt
N
C
H
Cl
52,70 7,57
16,22 4,35
19,15
???????, %
52,90 7,40
16,01 4,63
20,00
?? ???? ??????? ?????? ?? ??????? ????????? ??????? ????????. ??????? ????????? ?????????? ?? 50 ?? 100 ??. ????, ???????, ??????? ?????????? ?? ?????????? ????????????????
«NC Soil Analysez FLASH EA 112 Series». ????? ??????? ?????????? 5-8 ??. ?????????? ?????
?????????? ??????? ???????? ? ??????????? ??????????????????? ??????????? ????????? ????????????? ???????.
?????????? ?????????????? ?????????????? ?? ????????????? ??pert Pro (PANalytical,
??????????) ? ?????????? ?? ??????-????????, ?????????? ????????????????? ??????????
PIXel ? ?????????? ??????????????. ???????????? CuK?-?????????. ???????? ?????? ??
10 ?? 90° ? ????? 0,026°.
??????????? ?????????? ???????? ?? ??????? NET2SCH STA 449 ? ? ???????????? ???
????????? ????? ? ????????? ?????????. ?????????? ????????? ? ????????? ?????????? ??
20 ?? 1000 °? ?? ????????? 10 °? ? ??????. ????? ??????? ?????????? ?????????? 10 ??.
??-??????? ?????????? ?????????????? ? ??????? 4000 ? 400 ??-1 ? ????????? KBr ?? ??????? ??-????? ??????????? «Vector-22».
??????????? ??????? ?????????? ??????? ?? ???????????????? «Specord UV-VIS». ????????? ????????? ???????????? ???????? ? ??????? 28 000?46 000 ??-1.
?????????????
??????????????
???????????
??????????
?????-????????????????????(II) ??????? ??? t = 20 °? ? 0,5 ? KCl (??? ?????????? ?????????). ??? ??????? ?????????? ????????? ?? 10 ??????. ????? ??????? ??????????? ?? 0,002 ?? 1 ?. ?? ?????????? ? 100 ?? 0,5 ? KCl ? ???????????????? ??? t = 20 °?. ????? ???? ???????????? ?????
??????????? ??????. ????? ?????????? ??????-?????????? ???????? ????????? ??????????
?????? ???????????????, ???????? ?? ????????? ???????? ??????? ? ?????? ??? ?????????
???????????.
?????????? ? ??????????
????????????? ????? ??????? ??????? ?????????????? ??????????? ??????????
???????(II) ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2, ??????????? ? ??????
??????, ????????? ???????? ???????? ???????? ? ??????? ??????? ? ????????.
?????????? ??????????? ???????, ???, ??-?????????????, ??-????????????????? ???????????? ?????????? ???????????????? ? ??????? ??????????? ???????.
??????????????????? ???????????? ????????? ?????????? ??? ???????????? ??????,
?????? ????????? ? ????????? ???????????? ??????.
# 205 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
??? ?????????? ?????-[Pt(CH3NH2)i-(C3H7NH2)Cl2] ? ???????????? ??????????? ?????? ?
??????? ????????? ?21 ? = 28,439(3)?, ? = 6,057(2)?, ? = 6,055(3)?, ? = 93,59(2)°, V = 1041.28 ?3,
Z = 4.
??? ?????????? ?????-[Pt(CH3NH2)(C2H5NH2)Cl2] ? ???????????? ??????????? ?????? ?
??????? ????????? ?21/? ? = 11,761(3)?, ? = 12,690(3)?, ? = 17,080(2)?, ? = 90,43(3)°, V = 440.63
?3, Z = 2.
??? ?????????? ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2] ? ???????????? ??????????? ??????
? ??????? ????????? ?21/? ? = 18,094(2)?, ? = 6,633(2)?, ? = 9,345(3)?, ? = 90,72(3)°, V = 1121.38
?3, Z = 4.
????????? ??-?????????????????? ???????????? ????? ?????-[PtLL`Cl2], ??? L, L` ?
?H3NH2, ?2H5NH2 , i-C3H7NH2, ??????? ????????? ?????? ?????????? ?? ????????? ?????????
?????? [10-13]. ?????????? ????????? ? ????. 1.
???????? ??????????? ???????????? ????? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2,
i-C3H7NH2 ? ????????? ?????????? ?? 20 ?? 1000 °? ????????, ??? ??????? ?????????? ?????????? ??? ??????????? t1 ? ????????????? ??? t4. ??? ???? ??????????? ?????????? ?? ??????
??? ??????? ??? ??????????????? ??????? t1 ? t3. ???????? ?????? ????-???????? ?????????
????? ??? ??????????? t1 ?????????? ????? ??????, ? ??? ??????????? t2 ? ?? ??????????. ???
??????????? t3 ?????????? ????? ????-?????, ?????????? ????????????? ???????????? ????????????? ??????? ??? t4. ?? ?????? ?? ?????????? ?????? ?????, ??? ????????? ???????????
?? ????????????? ???????. ?????? ???????????? ??????? ????????? ? ????. 2.
??-?????????????????????? ???????????? ??????????? ?????????? ?????-[PtLL`Cl2],
??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2, ????????? ???????. ?????? ??????????? ?????????
???????????? ?????????? ?? ????? ????? ??? ?????????????? ??????????? ??????????
???????(II) ?????-???????????? ????????? ? ????. 3 ? ???????????? ??? ???????? ????????????? ???? ??????????.
??? ???????? ????????????? ??? ??????? ????????? ???? ????? ?? 10 ??????? ??????
?????, ?????????? ? 100 ?? 0,5 ? KCl ? ???????????????? ??? 20 °?. ????? ??????????
??????? 1. ????????? ????????????? ?????? (??-1)
[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2
?????????, ??-1
? (NH)
? (CH)
? (NH2)
? (CH3)
? (CH2)
? (NH2)
? (CN)
? (CH3)
? (NH2)
? (PtN)
?????-[Pt(CH3NH2)
(i-C3H7NH2)Cl2]
3266, 3238, 3218, 3144
3004, 2970, 2934
1590
1456, 1411
1393, 1338
1272, 1247
1038
998
745
518
? ??-???????? ?????????? ?????????? ??????????-[Pt(CH3NH2)
(C2H5NH2)Cl2]
3263, 3226, 3152
2983, 2937, 2888
1590
1452, 1410
1384, 1352
1271, 1240
1037
994
740
513
# 206 #
?????-[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
3251, 3220, 3144
2973, 2930, 2874
1587
1467, 1393
1347, 1324
1236
1037
940
751
520
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
??????? 2. ?????? ???????????? ??????? ?????????? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 ,
i-C3H7NH2
??????????
???????, %
????
??????
?????, %
??????????? ????????????? ?????, °?
t1
t2
45.21
190
42,98
222
198
????.
????.
(?H3NH2) (i-C3H7NH2)
54.79
54.77
(?H3NH2) (?2H5NH2)
57.02
57.07
(?2H5NH2) (i-C3H7NH2)
52.90
52.70
47.10
t3
t4
264
278
290
272
286
307
269
273
292
??????? 3. ???????? ???????????? ?????????? ?(????-1 ·? · ??-1) ?????????? ?????-[Pt(CH3NH2)
(i-C3H7NH2)Cl2], ?????-[Pt(CH3NH2)(C2H5NH2)Cl2], ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2]
? · 103, ??-1
?????-[Pt(CH3NH2)
(i-C3H7NH2)Cl2]
?, ?/(???? · ??)
?????-[Pt(CH3NH2)
(C2H5NH2)Cl2]
?, ?/(???? · ??)
?????-[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
?, ?/(???? · ??)
41
164
165
185
40
79
76
100
39
80
73
95
38
110
101
119
37
120
112
131
36
112
98
121
35
91
75
101
34
73
63
87
33
74
67
88
32
79
76
93
31
70
66
84
30
44
42
60
29
33
30
49
28
29
28
43
??????-?????????? ???????? ?????????, ? ??????? ?????????? ?????? ???? ? ???????????
??????? ?????????? ????????? ???????? ?????????? ???????????, ?????? ??????????????? ?
???????????. ??? ???? ?????-[Pt(CH3NH2)i-(C3H7NH2)Cl2] ????? ?????? ??????? ?? ??????????
????????? 5 ???, ??? ???? ?????-[Pt(CH3NH2)(C2H5NH2)Cl2] ? 4 ???, ? ??? ?????-[Pt(C2H5NH2)
(i-C3H7NH2)Cl2] ? 7 ???. ???????????? ??????? ?Pt ? ????/? ? ???????? ???????????? ?? ?????? ??-???????? ??????????, ?????? ??? ?????????? ? ?????? ??-???????? ?????????????? ?????????? ?????-[PtLL`Cl2], ??? L, L` ?H3NH2 , ?2H5NH2 , i-C3H7NH2 , ? ????? ?? ????????
????? ????????? ???????? ??????? ? ??????????????? ?????? ?????.
???????????? ?????? ???? ? ???????? ??????????? ?????????? ???????(II) ???????????????? ???????? ?? ??????? ? ??????????????????? ????????. ?????? ?? ?????????????
??? ???? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2, ? ?????? ?????? ????????? ? ????. 4.
# 207 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
??????? 4. ?????? ?? ????????????? ??? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2], ?????-[Pt(CH3NH2)(C2H5NH2)
Cl2], ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2]
????????
????????
?????[Pt(CH3NH2)
(i-C3H7NH2)Cl2]
?????[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
?????[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
?????????????,
?????
?????????????,
???????? ?
????????????
????????? ??
???????? ?????
?? ??????? ??????
?????????
????????,
????, ????/?
?????? ????, ?
????/?
??????????
??????? ?
????????
?????????, %
??????????
??????? ?
?????? ???? ,
%
54,79
54,65
0,189 ± 0,002
5,30·10 -3 ±
0,05·10 -3
5,25·10 -3 ±
0,03·10 -3
57,02
57,10
0,197 ± 0,003
5,75·10 -3 ±
0,03·10 -3
5,70·10 -3 ±
0,05·10 -3
52,70
52,60
0,028 ± 0,004
7,56·10 -4 ±
0,04·10 -4
7,50·10 -4 ±
0,06·10 -4
????????? ????????, ??? ????????????? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2,
i-C3H7NH2, ????, ?????? ????????????? ??????????? ????????? ?????????? [14]. ??????? ?
????????? ???????? ?????? ???????? ?????????????? ??????????, ??? ???????? ?? ?????????????.
??????
????? ???????, ????????????? ? ?????????? ??????????????? ???????????? ???????????
?????????? ???????(II) ????? ???????? ??????? ?????????????? ??????????? ??????????
?????-????????????????????(II) ????????? ???????? ??? ?????????? ? ??????? ??????? ?
????????. ???????? ?? ????????????????? ? ???????? ?????????? ??????? ???????????? ?
??????? ???, ???, ???????????????? ? ??-?????????????????. ????????? ?????? ?? ??????????? ???????????? ?????????? ? ?? ????????????? ????? ???? ??????? ??? ????????????? ????????????????? ?????????? ?? ???? ??????????? ?????????? ???????(II).
?????? ??????????
1. Rosenberg.W., Van Camp.L., Trosko.J.S., Mansuor V.N. Platinum compounds: A new class of
potent antitumor agent// Nature. 1969. V. 222. P. 385-386.
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tricks // Encyclopedia of Cancer. Ed. Academic Press: San Diego CA. 1997. V. 1. P. 392-410.
3. Faggiani R., Lippert B., Lock C.J.L.and Rosenberg B. Hydroxo-Bridged Platinum(II) Complexes.
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Characterization and Vibrational Spectra // Inorgan. Chem. 1978. V. 17. ? 7. P. 1941-1945.
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Acta. 1982. V. 62. P. 187-191.
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1974. V. 12. P. 349.
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?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
6. Clear M.J., Hoeshele J.H. Studies on the Antitumor cyticity of Group VIII Transition Metal
Complexes Part I. Platinum(II) Complexes // Bioinorganic Chemistry. 1973. V. 2. P. 187.
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C.and Berners-Price S.J. Influence of amine ligands on the aquation and cytotoxicity of trans-diamine
platinum(II) anticancer complexes // J. Chem. Soc., Dalton. Trans., 2009. P. 3457-3466.
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donor sets // J. Med. Chem. 2006. V. 49. ? 1. P. 224.
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phosphines and amines as carrier ligands induce apoptosis in tumor cells resistant to cisplatin // J.
Med. Chem. 2007. V. 50. ? 9. P. 224.
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Complexes of platinum(II) // J. Amer. Chem. Soc. 1967. V. 89. ? 9. ?. 2007.
11. Arpalahti J., Lippert B., Schollhorn H., Thewalt U. Crystal Structures of Two Pt(II) Diamine
Compounds: trans-Pt(CH3NH2)2Cl2 and cis- Pt(CH3NH2)2Cl2 // Inorg. Chim. Acta. 1988. V. 153. P. 45.
12. ????????? ?.?., ?????? ?.?., ??????? ?.?. ??-??????? ?????????? ??????????????
???????? [Pt(CH3NH2)2Cl2] // ????. ?? ????. 1967. ?. 173. ?. 1113.
13. ????????? ?.?., ?????? ?.?., ??????? ?.?. ??-??????? ?????????????? ????????
[Pt(C2H5NH2)2Cl2] // ????. ???????. ?????. 1969. ?. 14. ? 1. ?. 227.
14. ??????? ?.?., ??????????? ?.?. C????? ? ??????-?????????? ???????????? ?????????? ?????-??????????-(????)???????(II) // ?????? ???. ?????. 2011. ???.4. ?. 377-383.
The Synthesis and Physico-Chemical Studies
of Nonsymmetric Complexes
Trans-Dichlorodiaminplatinum(II)
Alexander K. Starkov and Galina A. Kozuchovskaya
Institute of Chemistry and Chemical Technology,
Siberian Branch of the Russian Academy of Sciences
42, K. Marx Str., Krasnoyarsk, 660049 Russia
The new methods of synthesis and some physico-chemical properties of nonsymmetric ?omplexes
trans-dichlorodiaminplatinum(II) with the formula trans-[PtLL`Cl2], where L,L` = methylamine,
ethylamine, and isopropylamine were described. These methods allow increasing the yield and purity
of the substances. Their solubilites were studied at a temperature of 20° C in a solution of 0.5 M KCl.
To prove the identity, structure and characterization of physico-chemical properties of the complexes
the methods of elemental analysis, XRD, IR, thermogravimetric analysis, UV-spectrophotometry were
used.
Keywords: complex compounds of platinum, synthesis, physicochemical properties, amines.
# 209 #
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Journal of Siberian Federal University. Chemistry 2 (2013 6) 210-217
~~~
??? 621.355.2:546.34
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?
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?????? 660036, ??????????, ??. ????. ??????????, 28
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?????? 660036, ??????????, ?????????????, 50
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?????? 660049, ??????????, ??. ?. ?????????, 89
?
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?????? 660036, ??????????, ??. ?????????????, 50/24
Received 12.11.2012, received in revised form 22.01.2013, accepted 04.02.2013
???????? ????????????? ?????? ????????? ????????????? ?????-?????? ?????????????,
? ??????? ????????????? ????????? ??????????? ?? ??????????? ?????? ?????????????, ???????? ??????????????? ??????? ? ???????? ?????????????? ???????. ??
???? ????????????? ????????????? ?????????????? ??????????? ?????? ????????
?????????????? ?????. ???????????? ????????, ??? ???????????? ???????? ??????????
???? ??????????? ? ?????? ????????????? ?????????????? ??????? ? ???????? ?????. ??
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??? ??? ?????? ????????-????? ? 221 ??·?/?. ??????? ???????????????? ??????? ???????????,
??? ? ???????? ?????????????? ????????????? ?????? ????????? ???????????? ?????????,
? ?????????????? ?????? ???????????.
???????? ?????: ?????-?????? ????????????, ????????-?????, ????????????? ??????,
???????? ???????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: acbka1346@mail.ru
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????????
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???????????, ????????? ???????? ?????????? ???????? ??????????? ??????? (????????,
??????? ????????, ???????? ????- ? ???????????, ???????????? ??????????). ???????????? ??? ????? ??????? ??????????? ??????????? ???? ??????????? ? ?? ??????? ???????? ???????????????: ??????? 180?400 ?? · ?/??, ????????? ???? 0,1-100 ??/?? 2. ?????? ??
???? ???? ???????????? ????? ???????? ??????????? ?????????? ??????? ???. ???? ??
???????? ????????? ??????? ? ?????????? ???????? ??????????? ????????? ?????????, ??
??????????? ??????????, ????? ??? ??????? [1], ??????????? ?? ?????? Si [2], ?????? [3],
??? ?????????????? ??????????? ???? ????? ?? 400 % ? ?????????? ???????????. ????????????? ?????????? ?????????? ???????? ????????? ?????? ?? ????? ??? ?? 10 % ???
????????? ????? ?????. ? ?????? [4] ????????, ??? ?? ???????? ????????????????? ?????????????? ?????????? (????????????), ???????????? ??? ????????? ????? ????? ? ??????????
?????????, ???????????? ??????? ????????? ????????? ????????? ??????????? ????????. ?
??????????????? ??????? ?????????? ????? ???????? ??????????? ?????????? 3,35 Е, ???
????????? ????????? ? ??? ????? ????? (?????? ???? 0,68 Е). ?? ??? ????????? ???? ?????
?????????? ?????????? ???? ?? 0,376 Е, ??????? ???????? ?? ?????? ??????? ? ????????
?????????????? (500-1000) ?????????????. ????????, ??? ????????????? ?????? (??) ?????
?????????? ????? ?????? ?????? ?? 0,06 Е, ??? ? ??????????????? [5]. ???????????? ?????
????? ? ?? ????? ????????? ? ??????? ??????????? ?????????? ?????????, ??? ? ?????????????? ???????, ? ??????, ? ?????????? ?????? ?????-?????? ???????????? ??????????. ?
?? ????? ?????????? ?????? ????? ?????, ??? ???????? ?????????? ???????? ??????? ???
? ?????????? ?? ??.
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????? ???? ????????? ?????? ?????. ?? ????? ??????????????? ????????????? ????????,
??????????? ???????????????? ??????? ? ??????? ?????? HyperChem, ? ????????? ????? ???? ?????????? ????????? Li+:C=1:3. ?????? ?????? [6] ???????? ????????????? ??????????? ?????????? ?????? ?????????? ? ???, ????????? ????????? ?? ?? ?????? ?? ???????? ?????? ?????????????. ?????? ??????? ????????? ????????? ? ????????? ?????????
????????? ????? Li4C60 ? ?????? ????????????? ????????????? ??????????, ???????????
??????????? ????????????? [7].
????? ???????, ?????????? ???????? ???????????? ??????????? ????????????? ??????????? ????????????? ? ???????, ?????????????? ?? ??????????? ?????? ????????-?????,
???????? ??????????????? ??????? ? ???????? ?????????????? ???????.
???????? ????????????
????????-???????? ?????? ???? ???????? ??????? ????????????? ??????????????? ????????? ? ???????????????? ????????? ?? ???? ???-5. ?????? ???? ????????????? ?????? ?
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????????????? ????????? ????? ?????????? ? ????? ?? ?????? ??????. ?????????, ????????# 211 #
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??? ?? ?????????????? ???-4, ????????? ???????????????? ??????? ?????????? ??????????? ??????, ??????? ????????? 600 ??.
?? ????????? ?? ????????, ????????? ? ?????? [8]. ? ???????? ??????????????? ???????
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?????????? ???????. ??????? ?????????? ????????? 13 ??, ??????? ? 1 ??.
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??????. ????? ?????????? ? ???? ???????? ????????? 13 ?? ??????? ???????? ?? ?????????????? ?????. ????? ???? ?? ?????????? ???????????? ?????? ??????? ? ????????? ????????????. ? ???????? ??????????? ???????????? ???????????? ??????? LiBr ? ????????????????
(?4?8?).
???????????? ????????????? ????????? ? ???????? ????????? ??????? ???? ?? ???????????? SPECS ????? SPECS Gmbh.
????????? ?????????????? ???? ???????? ? ??????? ??????????? ??-1109, ? ???????????? ?? ?????????? ±(0,0015·U??? + 1 ?.?.?.) ? ?? ???? ±(0,002·I??? + 10 ?.?.?.).
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t
Q і Idt ,
0
(1)
??? Q ? ??????? ????????????, I ? ??? ???????, t ? ????? ???????.
????????? ?????????????? ???????????? ? ?????? ?? ????????-???????? ?????? ???????????? ?? ???. 2. ??? ?????? ??????? ???????? ???? ????? ??????, ? ??? ??????????? ???????? ??????????????? ? ?? ???????? ??????????? ?? ???????????. ??????????? ?????????? ??????? ? ???????? ??????????????. ??? ????????? ?? ??????? ??????????? ????????
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????????? ??? ????????? ????? ? ??????? ???????.
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?.?. ???????, ?.?. ??????? ????????? ??????????? ??????? ?? ????? ????? ?????????? ? ????????-?????????
?
?
???. 6. ?????????? ???????? ??????????? ???????? ?????????? ???????? ?? (?) ? ????? (?) ??????-???????
????????????. ????? ?? ??????? ????????? ?????????????? ??????????
?
?
???. 7. ?????????? ???????? ??????????? ???????? ???????? ?????????????? ??????? ?? (?) ? ????? (?)
??????-??????? ????????????. ????? ?? ??????? ????????? ?????????????? ??????????
????????????? ???????? ??????????? ???????? ? ??? ? ? ?????? ?????? ?????????. ?????????? ?? ????????? ?????????? ?? ??? ???????????? ? ?????? ?????????????? ???????????.
???? ?????????, ??? ??????? ????????????? ????????? ?? ?????????????? ??????? ??????
????????? ????????, ?? ?????? ???????????? ????? ???? ????????? ?? ??????? ?????? [10]:
' 2T (rad ) O / ( D cos T 0 ),
(2)
??? ?2? ? ?????? ?????????????? ???? (???), ? ? ????? ????? ?????????????? ????????? (Е),
? 0 ? ???? ????????? (????), D ? ?????? ????????????, ???????????? ???????.
??? ??? ???????????, ???? ????? ??? ????????? ?????????? ???? ?????????? ???????
? ????????????? ????? ????, ??????? ??????????? ????????????? ????????, ??? ???????? ?
?????????? ?????????? ??????. ??? ?????????????? ??????????? ???????? ???????????? ?
?????????????? ??????? ? ??????? ?????????????? ??????????? 3,36 Е ?? 13,57 Е.
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??????? 1. ?????????? ??????? ????????? ???????? ????????????
?????????????? ?????????
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????????????? ??????
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? 3,36
? 3,38
? 3,36
? 3,41
?????? ???????????? ????????? ??????, Е
49,87
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?????? ???????????? ??????? ????? ????????
??????????????, Е
36,3
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16,34
??????????? ??????????????? ?????? ???????? ??????????, ??? ? ???????? ?????????????? ?????????? ???????? ???????????? ??????????? ?????????. ????? ????????? ?
????????? ?????????????? ??????? ?? ???????????. ??????? ????? ?????? ? ????????????
??? ?????????, ??? ? ????????? ?????????? ?????????????? ??????? ? ???????? ??????????????.
??????
????????, ??? ?????? ????????-????? ? ??????? ?????-??????? ???????????? ????????
???????? ???????? 221 ??·?/?, ??? ????? ? 1,5 ?????? ?????????????? ???????? ??? ???????.
??????? ???? ???????????, ??? ??????? ????????? ???? ? ?? ?? ????? 1 ???. ??????????
???????? ???????? ??????? ??? ?????? ??????? ????????? ????, ??????? ????????? 224 ??·?/?.
?? ???????????? ????????? ?????????????? ??????? ? ???????? ????????? ????? ????? ?
??????? ??????? ????????? ??????? ??????????? ?? 0,06 Е ?????????????? ??????????
?? ????????? ? ?????????????? ????????. ??????????????? ???????????? ????????, ???
?????????????? ? ?????????????? ??????????????? ??????? ? ???????????? ??????????????
??????? ? ??????????? ????????? ? ?????? ?????? ? ????????????? ? ?? ??????.
?????? ????????? ??? ????????? ????????? ??? «??????? ? ??????-??????????????
????? ????????????? ??????» ?? 2009-2013 ???? (?????? ? 2012-1.2.2-12-000-2003-015;
?????? ? 2012-1.2.1-12-000-2004-2205) ? ???? ? 12-03-31439, ?????? ???????????????
???????????? ??? ???????? ? ?? ??? ? 24.
?????? ??????????
1. ?? ?. ?????????? ???????? ??????? ???????? ??????????? ?????? ??? ???????? ????????????? [??????????? ??????]: ???????? ??????: ??????? ?????????? ?????. URL: http://
www.chemport.ru/datenews.php?news=1336 (???? ????????? 01.12.2011).
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5. ???????? ?.?., ?????? ?.?., ??????? ?.?., ?????????? ?.?., ??????? ?.?. // ?????? ?
???. 2003. ?. 29. ?. 22. ? 23-28.
# 216 #
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?.?. ???????, ?.?. ??????? ????????? ??????????? ??????? ?? ????? ????? ?????????? ? ????????-?????????
6. ????? ?.?., ??????????? ?.?., ???????????? ?.?. // ?????????? ??????????. 2010. ? 27.
?. 28-32.
7. Ricco M., Belli M., Mazzani M., Pontiroli D.//Phys. Rev. Lett. 2009. Vol. 102.
8. ??????? ?.?. ?????????? ?????? ?????????? // ??????? ? ??????? ????????????. 2000.
?1. ?. 5-15.
9. ?????? ?.?., ?????????? ?.?., ??????? ?.?. ??????????? ???????? ??? ????????????
????? ? ??????: ??????????? ????????? ?????? // ????????????. 2008. ?. 44. ?. 602-608.
10. ????? ?. ?????????????? ??????????. ?????? ? ????????. ?.: ?????????, 1961. 326 ?.
Comparison of the Sorption Capacitance
of Ion-Lithium Graphite,
Fullerene-Lithium Anode
Taisia A. Leonovaa,
?leksander I. Dudnikb, Natalia G. Vnukovaa,b,c,
Irina V. Osipovaa,b, Gari A. Glushenkob,c,
Evgenie V. Tomashevichd and Grigory N. Churilova,b,c
a
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Institute of Physics SB RAS
50 Akademgorodok, Krasnojarsk, 660036 Russia
c
Krasnoyarsk State Pedagogical University named after V. P. Astafiev
89 Adi Lebedevoi Str., Krasnoyarsk, 660049 Russia
d
Institute of Chemistry and Chemical Technology SB RAS
50/24 Akademgorodok, Krasnojarsk, 660036 Russia
The comparative analysis of the lithium-ion batteries discharge characteristics was carried out. The
negative electrodes were produced from composite film fulleride-lithium, plates of hexagonal graphite
and plates of turbostratic graphite. The metallic lithium plates were used as positive electrodes in all
considered batteries. It was shown that the maximum value of discharge current was achieved with
using turbostratic graphite as anode. The active layer of lithium ion intercalations in turbostratic
graphite was 600 nm according to X-ray photoelectron spectroscopy results. For the active area the
average specific capacitance was 244 mA · h / g, while for the film of fullerene-Li ? 221 mA · h / g. By
X-ray analysis it was determined that structure of turbostratic graphite was stable during recycling,
when the hexagonal graphite was destroyed.
Keywords: lithium-ion battery, fulleride-lithium, turbostratic graphite, specific capacitance.
???? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
7. Colombo I., Grassi G., Grassi M. Drug mechanochemical activation // Journal of Pharmaceutical
Sciences. 1998. V. 98. ? 5. P. 3961-3986.
8. ?????????? ?.?., ??????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?.,
???????? ?.?. ??????? ???????????? ????????? ?? ???????? ???????? ? ?? ????? ? ???????????????? ?????????? // ????? ????????? ??????????. 2011. ?2. ?.211-214.
9. ??????????? ?. ?., ????????? ?. ?., ?????????? ?. ?., ????? ?. ?., ????????? ?. ?.,
???????? ?. ?. ????????? ??????????? ?????????? ???????? ? ????????????????????? ?
?????????????????? // ?????? ?????????? ???????????? ????????????. ?????. 2012. ?.5, ? 1.
?. 52-60.
10. ????????? ?. ?., ?????? ?. ?., ?????????? ?.?. ??????????????? ??????????? ?
???????? ? ??????????? ????????????? (?????) // ????? ????????????? ?????. 2003. ? 1.
?. 7-37.
11. ???????? ?.?., ?????? ?.?., ?????????? ?.?., ????????? ?.?., ??????? ?.?., ?????????
?.?., ???????? ?.?., ?????? ?.?. ???????????????? ????????? ? ????????????????? ?????????? ??????????????? ?????????? ???????????????? ? ????????????? ??????? // ????????
???, ????? ??????????. 2008. ?6. ?. 1274?1282.
12. ?????? ?? ? 2337710. ??????????????? ????????????? ?????????? ? ?????? ?? ????????? / ?????? ?.?., ?????????? ?.?., ????????? ?.?., ???????? ?.?. 2008. ???. 31.
13. ????????? ?.?., ???????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?., ??????
?.?., ?????????? ?.?., ??????? ?.?., ?????? ?.?. ??????????? ??????????? ???????????????? ?? ??????????? ????????? ??? ???????????????? ????????? ? ????????????? ????????
????????? // ????? ????????????? ?????. 2009. ?3. ?. 49?56.
14. ?????? ?? ? 2324700. ?????? ????????? ????????? ?????????? / ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?. 2008. ???. ? 14.
15. ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?. ?????? ????????? ????????????????// ?????? ?? ? 2273646. 2006. ???. ? 10.
16. Boldyrev V.V. Mechanochemistry and mechanical activation// Materials Science Forum.1996.
Vols. 225-227. P. 511 520.
17. Zamay A. S., Zamay T. N. Change in Physicochemical Parameters of Membranes of Ehrlich
Ascite Adenocarcinoma in the Course of Tumor Growth // Doklady Biochemistry and Biophysics.
2005. Vol. 402. P. 197?199.
18. Liu Z.M., Chen G.G., Vlantis A.C., Tse G.M., Shum C.K., van Hasselt C.A. Calcium-mediated
activation of PI3K and p53 leads to apoptosis in thyroid carcinoma cells // Cellular and Molecular Life
Sciences. 2007. Vol. 64, ? 11. P. 1428-1426.
19. Clapham D.E. Calcium Signaling // Cell. 2007. Vol. 131, ? 6. P. 1047?1058.
20. Neher E., Sakaba T. Multiple roles of calcium ions in the regulation of neurotransmitter release
// Neuron. 2008. Vol. 59, ? 6. P. 861-872.
21. ????? ?.?., ????? ?.?. ??????? ??? ?? ???????????? ???????? ??????? ? ????????
??????? ????????? ?????? ? ???????? ?? ????? // ????????. 2006. ?. 71, ? 10. ?. 1347-1353.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ???????????? ?????????????? ????????? ???????? ? ??? ????????????????? ??????????
The Mechanocomposite of Betulin Diacetate
and its Antitumor Activity
Svetlana A. Kuznetsovaa,b, Tatyana P. Shakhtshneiderc,d,
Mikhail A. Mikhailenkoc,d, Yuriy N. Malyara,
Anna S. Zamaya,e and Vladimir V. Boldyrevc,d
a
Institute of Chemistry and Chemical Technology SB RAS
50/24, Akademgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk,660041 Russia
c
Institute of Solid State Chemistry and Mechanochemistry SB RAS
18 Kutateladze St., Novosibirsk, 630128 Russia
d
Research and Educational Center ?Molecular Design
and Ecologically Safe Technologies?
2 Pirogov St., Ch. Building, 125, Novosibirsk, 630090 Russia
e
Krasnoyarsk State Medical University
named after Professor V.F. Voyno-Yasenetsky,
1 Partizan Jeleznyak St., Krasnoyarsk, 660022 Russia
Using gel-penetrating chromatography, it has been shown that mechanochemical treatment of a
mixture of arabinogalactan (AG) with betulin diacetate (DAB) in a ball mill led to change of the
molecular weight distribution (MWD) of AG. The presence of DAB in the mixture promoted restoration
of MWD after dissolving the mechanically activated mixture in water and solvent evaporation. The
formation of intermolecular complex DAB with AG at dissolution of initial and mechanically activated
mixtures in water was suggested. It was shown that the mechanocomposites DAB with AG had the
ability to induce cells in ascites Ehrlich carcinoma cell elimination processes mediated disturbance
of ion homeostasis.
Keywords: betulin diacetate, arabinogalactan, mechanochemical treatment, dissolution, gelpenetrating chromatography, antitumor properties.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 203-209
~~~
??? 541.49+546.92+539.26
?????? ? ??????-?????????? ????????????
?????????????? ??????????
?????-????????????????????(II)
?.?. ???????*, ?.?. ???????????
???????? ????? ? ?????????? ?????????? ?? ???
?????? 660049, ??????????, ??. ?. ??????, 42
Received 05.12.2012, received in revised form 16.01.2013, accepted 03.02.2013
??????? ????? ??????? ??????? ? ????????? ??????-?????????? ???????? ??????????????
?????????? ?????-?????????????????????(II) ? ???????? ?????-[PtLL`Cl2], ??? L, L` =
?????????, ???????? ? ?????????????. ??? ??????????? 20 °? ? ???????? 0,5 ? KCl ???????
?? ?????????????. ??? ?????????????? ????????????????, ???????? ? ??????????????
??????-?????????? ??????? ?????????????? ?????????? ???????????? ?????? ???????????
???????, ???, ???, ????????????????, ??-?????????????????.
???????? ?????: ??????????? ?????????? ???????, ??????, ??????-?????????? ????????,
?????.
???????? ???-??????? ???-[Pt(NH3)2Cl2] ???????? ????????????? ??????????? [1]. ?? ???????? ? ??????? ?????????? ???????????. ??? ????? ???? ??????? ??????? ????????. ???
?????????? ?????? ???? ?? ????? ?????? ???????????? ? ???????? ?????????????????? ????????? [2]. ????? ?? ?????? ??????? ??? ??????? ????????????????? ?????????? ???- ?
?????-????????????????????(II) ???????? ???????? ? ???????????? ??????????????? ???
????????? ????????? ???? ??????????: ???????? ????????? ???-??????? ??????????? ??????
???????? ????????? ?????-???????, ????????? ???? ???-?????? ???????? ????? ? ??????????
???? ?? ??????? ???, ? ?????-?????? ???????? ? ??????? ? ???????????? ???????????? ???????? ? ??????????????, ?????????? ? ??. ???????? ????????? ????? ???????????? ??????
? ???????, ??????? ???????? ???????????? ??? ??? ???-, ??? ? ??? ?????-???????? ??????????? ?????????? ???????(II) [3,4].
????????????? ??????????????, ??? ????????? ?????-?????? ?????????? ??????? ???[Pt(NH3)2Cl2] ?? ???????, ?? ? ??? ?????????? ????????? ?????-???????????? ????? ?? ???????? ????????????????? ?????????? [5, 6]. ?? ?????? ??????????, ??? ????????? ????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: kaz@icct.ru
# 203 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
NH3 ? ?????-[Pt(NH3)2Cl2] ?? ?????? ????? ???? ?????????? ?????-[PtLL1Cl2], ??????? ?????
???????? ???????????????? ? ????????????? ?????? ???? ?? ???????, ??? ? ???-[Pt(NH3)2Cl2]
[7]. ????????????????? ?????????? ??????????? ?????????? ???????(II) ?????-????????????
????? ?????????? ?? ???? ????????? ???????? ?????????? ??????? ????????, ??????? ?????
????????? ???????? ????????? ????????? ???????? ? ?????????? ???????. ???????? ????????, ???????????????? ? ?????? ???????, ????????? ???????????? ????????? ????????????????? ?????????? ???? ?????????? [8, 9].
?????????? ????????? ?????-???????????? ??-???????? ???????????? ??????? ??????? ? ?????????????? ????????????? ????? ?????????? ?????????????? ??????????,
????????? ?????????? ???????????? ??????????? ??? ???-???????. ??????? ????????
??????-??????????? ???????? ????? ?? ?????????, ??????????????? ?? ????????? ????????
? ?????? ??????????, ????????? ?????? ? ????????????? ?????????????? ?????????? ????????????????? ?? ????? ???????.
????????????????? ?????
??? ????????? ??????????? ?????????? ?????-???????????? ???????? ????????? ???????????????? ????? L ?? ???? ???-[Pt(L)2Cl2] ? ????? L` c ???????????? ??????????? ?????????? ???????(II) ? ??????????? ???????????? ?? ? ??????? ??????? ? ???????? ?????????.
???-[Pt(L)2Cl2] + 2 L` = [Pt(L)2 (L`)2]Cl2
[Pt(L)2 (L`)2]Cl2 + 2HCl = ?????-[PtLL`Cl2] + L·HCl + L`·HCl , ??? L,L` = CH3NH2, ?2H5NH2, i-C3H7NH2.
?????? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2]. ? 1,5 ? ???-[Pt(i-C3H7NH2)2Cl2] (3,9·10 -3 ???) ????????? 0,52 ? CH3NH2·HCl (7,8·10 -3 ???) ? 15 ?? H2O. ????? ? ???????? ???? ????? ??? ?????????
??????????? ?????????? 1,5 ?? CH3NH2 ? ????????? ??? 40 °?, ???? ??????? ?? ????????????.
??????? ????????? ? ???????????????. ????????? 15 ?? ??????? ??????? 12? ? ????????? ?? ?????? ? ???????? ????????? ? ??????? 8 ?. ?????????? ?????? ??????? ?????????,
???????? ?????? ???????????????, ????????? ??????? ? ??????. ?????????? ???????????
????????? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2] ? 1,02 ?, ??? ????????? 82 % ?? ??????????????.
?????????? ??????????? ??????? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2]
?????????, %
Pt
N
C
H
Cl
54,77 7,86
13,49 3,96
19,91
???????, %
54,79 7,75
13,58 3,80
20,06
?????? ?????-[Pt(CH3NH2)(?2H5NH2)Cl2] ? 2 ? ???-[Pt(?2H5NH2)2Cl2] (5,6·10-3 ???) ?????????
0,756 ? CH3NH2·HCl (1,12·10-3 ???) ? 15 ?? H2O. ????? ? ???????? ???? ????? ??? ????????? ??????????? ?????????? 2 ?? CH3NH2 ? ????????? ??? 40 °?, ???? ??????? ?? ????????????. ???????
????????? ? ???????????????. ????????? 15 ?? ????????????????? ??????? ??????? ? ????????? ?? ?????? ? ???????? ????????? ? ??????? 8 ?. ?????????? ?????? ??????? ?????????,
???????? ?????? ???????????????, ????????? ??????? ? ??????. ?????????? ???????????
????????? ?????-[Pt(CH3NH2)(?2H5NH2)Cl2] 1,50 ?, ??? ????????? 78 % ?? ??????????????.
?????????? ??????????? ??????? ?????-[Pt(CH3NH2)(?2H5NH2)Cl2]
?????????, %
Pt
N
C
H
Cl
57,02 8,19
10,53 3,83
20,72
???????, %
57,07 8,30
10,67 4,00
21,00
# 204 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
?????? ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2] ????? ??? ????? ?? ????????, ??? ? ?????? ????
?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2], ?????? ? 1,5 ? ???-[Pt(i-C3H7NH2)2Cl2] (3,9·10 -3 ???) ?????????
0,64 ? C2H5NH2·HCl (7,9·10 -3 ???) ? 15 ?? H2O. ????? ? ???????? ???? ????? ??? ????????? ??????????? ?????????? 2 ?? ???????? ????????? ? ????????? ??? 40 °?, ???? ??????? ?? ????????????. ? ???????????? ???????? ?? ?????? ??????????? ????????? 15 ?? ?????????????????
??????? ???????. ?????? ??????-??????? ?????. ????? 1,15 ?, ??? 80 % ?? ??????????????.
?????????? ??????????? ??????? ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2]
?????????, %
Pt
N
C
H
Cl
52,70 7,57
16,22 4,35
19,15
???????, %
52,90 7,40
16,01 4,63
20,00
?? ???? ??????? ?????? ?? ??????? ????????? ??????? ????????. ??????? ????????? ?????????? ?? 50 ?? 100 ??. ????, ???????, ??????? ?????????? ?? ?????????? ????????????????
«NC Soil Analysez FLASH EA 112 Series». ????? ??????? ?????????? 5-8 ??. ?????????? ?????
?????????? ??????? ???????? ? ??????????? ??????????????????? ??????????? ????????? ????????????? ???????.
?????????? ?????????????? ?????????????? ?? ????????????? ??pert Pro (PANalytical,
??????????) ? ?????????? ?? ??????-????????, ?????????? ????????????????? ??????????
PIXel ? ?????????? ??????????????. ???????????? CuK?-?????????. ???????? ?????? ??
10 ?? 90° ? ????? 0,026°.
??????????? ?????????? ???????? ?? ??????? NET2SCH STA 449 ? ? ???????????? ???
????????? ????? ? ????????? ?????????. ?????????? ????????? ? ????????? ?????????? ??
20 ?? 1000 °? ?? ????????? 10 °? ? ??????. ????? ??????? ?????????? ?????????? 10 ??.
??-??????? ?????????? ?????????????? ? ??????? 4000 ? 400 ??-1 ? ????????? KBr ?? ??????? ??-????? ??????????? «Vector-22».
??????????? ??????? ?????????? ??????? ?? ???????????????? «Specord UV-VIS». ????????? ????????? ???????????? ???????? ? ??????? 28 000?46 000 ??-1.
?????????????
??????????????
???????????
??????????
?????-????????????????????(II) ??????? ??? t = 20 °? ? 0,5 ? KCl (??? ?????????? ?????????). ??? ??????? ?????????? ????????? ?? 10 ??????. ????? ??????? ??????????? ?? 0,002 ?? 1 ?. ?? ?????????? ? 100 ?? 0,5 ? KCl ? ???????????????? ??? t = 20 °?. ????? ???? ???????????? ?????
??????????? ??????. ????? ?????????? ??????-?????????? ???????? ????????? ??????????
?????? ???????????????, ???????? ?? ????????? ???????? ??????? ? ?????? ??? ?????????
???????????.
?????????? ? ??????????
????????????? ????? ??????? ??????? ?????????????? ??????????? ??????????
???????(II) ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2, ??????????? ? ??????
??????, ????????? ???????? ???????? ???????? ? ??????? ??????? ? ????????.
?????????? ??????????? ???????, ???, ??-?????????????, ??-????????????????? ???????????? ?????????? ???????????????? ? ??????? ??????????? ???????.
??????????????????? ???????????? ????????? ?????????? ??? ???????????? ??????,
?????? ????????? ? ????????? ???????????? ??????.
# 205 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
??? ?????????? ?????-[Pt(CH3NH2)i-(C3H7NH2)Cl2] ? ???????????? ??????????? ?????? ?
??????? ????????? ?21 ? = 28,439(3)?, ? = 6,057(2)?, ? = 6,055(3)?, ? = 93,59(2)°, V = 1041.28 ?3,
Z = 4.
??? ?????????? ?????-[Pt(CH3NH2)(C2H5NH2)Cl2] ? ???????????? ??????????? ?????? ?
??????? ????????? ?21/? ? = 11,761(3)?, ? = 12,690(3)?, ? = 17,080(2)?, ? = 90,43(3)°, V = 440.63
?3, Z = 2.
??? ?????????? ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2] ? ???????????? ??????????? ??????
? ??????? ????????? ?21/? ? = 18,094(2)?, ? = 6,633(2)?, ? = 9,345(3)?, ? = 90,72(3)°, V = 1121.38
?3, Z = 4.
????????? ??-?????????????????? ???????????? ????? ?????-[PtLL`Cl2], ??? L, L` ?
?H3NH2, ?2H5NH2 , i-C3H7NH2, ??????? ????????? ?????? ?????????? ?? ????????? ?????????
?????? [10-13]. ?????????? ????????? ? ????. 1.
???????? ??????????? ???????????? ????? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2,
i-C3H7NH2 ? ????????? ?????????? ?? 20 ?? 1000 °? ????????, ??? ??????? ?????????? ?????????? ??? ??????????? t1 ? ????????????? ??? t4. ??? ???? ??????????? ?????????? ?? ??????
??? ??????? ??? ??????????????? ??????? t1 ? t3. ???????? ?????? ????-???????? ?????????
????? ??? ??????????? t1 ?????????? ????? ??????, ? ??? ??????????? t2 ? ?? ??????????. ???
??????????? t3 ?????????? ????? ????-?????, ?????????? ????????????? ???????????? ????????????? ??????? ??? t4. ?? ?????? ?? ?????????? ?????? ?????, ??? ????????? ???????????
?? ????????????? ???????. ?????? ???????????? ??????? ????????? ? ????. 2.
??-?????????????????????? ???????????? ??????????? ?????????? ?????-[PtLL`Cl2],
??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2, ????????? ???????. ?????? ??????????? ?????????
???????????? ?????????? ?? ????? ????? ??? ?????????????? ??????????? ??????????
???????(II) ?????-???????????? ????????? ? ????. 3 ? ???????????? ??? ???????? ????????????? ???? ??????????.
??? ???????? ????????????? ??? ??????? ????????? ???? ????? ?? 10 ??????? ??????
?????, ?????????? ? 100 ?? 0,5 ? KCl ? ???????????????? ??? 20 °?. ????? ??????????
??????? 1. ????????? ????????????? ?????? (??-1)
[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2
?????????, ??-1
? (NH)
? (CH)
? (NH2)
? (CH3)
? (CH2)
? (NH2)
? (CN)
? (CH3)
? (NH2)
? (PtN)
?????-[Pt(CH3NH2)
(i-C3H7NH2)Cl2]
3266, 3238, 3218, 3144
3004, 2970, 2934
1590
1456, 1411
1393, 1338
1272, 1247
1038
998
745
518
? ??-???????? ?????????? ?????????? ??????????-[Pt(CH3NH2)
(C2H5NH2)Cl2]
3263, 3226, 3152
2983, 2937, 2888
1590
1452, 1410
1384, 1352
1271, 1240
1037
994
740
513
# 206 #
?????-[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
3251, 3220, 3144
2973, 2930, 2874
1587
1467, 1393
1347, 1324
1236
1037
940
751
520
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
??????? 2. ?????? ???????????? ??????? ?????????? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 ,
i-C3H7NH2
??????????
???????, %
????
??????
?????, %
??????????? ????????????? ?????, °?
t1
t2
45.21
190
42,98
222
198
????.
????.
(?H3NH2) (i-C3H7NH2)
54.79
54.77
(?H3NH2) (?2H5NH2)
57.02
57.07
(?2H5NH2) (i-C3H7NH2)
52.90
52.70
47.10
t3
t4
264
278
290
272
286
307
269
273
292
??????? 3. ???????? ???????????? ?????????? ?(????-1 ·? · ??-1) ?????????? ?????-[Pt(CH3NH2)
(i-C3H7NH2)Cl2], ?????-[Pt(CH3NH2)(C2H5NH2)Cl2], ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2]
? · 103, ??-1
?????-[Pt(CH3NH2)
(i-C3H7NH2)Cl2]
?, ?/(???? · ??)
?????-[Pt(CH3NH2)
(C2H5NH2)Cl2]
?, ?/(???? · ??)
?????-[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
?, ?/(???? · ??)
41
164
165
185
40
79
76
100
39
80
73
95
38
110
101
119
37
120
112
131
36
112
98
121
35
91
75
101
34
73
63
87
33
74
67
88
32
79
76
93
31
70
66
84
30
44
42
60
29
33
30
49
28
29
28
43
??????-?????????? ???????? ?????????, ? ??????? ?????????? ?????? ???? ? ???????????
??????? ?????????? ????????? ???????? ?????????? ???????????, ?????? ??????????????? ?
???????????. ??? ???? ?????-[Pt(CH3NH2)i-(C3H7NH2)Cl2] ????? ?????? ??????? ?? ??????????
????????? 5 ???, ??? ???? ?????-[Pt(CH3NH2)(C2H5NH2)Cl2] ? 4 ???, ? ??? ?????-[Pt(C2H5NH2)
(i-C3H7NH2)Cl2] ? 7 ???. ???????????? ??????? ?Pt ? ????/? ? ???????? ???????????? ?? ?????? ??-???????? ??????????, ?????? ??? ?????????? ? ?????? ??-???????? ?????????????? ?????????? ?????-[PtLL`Cl2], ??? L, L` ?H3NH2 , ?2H5NH2 , i-C3H7NH2 , ? ????? ?? ????????
????? ????????? ???????? ??????? ? ??????????????? ?????? ?????.
???????????? ?????? ???? ? ???????? ??????????? ?????????? ???????(II) ???????????????? ???????? ?? ??????? ? ??????????????????? ????????. ?????? ?? ?????????????
??? ???? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2 , i-C3H7NH2, ? ?????? ?????? ????????? ? ????. 4.
# 207 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
??????? 4. ?????? ?? ????????????? ??? ?????-[Pt(CH3NH2)(i-C3H7NH2)Cl2], ?????-[Pt(CH3NH2)(C2H5NH2)
Cl2], ?????-[Pt(C2H5NH2)(i-C3H7NH2)Cl2]
????????
????????
?????[Pt(CH3NH2)
(i-C3H7NH2)Cl2]
?????[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
?????[Pt(C2H5NH2)
(i-C3H7NH2)Cl2]
?????????????,
?????
?????????????,
???????? ?
????????????
????????? ??
???????? ?????
?? ??????? ??????
?????????
????????,
????, ????/?
?????? ????, ?
????/?
??????????
??????? ?
????????
?????????, %
??????????
??????? ?
?????? ???? ,
%
54,79
54,65
0,189 ± 0,002
5,30·10 -3 ±
0,05·10 -3
5,25·10 -3 ±
0,03·10 -3
57,02
57,10
0,197 ± 0,003
5,75·10 -3 ±
0,03·10 -3
5,70·10 -3 ±
0,05·10 -3
52,70
52,60
0,028 ± 0,004
7,56·10 -4 ±
0,04·10 -4
7,50·10 -4 ±
0,06·10 -4
????????? ????????, ??? ????????????? ?????-[PtLL`Cl2], ??? L, L` ? ?H3NH2 , ?2H5NH2,
i-C3H7NH2, ????, ?????? ????????????? ??????????? ????????? ?????????? [14]. ??????? ?
????????? ???????? ?????? ???????? ?????????????? ??????????, ??? ???????? ?? ?????????????.
??????
????? ???????, ????????????? ? ?????????? ??????????????? ???????????? ???????????
?????????? ???????(II) ????? ???????? ??????? ?????????????? ??????????? ??????????
?????-????????????????????(II) ????????? ???????? ??? ?????????? ? ??????? ??????? ?
????????. ???????? ?? ????????????????? ? ???????? ?????????? ??????? ???????????? ?
??????? ???, ???, ???????????????? ? ??-?????????????????. ????????? ?????? ?? ??????????? ???????????? ?????????? ? ?? ????????????? ????? ???? ??????? ??? ????????????? ????????????????? ?????????? ?? ???? ??????????? ?????????? ???????(II).
?????? ??????????
1. Rosenberg.W., Van Camp.L., Trosko.J.S., Mansuor V.N. Platinum compounds: A new class of
potent antitumor agent// Nature. 1969. V. 222. P. 385-386.
2. Pil P., Lippard S.J., Bertino J.R. Leaning from the past teaching old platinum compounds new
tricks // Encyclopedia of Cancer. Ed. Academic Press: San Diego CA. 1997. V. 1. P. 392-410.
3. Faggiani R., Lippert B., Lock C.J.L.and Rosenberg B. Hydroxo-Bridged Platinum(II) Complexes.
3. Bis[cyclo-tri-?-hydroxo-tris(cis-diammineplatinum(II)] Trisulfate Hexahydrate. Crystallographic
Characterization and Vibrational Spectra // Inorgan. Chem. 1978. V. 17. ? 7. P. 1941-1945.
4. Bignozzi C.A., Bartpcci C., Maldotti A.and Carassiti V. Photochemistry of Dimeric and
Trimeric Hydroxo-bridget Diammine Platinum(II) Complexes in Aqueous Solution // Inorg. Chim.
Acta. 1982. V. 62. P. 187-191.
5. Clear M.J. Transition Metal Complexes in Cancer Chemotherapy // Coordination Chem. Rev.
1974. V. 12. P. 349.
# 208 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ???????????. ?????? ? ??????-?????????? ???????????? ??-???????????? ???????????
6. Clear M.J., Hoeshele J.H. Studies on the Antitumor cyticity of Group VIII Transition Metal
Complexes Part I. Platinum(II) Complexes // Bioinorganic Chemistry. 1973. V. 2. P. 187.
7. Cubo L., Quiroga A.G., Junyong Zhang, Thomas D.S., Carnero A., Navarro-Ranninger
C.and Berners-Price S.J. Influence of amine ligands on the aquation and cytotoxicity of trans-diamine
platinum(II) anticancer complexes // J. Chem. Soc., Dalton. Trans., 2009. P. 3457-3466.
8. Quiroga A.G., Perez J.M., Alonso C.et al. Novel trans-platinum(II) complexes with N2O2
donor sets // J. Med. Chem. 2006. V. 49. ? 1. P. 224.
9. Ramos-Lima F.J., Quiroga A.G., Garcia-Serrede B.et al. New trans-platinum drugs with
phosphines and amines as carrier ligands induce apoptosis in tumor cells resistant to cisplatin // J.
Med. Chem. 2007. V. 50. ? 9. P. 224.
10. Watt G.W., Hutchinson B.B., Kett D.S. The Infrared Spectra and Structure of Methylamine
Complexes of platinum(II) // J. Amer. Chem. Soc. 1967. V. 89. ? 9. ?. 2007.
11. Arpalahti J., Lippert B., Schollhorn H., Thewalt U. Crystal Structures of Two Pt(II) Diamine
Compounds: trans-Pt(CH3NH2)2Cl2 and cis- Pt(CH3NH2)2Cl2 // Inorg. Chim. Acta. 1988. V. 153. P. 45.
12. ????????? ?.?., ?????? ?.?., ??????? ?.?. ??-??????? ?????????? ??????????????
???????? [Pt(CH3NH2)2Cl2] // ????. ?? ????. 1967. ?. 173. ?. 1113.
13. ????????? ?.?., ?????? ?.?., ??????? ?.?. ??-??????? ?????????????? ????????
[Pt(C2H5NH2)2Cl2] // ????. ???????. ?????. 1969. ?. 14. ? 1. ?. 227.
14. ??????? ?.?., ??????????? ?.?. C????? ? ??????-?????????? ???????????? ?????????? ?????-??????????-(????)???????(II) // ?????? ???. ?????. 2011. ???.4. ?. 377-383.
The Synthesis and Physico-Chemical Studies
of Nonsymmetric Complexes
Trans-Dichlorodiaminplatinum(II)
Alexander K. Starkov and Galina A. Kozuchovskaya
Institute of Chemistry and Chemical Technology,
Siberian Branch of the Russian Academy of Sciences
42, K. Marx Str., Krasnoyarsk, 660049 Russia
The new methods of synthesis and some physico-chemical properties of nonsymmetric ?omplexes
trans-dichlorodiaminplatinum(II) with the formula trans-[PtLL`Cl2], where L,L` = methylamine,
ethylamine, and isopropylamine were described. These methods allow increasing the yield and purity
of the substances. Their solubilites were studied at a temperature of 20° C in a solution of 0.5 M KCl.
To prove the identity, structure and characterization of physico-chemical properties of the complexes
the methods of elemental analysis, XRD, IR, thermogravimetric analysis, UV-spectrophotometry were
used.
Keywords: complex compounds of platinum, synthesis, physicochemical properties, amines.
# 209 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 2 (2013 6) 210-217
~~~
??? 621.355.2:546.34
????????? ??????????? ???????
?? ????? ????? ??????????
? ????????-???????? ??????
?.?. ????????*, ?.?. ???????, ?.?. ????????,?,?,
?.?. ????????,?, ?.?. ?????????,?,
?.?. ??????????, ?.?. ????????,?,?
?
????????? ??????????? ???????????
?????? 660036, ??????????, ??. ????. ??????????, 28
?
???????? ?????? ??. ?.?. ?????????? ?? ???
?????? 660036, ??????????, ?????????????, 50
?
??? ??? «???????????? ???????????????
?????????????? ??????????? ??. ?.?. ?????????»
?????? 660049, ??????????, ??. ?. ?????????, 89
?
???????? ????? ? ?????????? ?????????? ?? ???
?????? 660036, ??????????, ??. ?????????????, 50/24
Received 12.11.2012, received in revised form 22.01.2013, accepted 04.02.2013
???????? ????????????? ?????? ????????? ????????????? ?????-?????? ?????????????,
? ??????? ????????????? ????????? ??????????? ?? ??????????? ?????? ?????????????, ???????? ??????????????? ??????? ? ???????? ?????????????? ???????. ??
???? ????????????? ????????????? ?????????????? ??????????? ?????? ????????
?????????????? ?????. ???????????? ????????, ??? ???????????? ???????? ??????????
???? ??????????? ? ?????? ????????????? ?????????????? ??????? ? ???????? ?????. ??
??????????? ????????????? ??????????????? ????????????? ???????????, ??? ???????
????????? ???? ????????? ????? ????? ??? ?????????????? ??????? ?????????? 600 ??. ???
?????? ???????? ??????? ??????? ???????? ???????? ??????? ????????? 244 ??·?/?, ? ?? ?????
??? ??? ?????? ????????-????? ? 221 ??·?/?. ??????? ???????????????? ??????? ???????????,
??? ? ???????? ?????????????? ????????????? ?????? ????????? ???????????? ?????????,
? ?????????????? ?????? ???????????.
???????? ?????: ?????-?????? ????????????, ????????-?????, ????????????? ??????,
???????? ???????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: acbka1346@mail.ru
# 210 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ??????? ????????? ??????????? ??????? ?? ????? ????? ?????????? ? ????????-?????????
????????
?????-?????? ???????????? (???) ? ??????? ?????? ????? ??????? ???????? ???
???????????, ????????? ???????? ?????????? ???????? ??????????? ??????? (????????,
??????? ????????, ???????? ????- ? ???????????, ???????????? ??????????). ???????????? ??? ????? ??????? ??????????? ??????????? ???? ??????????? ? ?? ??????? ???????? ???????????????: ??????? 180?400 ?? · ?/??, ????????? ???? 0,1-100 ??/?? 2. ?????? ??
???? ???? ???????????? ????? ???????? ??????????? ?????????? ??????? ???. ???? ??
???????? ????????? ??????? ? ?????????? ???????? ??????????? ????????? ?????????, ??
??????????? ??????????, ????? ??? ??????? [1], ??????????? ?? ?????? Si [2], ?????? [3],
??? ?????????????? ??????????? ???? ????? ?? 400 % ? ?????????? ???????????. ????????????? ?????????? ?????????? ???????? ????????? ?????? ?? ????? ??? ?? 10 % ???
????????? ????? ?????. ? ?????? [4] ????????, ??? ?? ???????? ????????????????? ?????????????? ?????????? (????????????), ???????????? ??? ????????? ????? ????? ? ??????????
?????????, ???????????? ??????? ????????? ????????? ????????? ??????????? ????????. ?
??????????????? ??????? ?????????? ????? ???????? ??????????? ?????????? 3,35 Е, ???
????????? ????????? ? ??? ????? ????? (?????? ???? 0,68 Е). ?? ??? ????????? ???? ?????
?????????? ?????????? ???? ?? 0,376 Е, ??????? ???????? ?? ?????? ??????? ? ????????
?????????????? (500-1000) ?????????????. ????????, ??? ????????????? ?????? (??) ?????
?????????? ????? ?????? ?????? ?? 0,06 Е, ??? ? ??????????????? [5]. ???????????? ?????
????? ? ?? ????? ????????? ? ??????? ??????????? ?????????? ?????????, ??? ? ?????????????? ???????, ? ??????, ? ?????????? ?????? ?????-?????? ???????????? ??????????. ?
?? ????? ?????????? ?????? ????? ?????, ??? ???????? ?????????? ???????? ??????? ???
? ?????????? ?? ??.
????? ????, ??????? ????? ??????????? ??????????? ??????????? ? ????????, ??????? ? ??????? ???? ???????? ???????? ? ????????. ???????????? ?????? ??? ???????
????????? ???????? 8 ??????????????? 
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