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Патент USA US3094527

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June 18, 1963
N. F. STANLEY
3,094,517
PROCESS FOR TREATING A POLYSACCHARIDE 0F
smwzsus OF THE GIGARTINACEAE
AND SOLIERIACEAE FAMILIES
Filed Dec. 29, 1958
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H
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H
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H
OH
H
OH
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INVENTOR
NORMAN
F. STANLEY
av
W
ATTO R N EYS
United States Patent O?ce
3,094,517
Patented June 18, 1963
2
1
The gel-forming properties of the seaweed mucilages
whose improvement is the object of this invention involve
two distinct types of phenomena. One of these is that
involving the formation of an aqueous gel composed
essentially of the mucilaginous material and water. Other
materials may be present and may by their presence affect
certain properties of the gel, but in general are not es
sential to the formation of this type of gel. Gels of this
12 Claims. (Cl. 260—209)
type are thermally reversible, liquefying on heating and
This invention relates to certain valuable discoveries 10 regelling on cooling. Firm gels of this type may con
tain from about 0.5% to several percent of mucilaginous
in connection with the treatment of seaweeds which con
material, the amount used depending on the type and
tain mucilaginous materials of the type found in certain
quality of the mucilaginous material and on the gel
marine plants of the class Rhodophyceae, and in particu
strength desired. The tendency of the mucilaginous ma
lat of certain marine plants of the Gigartinaceae and
Solieriaceae families thereof, and of the mucilaginous 15 terial to form a gel of this type is principally controlled
3,094,517
PROCESS FOR TREATING A POLYSACCHARIDE
OF SEAWEEDS OF THE GIGARTINACEAE AND
SOLIERIACEAE FAMILIES
Norman F. Stanley, Rockland, Maine, assignor to Marine
Colloids, Inc, a corporation of Delaware
Filed Dec. 29, 1958, Ser. No. 783,173
by the cation or cations associated with the monoester
materials as contained in, or extracted from, said sea
weeds. Among these seaweeds one may mention as
sulfate groups present in the molecule of mucilaginous
material.
In the case of carrageenan, the mucilaginous material
typical Chondrus crispus (carrageen or Irish moss),
Gigartina stellata, Gigartina radula, Eucheuma striata,
and Eucheuma cottonii.
The novel procedures herein disclosed ‘as a part of this
invention result in the production from the aforesaid sea
weeds, or from mucilaginous materials extracted there
of Irish moss, if the cation so associated is sodium or
lithium, the carrageenan forms no gel whatsovere with
water. If the cation so associated is calcium, barium, or
mucilaginous materials possess gel-forming properties in
carrageenan will form aqueous gels of high strength, as
measured by the Bloom gelometer. The presence of a
strontium, the carrageenan will form aqueous gels of
low strength, as measured by the Bloom gelometer. If
from, of new and hitherto unknown mucilaginous ma
terials of a modified nature, such that these modi?ed 25 the cation so associated is potassium or ammonium, the
a degree not hitherto attained in mucilaginous materials
gel-forming cation together with a non-gel-forming cation
(e.g., potassium with sodium) imparts to the carrageenan
as known to exist in or to be prepared from the afore
said seaweeds by prior known methods.
These pro
cedures were originally based on the belief that the gel
30 an ‘intermediate degree of aqueous gel-forming ability.
forming properties characteristic of mucilaginous ma
terials of the type found in certain marine plants of the
On the other hand, two or more gel-forming cations (e.g.,
calcium and potassium) may act synergistically to impart
to the carrageenan a greater aqueous gel-forming ability
class Rhodophyceae are due to the nature and structural
arrangement of certain acid-functional groups known to 35 than would result from the presence of either cation with
out the other. Other factors which affect the ability of
be a part of the molecular structure of such mucilaginous
the mucilaginous material to form thermally reversible
aqueous gels are the degree of polymerization of the mu
cilaginous material and the structural relationship of the
tural features of the molecule of mucilaginous material.
It is my belief that these structural features, while not 40 monoester sulfate groups to the polysaccharide portion of
the molecule of mucilaginous material.
directly functional in producing gel formation, act to
The nature of the cation or cations associated with car
determine the nature and extent of the gelling phenomena
rageenan may be controlled:
induced by the aforesaid acid-functional groups. It may
(‘1) Through the method of extraction employed upon
be that the molecular structures of the mucilaginous ma
materials, and further that the stability and reactivity of
said acid-functional groups are in?uenced by other struc
terials as they naturally occur in, and are ordinarily ex
tracted from, the aforesaid seaweeds are such as to block
or sterically hinder the functional groups from reacting
the seaweed;
(2) By chemical treatment of the seaweed prior to the
extraction of the carrageenan; or
(3) By chemical treatment of the carrageenan subse
quent to its extraction from the seaweed.
Methods for accomplishing this control of the cation
occurring seaweed mucilages in accordance with the pro
cedures of this invention seemingly alters their molecular 50 content of seaweed extracts have hitherto been disclosed,
fully to produce the gel-forming effects of which they are
potentially capable.
Modi?cation of these naturally
structures in such a way as to relieve this blockage and/ or
are well known in the art, and are not per se claimed as a
part of this invention. Such alterations in the cation con
produce a polysaccharide structure inherently more fa
tent of carrageenan are fully reversible in the same sense
vorable to gel formation through reaction via the func
that the altered carrageenan may be further treated to
tional groups.
Seaweed mucilages as a class are of a polysaccharide 55 restore the cation composition of the original carrageenan,
and that this restoration fully regenerates the original car
nature. Seaweed mucilages of the type to which the prac
rageenan. It is to be concluded, therefore, that alter
tice of this invention is applicable are further character
ations in the cation content of the carrageenan ordinarily
ized by containing a relatively high percentage of sulfur,
are unattended by any change in the nature, number, or
in the range of about ?ve to about thirteen percent of the
dry mucilaginous material. This sulfur is known to be 60 fuctionality of the monoester sulfate groups themselves.
present therein as a monoester sulfate in which one
The presence of these groups and the mode whereby they
valence of the sulfate group is esteri?ed to the polysac
charide portion of the molecule of mucilaginous mater
ial, which the other valence is anionic in nature and thus
65
is available for association with a cation. The mono
ester sulfate groups constitute acid-functional portions
of the molecule of mucilaginous material. The nature of
the cation or cations associated with these monoester sul
fate groups is known to be a factor influencing the chemi
70
cal and physical characteristics of those seaweed muci
lages which contain said groups.
are attached to the polysaccharide portion of the molecule
of carrageenan thus constitute an essential and intrinsic
chemical characteristic of the carrageenan in the sense
that these groups are functional in bonding the cations
to the polysaccharide portion of the molecule of mucila
ginous material, irrespective of the cations involved.
The foregoing observations regarding the in?uence of
cations on the aqueous gel-forming ability of the car
rageenan of Irish moss, and ‘likewise those regarding
means of altering the cation content of carrageenan, also
3,094,517
4
apply mutatis mutandis to mucilaginous materials occur
ring in certain other seaweeds. Said mucilaginous mate
rials belong to the group characterized by a relatively
high content of monoester sulfate. It does not follow,
however, that all seaweed mucilages which contain much
monoester sulfate invariably will be gelled by certain
cations, and most notably by the potassium cation. It
is seemingly the case that the structural relationship be
tween the monoester sulfate groups and the polysaccha
fate groups attached to the polysaccharide chains of the
mucilaginous material are bonded by polyvalent cations
to anionic carboxyl or ester phosphate groups attached to
the polypeptide chains of the proteins. The resulting
protein-cation-polysaccharide compound is thus cross
linked and is highly disposed to gel formation. The poly
valent cation involved in the cross-linkages is calcium
which is furnished by the casein of the milk. This is
demonstrated by the observation that the formation and
ride portion of the molecule of mucilaginous material 10 strength of the milk gel is virtually independent of the
must be of the proper nature for aqueous gel formation
to occur. Likewise, it cannot be concluded that a high
monoester sulfate content is characteristic of all aqueous
cation or cations associated with the mucilaginous mate
rial. Thus a seaweed mucilage in which sodium is the
cation forms a gel with milk, although it will not gel with
gel-forming seaweed mucilages. Thus agar, the mucilagi
water.
nous material occurring in various seaweeds of the Geli
diaceae and Gracilariaceae families, is notable for its abil
same strength, as measured by the Bloom gelometer, as
Moreover, this gel will have substantially the
will be obtained under identical conditions using muci
laginous material containing potassium or any other
little monoester sulfate, and even this can be removed
cation. On the other hand, if the milk is treated, as with
without impairing the aqueous gel‘forming ability of the
a cation exchange resin, to replace the calcium and other
agar. Seemingly a different mechanism for gel formation 20 cations associated with the casein by sodium, the result~
is involved in the formation of aqueous agar gels, and
ing “sodium milk” cannot ordinarily be gelled by the
this must be distinguished from the aqueous gelling mech
mucilaginous material regardless of the cation associated
anism involved in the case of the high monoester sulfate
therewith. This is the case since at the low concentra
mucilages with which this invention is concerned.
tions ordinarily required of the mucilaginous material for
It is an object of this invention to provide methods for
milk gel formation the amount of cations contributed by
improving the ability of a certain class of mucilaginous
the mucilaginous material is small compared to that fur
materials, of the type derived from marine plants of the
nished by the milk. Hence, in so far as the gelling of
class Rhodophyceae, to form thermally reversible gels
milk by the mucilaginous material is controlled by the
with water. This improvement is effected through modi
cations present, those furnished by the milk predominate
?cation of the structural relationship of the monoester 30 in effecting this control. Likewise l have found that when
sulfate groups to the polysaccharide portion of the mole
the calcium and other cations associated with the casein
cule of mucilaginous material.
of milk are substantially all replaced by potassium, the
The class of mucilaginous materials to which this in
resulting "potassium milk” does not gel with the mucilagi
Vention applies is that comprising mucilaginous materials
nous material.
having monoester sulfate contents in the range of about 35
On the other hand, a milk wherein all of the potassium
normally present in natural milk has been replaced by
5% (as sulfur) to about 13% (as sulfur) of the mois
ture-free mucilaginous material. In particular, this in
sodium, leaving the calcium content unchanged, is gelled
vention applies to mucilaginous materials which occur in
by the mucilaginous material, but the resultant gel is
certain marine plants of the Gigartinaceae and Solieri
weaker than one prepared from natural milk which con
aceae families, the carrageenan of Irish moss being an
tains both calcium and potassium. It thus seems that
example of such a mucilaginous material.
the potassium acts synergistically with the calcium to
The other type of gel-forming phenomenon, character
yield a stronger gel than that obtained with calcium in
istic of the seaweed mucilages whose improvement is an
the absence of potassium.
object of this invention, and the type with which this in
While the foregoing explanation of the mechanism in
vention is principally concerned, is that involved in the
volved in the gelling of milk by mucilaginous materials
formation of a gel with milk. Gels of this type when
of the high monoester sulfate type is plausible and is be
sweetened and ?avored constitute the well-known blanc
lieved by me to be true, other mechanisms are certainly
ity to form strong aqueous gels, although it contains very
mange and have long been used as an article of food
conceivable, and for this reason I do not wish that what
representing undoubtedly the earliest usage made of the
I claim ‘as my invention, as it applies to milk gels and
carrageenan of Irish moss. Despite their long and well 50 their formation, shall be construed as limited to milk gels
formed by the said mechanism.
known usage, the ‘literature discloses little evidence that
these gels have ever been thoroughly investigated or clear
The gelling effect which the mucilaginous material
ly distinguished from the type of gel which is obtained
exerts on milk may be evaluated in terms of the strength,
with the mucilaginous material and water alone, notwith
as measured by the Bloom gelometer, of a gel prepared
standing the fact that the behavior of these mucilaginous
from the mucilaginous material and milk under certain
materials toward milk is of basic importance not only with
standard conditions. Such a measurement I have found
regard to their use in puddings of the blanc mange type,
to be quite reproducible and accordingly have adopted it
but also in the numerous other applications wherein they
as an index of milk reactivity whereby various prepara
are used to stabilize dairy products, such as chocolate milk,
tions of mucilaginous material may be rated with respect
60 to their gelling effect on milk. This index of gelling
ice cream, cheese foods, and the like.
The type of gel which these mucilaginous materials
ability is hereinafter referred to as “milk reactivity.”
form with milk differs fundamentally from the type of
The technique whereby I determine the aforesaid milk
gel which they form with water alone. The solids of the
reactivity index is essentially as follows: A dispersion con
milk, and in particular the casein and other proteinaceous
taining 0.154% of the dried, pulverized, mucilaginous ma
components of the milk are essential to the formation of
the milk gel. That this gel formation is not a simple
gelling of the mucilaginous material with the water con~
terial is prepared in fresh homogenized whole milk. Dis
solution of the mucilaginous material is effected by heating
this dispersion to boiling. The resulting mucilage-rnilk
sol is then cooled to 10° C., whereupon it sets to a gel.
tent of the milk is strikingly shown by the small amounts,
This gel is aged for two hours at 10°. It is then tested at
in the range of about 0.05% to about 0.50%, of the muci
laginous material required to make a ?rm gel with milk. 70 10° by means of a Bloom gelometer equipped with a
plunger of 1 inch diameter. The strength of the gel is
The gelling of milk by the mucilaginous material seem
measured as the weight in grams required to force this
ingly involves chemical reactions of the mucilaginous ma
plunger to a depth of 4 mm. into the gel when the weight
terial with the proteins of the milk. One such type of
is applied to the plunger at the rate of 40 grams per sec
reaction may be that wherein the anionic monoester sul
ond. This strength of the milk gel, prepared from the
3,094,517
7
8
moved in this manner without severely depolymerizing
the polysaccharide portion of the molecule. As will sub
sequently ‘be shown, it is seemingly the case that ‘any al
Although the molecular structure of lambda-carragee
kali can effect a loosening or detachment of the carbon
nan has not as yet been completely elucidated, it is
believed to consist largely of linear chains of D-galactose
residues joined by 1,3'-g1ycosidic linkages and with a
oxygen-sulfur bond attaching the monoester sulfate to
the polysaccharide portion of the carrageenan molecule,
monoester sulfate group attached to carbon 4 of each
galactose. This feature of the structure of lambda-car
but that this reaction is completely reversible so that no
extensive removal of the monoester sulfate groups can
occur except in the presence of a reagent such as barium
rageenan is shown as a structural formula in FIGURE l.
The other constituent of Irish moss mucilage, kappa
carrageenan, has been more thoroughly characterized than
hydroxide, which is capable of removing the liberated 10 has lambda-carrageenan. The molecule of kappa-car
rageenan is believed to consist of a main linear chain
sulfuric acid from the reaction scene.
made up of alternate D- galactose and 3,6-anhydro-D
galactose residues. Each D-igalactose residue carries a
The resistance of the milk reactivity of the mucilagi
nous materials which are the subject of this invention
monoester sulfate group on carbon 4 and is beta-1,4’
sistance of the mon-oester sulfate groups to removal from 15 iglycosidically linked to an adjacent 3,6-anhydro-D-galac
tose residue. Each 3,6-anhydro-D-galactose residue is
said mucilaginous materials. I have discovered that
alpha-1,3'- glycosidically linked to an adjacent D-galac
Where the monoester sulfate groups can be successfully
tose residue and is unsulfated. A short side chain, be
attacked, as by the method of alkaline hydrolysis herein
lieved to consist of a single D-galactose residue with
above described, the milk reactivity of the mucilaginous
material is ‘also affected. One might reasonably expect 20 monoester sulfate groups attached at carbons 3 and 4,
is 1,6'-glyoosidically linked to each ?fth D-galactose unit
that if the number of monoester sulfate groups in the
of the main chain. The presently accepted structural
molecule of :mucilaginous material is decreased, as is
formula of kappa-carrageenan is as shown in FIGURE 2.
the case by the above method, the sites for cross-link
On the basis of the above structures presently accepted
age ‘with the casein of the milk ‘are thereby reduced and
a reduction of the milk reactivity of the so~treated muci 25 for lambda- and kappa-carrageenan, their compositions
in terms of percentages of sulfate groups and hexose
laginous material would result. The actual effect which
to alteration by hitherto known methods parallels the re
residues composing said structures have been calculated.
the aforesaid treatment achieves, however, is, surpris
In the course of my investigations as to the nature of
ingly, that of a substantial increase in milk reactivity.
the structural changes effected in carrageenan by the
This anomaly has led to the hypothesis that decrease of
the number of monoester sulfate groups in the molecule 30 practice of my invention, these individual fractions of
carrageenan were isolated and separately subjected to
of mucilaginous material within the range achieved in
my investigations is, at most, of secondary signi?cance
in the control of milk reactivity, and that the primary
effect, with respect to milk reactivity, of the alkaline
alkaline hydrolysis in accordance with the practice of
this invention. Analytical data on these fractions, and
the remaining monoester sulfate groups into a con?gura
tion conducive to ‘a net increase in the milk reactivity of
the aforesaid theoretical values calculated from the above
structural formulas:
on unfractionated carrageenan before and after alkaline
hydrolysis is one of an intramolecular rearrangement of 35 hydrolysis, are presented in Table 1 in comparison with
TABLE 1
the mucilaginous material.
I have further discovered, in con?rmation of the hy
pothesis alluded to in the preceding paragraph, that an 40
alteration of the milk reactivity of the mucilaginous ma
_
Material
terials which are the subject of this invention can be
achieved with little or no change in the monoester sul
fate contents thereof.
To achieve this result I employ
Na )t-carragcennte
(theoretical) _____ __
provement of milk reactivity by this method the use of
tionation) _______ __
a strong ‘alkali effects ‘an undesirably severe depolymeriza
ti-on of the mucilaginous material.
55
Recent discoveries in regard to the molecular struc
ture of the carrageenan of Irish moss lend credence to
my theory hereinabove set forth. ‘Studies of this sea
weed mucilage indicate that it is a mixture consisting
predominantly of two polysaccharides known as lambda 60
carrageenan and kappa-carrageenan which are present in
the unfnactionated carrageenan in about equal amounts.
A distinguishing difference between these ‘two polysac
char-ides is that kappa-carnageenan is precipitated or
erties of unfractionated carrageenan, as ordinarily ex
tracted from Irish moss, appear to be due to the kappa
fraction thereof; likewise, evidence has been presented
(Smith, Canadian Journal of Technology, vol. 31, pp.
209-212 (1953)) that the milk reactivity of said unfrac
tionated carrageenan is due to its kappa fraction.
Aqueous
g
Vis
strength a coslty 4
0
36. 4
__________________________ ._
33. 7
27. 9
__________________________ ._
Na k-carrageeuate
tioned, but instead of ‘barium hydroxide I use an alkali
(theoretical) _____ __
Na )t-carrageenate
which does not remove the sulfur of the rnucilaginous
(prepared by trac
tionatlon) _______ N
material as an insoluble sulfate. A mild alkali, such as
salt of Ca(OH),
calcium hydroxide, is to be preferred to a strong alkali 50 Natreated
N a A-car
rageenate ........ _such ‘as sodium hydroxide, ‘as with the amount of alkali
Na k-carrageenatc
and at the temperatures which are optimal for the im
(prepared by trac
gelled by potassium ions, whereas lambda-carnageenan
Milk
reactivity I
percent 1
‘an alkali treatment similar to that hereinabove men
lacks this so-called “potassium sensitivity.” This differ
ence in behavior toward potassium ions is employed for
the fractionation of carrageenan into the aforesaid lambda
and kappa constituents. The aqueous gel-forming prop
3,6
anhydro
S04,
galactose, percent 1
2. 91
36. 49
(B)
14. 97
37. 85
(1)
27. 69
25. 81
40. 1
(6)
45
4. 6
6
185. 0
9
Na salt of Ca(OH)r
treated Na k-car
rageenate ________ __
27. 70
28. 06
68. 0
339. 7
5
(unfraetionated)-..
Na salt of Oa(0II),
treated unfrac
tionated Na
17. 86
31. 87
45. 7
239. 7
106
carraguenate _____ __
26. 66
28. 54
122. 6
290. 2
19
21. 84
31.00
(5)
Na carrageenate
Na salt of Ba(OH)z
treated Na x-car
ragcenate ________ _ _
________ -.
6
1 Percent based on moisture-free material.
“Strength of gel containing 0.154% material (not cor
rected for ‘moisture content) in whole milk, in grams at
10° C. as measured by :1 Bloom gelometer equipped with a
65 1" diameter plunger.
“Strength of aqueous gel, containing 1.5% material (not
corrected for moisture content) plus K-Cl e trivalent to
twice the nionoester sulfate or the material, 11 grams at
710° C. as measured by u Bloom gelometer equipped with a
70
0.5" diameter plunger.
4Viscosity of 0.5% aqueous solution of material (not
corrected for moisture content), in centipoises at 25° C.
as measured by a MacMichael vlscosirneter.
5 Gel too weak to measure.
7 Trace of gel.
The analytical data given above for the sodium‘lambda
and kappa-carrageenates differ somewhat from the theo_
3,094,517
retical values therefor, but are close to results found by
other investigations of carrageenan fractions. (Smith,
O’Neill and Perlin, Canadian Journal of Chemistry, vol.
33, pp. 1352-1360 ( 195 5 ); O'Neill, Journal of the Ameri
can Chemical Society, vol. 77, pp. 6324-6 (1955)).
Some divergence from theoretical values is to be expected
due to the practical dii?culty of obtaining completely
separated fractions.
10
the differences apparently being accountable to the effect
of neighboring structures on said glycosidic bonds. The
structure of lambda—carrageenan as shown in Formula 1
does not indicate any such differences in the glyeosidic
bonds; however, as previously stated, this pclysaccharide
has not as yet been completely characterized and the
possibility of more than one type of glycosidic bond
and/ or ester sulfate structure cannot be precluded.
The decrease in viscosity observed on the aforesaid
Comparsion of the above analytical data for the car
alkaline hydrolysis of lambda‘carrageenan indicates that
rageenan fractions, as well as for the unfractionated 10 the new polysaccharide obtained thereby is less highly
carrageenan, before and after alkaline hydrolysis reveals
polymerized than its precursor. This has been con?rmed
that the lambda fraction undengoes a pronounced change
‘by
ultracentrifugation studies and by determination of
in chemical composition on said hydrolysis, this change
reducing end groups. The latter determination indicates
consisting in the formation therein of a large percentage
that the new polysaccharide has an average molecular
of 3,6-anhydrogalactose residues, a structural feature 15 weight, which is about one-third that of the precursive
normally associated with kappa-carrageenan and not pres
lambda-carrageenan.
ent in normal lambda-carrageenan. One cannot con
Presently available information is insufficient to permit
clude, ‘however, that alkaline hydrolysis has converted
complete elucidation of the structure of the aforesaid
any substantial portion of the lambda-carrageenan to
new polysaccharide nor of the mechanism of its forma
kappa-carrageenan. Such a conversion should result in 20 tion from lambda-carrageenan. However, it is possible
a mark-ed decrease in monoester sulfate content. How
ever, when the hydrolysis was conducted with calcium
hydroxide no such decrease was found, sulfate analyses
indicating ?rst the ratio of monoester sulfate groups
to galactose plus anhydrosugar residues was very close
to 100% for both the untreated lambda-carrageenan
and the product obtained from it on hydrolysis with cal
to offer an hypothesis as to said structure and mechanism
based on known properties of carbohydrate sulfates.
Such an hypothesis must account for the extensive forma
tion of 3,6-anhydro rings on alkaline hydrolysis of
lambda-carrageenan. It is known that anhydro rings are
formed by the alkaline hydrolysis of carbohydrates con
cium hydroxide. On the other hand, hydrolysis with
taining sulfate and hydroxyl groups in certain configura
hydrolysis of lambda- carrageenan with either calcium
results in cleavage of the sulfate with Walden inversion
hydroxide or barium hydroxide. Onegrnust conclude,
therefore, that alkaline hydrolysis according to the prac
tice of this invention when applied to lambda-carragee
involved. Such an ethylene oxide ring, if properly sit
unknown polysaccharide, said polysaccharide containing
Another configuration, and one leading directly to 3,6
anhydro ring formation, is that wherein the carbohydrate
tions relative to each other (Percival, Quarterly Reviews
barium hydroxide, a reagent which I have found will re
move monoester sulfate groups when employed accord 30 (London), vol. 3, pp. 369-384 (1949)). One such con
?guration leading to anhydro ring formation is that where
ing to the practice of this invention, resulted in a de
in the carbohydrate contains a hydroxyl group on a car
crease in sulfate content to 85% of that of the untreated
bon atom adjacent to a carbon atom carrying a sulfate
lambda-carrageenan. Furthermore, no substantial de
group in the trans-con?guration relative to the hydroxyl'.
velopment of either aqueous gel-forming ability or milk
Mild treatment of such a carbohydrate sulfate with alkali
reactivity typical of kappa-carrageenan was obtained by
of the carbon atom which carried the sulfate and forma
tion of an ethylene oxide ring between the carbon atoms
nan results in the production of a new and hitherto 40 uated, may further rearrange into a 3,6-anhydro ring.
substantial number of anhydrosugar residues, believed
to be of the 3,6-anhydro type, and either substantially
is sulfated at carbon 6 and ‘has a free hydcoxyl group
at carbon 3. In this case mild alkaline hydrolysis results
the same ratio monoester sulfate groups to galactose
in cleavage of the sulfate and formation of a 3,6-anhydro
residues plus anhydrosugar residues as occur in the pre 45
ring.
cursive lambda-carrageenan, on a substantially smaller
Neither of the above conditions for anhydro ring
ratio thereof, the latter case occurring when the alkali
formation appears to be present in lambda-carrageenan
employed to effect the hydrolysis is one capable of ir
as conventionally represented by the structure of FIGURE
reversibly splitting o? monoester sulfate groups from the
polysaccharide chain. For the purpose of characteriza
tion I consider that this new polysaccharide has substan
1. ‘Furthermore, the practice of my invention has been
found to require alkaline hydrolysis under relatively
severe conditions, which may be taken to indicate that
tially the same ratio of monoester sulfate groups to galac
the lambda-carrageenan structure is not inherently. favor
tose residues plus anhydrosugar residues as that of
able for the chemical changes claimed as a part of my
larnbda-carrageenan when analysis indicates a ratio fall
invention.
Nevertheless, it is evident that said chemical
55
ing within the range of 90% to 110%, and that a ratio
changes do involve anhydro ring formation, and hence
of less than 90% indicates that an appreciable amount
it is a reasonable conjecture that the initial action of
of monoester sulfate has been removed from the poly
the alkali on the resistant lambda-carrageenan structure
saccharide chain. My investigations indicate that this
new polysaccharide derived from lambda-carrageenan
may be one of rearrangement of said structure into a
con?guration which can lead to anhydro ring formation.
may have a ratio of monocster sulfate groups to galactose 60 Such a postulated rearrangement may be one wherein
plus an-hydrosugar residues as low as 30%. In its lack
a sulfate vgroup migrates from carbon 4 to carbon 6,
of gel-forming properties, this new polysaccharide per se
closely resembles lambda-carrageenan. Further evidence
while the 1,3'-glycosidic linkage migrates to the 4' posi
tion vacated by the sulfate, as shown ‘by reference to
l and 3. The resulting structure (FIGURE
by its infrared absorption spectrum. This shows little 65 FIGURES
3) then is favorable for the formation of a 3,6-anhydro
change from larnbda-carrageenan in a peak at 1230 cmrl,
ring by cleavage of the sulfate on carbon 6. Since
which has been correlated to the sulfate group and ap
the product formed by alkaline hydrolysis of lambda
pearance of a strong peak at 935 cm.~1 which has been
carragecnan contains substantially the same amount of
correlated to the 3,6-anhydro ring. Changes are also
monoester sulfate as the precursive Iarbda-carrageenan
70
observed in the fine structure of a broad peak in the
itself, it must be assumed that the sulfate cleaved from
1000-1100 cm.‘1 region which I believe to be associated
carbon 6 further migrates to some other available posi
with the glycosidic carbon-oxygen-carbon ‘bonds of the
tion, possibly to carbon 2 of the lgalactose residue in
as to the nature of this new polysaccharide is furnished
polysaccharide structure. The complex nature of this
volved or to carbon 2 or carbon 6 of an adjacent galactose
peak may be interpreted as indicating the presence of
three, or possibly more, different types of glycosidic ‘bond, 75 residue (FIGURE 4).
3,094,517
11
12
It can be seen that the postulated structure (FIGURE
as a contaminant in said preparation of kappa-carrageenan.
4) of alkali-modi?ed lambda-carrageenan has certain
Evidence has been cited (Bayley, supra) that normal
lambda- and kappa-carrageenans as they naturally occur
structural features characteristic of kappa-carrageenan
(FIGURE 2), notably 3,6-anhydro-D-galactopyranose
in unfractionated carrageenan are not present therein as
residues and heta~1,4'-glycosidic linkages attached thereto.
a simple mixture, but coexist in a de?nite structural rela
tionship to one another and thus may be said to form a
Additional evidence for the presence of these structures
in alkali-modi?ed lambda-carrageenan is ‘found on com
single compound, though evidently a loosely bonded one.
It is my hypothesis that the alkaline hydrolysis of lambda
parison of the infrared spectra of lambda-carrageenan,
alkali-modi?ed lambda-carrageenan, and kappa-carragee
carragcenan produces a new polysaocharide which is like
nan. The salient features of these spectra are given in
wise capable of associating with kappa-carrageenan to
10
Table 2.
form an addition compound which is not only more ?rmly
TABLE 2
TVave number, cmrl
Sample
935
Lambda ____________ __
Trace of peak"
Modi?ed lambda.-.__ Intermediate pie
Kappa _____________ ._
1015
_
1070
1230
Peak ____________ or
Small peak"
__
Peak 0bSCL1Ted____
Large peak__
__
Large peak _______________ __do ________________ __
Large peak.
D0.
Intermediate peak.
The peaks at 935 cm.—1 and 1230 cm.‘1 have been
bonded than that consisting of normal lambda- and kappa
assigned to the 3,6-arrhydro ring and m-onoester sulfate, 25 carrageenans, ‘but also possesses ‘greatly enhanced milk re
respectively, as aforesaid, and are seen to agree well
activity and aqueous gel-forming ability. This compound,
with the analytical determinations of these moieties cited
in the case of the carrageenan of Irish moss, or compounds
in Table 1. The peaks at 1015 cm.—1 and 1070 cm.-I
analogous thereto in the case of other seaweed mucilages
occur in the band assigned to glycosidic carbon~oxygen~
‘found to be responsive to improvement of their gelling
30
carbon linkages, and if the peak at 1015 cm.—1 is assigned
properties through the practice of this invention I believe
to the alpha—1,3’-glycosidic linkage and that at 1070 cm."1
constitute the essential ingredient of the improved sea
to the beta-1,4'-glycosidic linkage, then the observed peaks
weed mucilages I wish to claim as parts of my invention.
agree with the known presence of the latter linkage in
Evidence that the participation of both the lambda
kappa-carrageenan and its postulated appearance in
and kappa-fractions of carrageenan is necessary to obtain
alkali-modi?ed lambda-carrageenan by rearrangement of 35 a high degree of improvement in milk reactivity through
a portion of the alpha-1,3'-glycosidic linkages present in
alkaline hydrolysis in accordance with the practice of this
the precursive lambda-carragcenan.
invention is aiTorded by the substantial increase in milk
Alkali-modi?ed lambda-carrageenan differs from kappa‘
carrageenan in that it may have additional monoester
reactivity cited in Table 1 for the alkali treatment of un
tractionated sodium carrageenate as compared with the
sulfate groups, attached either to the 3,6-anhydro-D 40 smaller increase found on alkali treatment of ‘a sodium
galactopyranose residues or to adjacent D-galactopyranose
kappa-carrageenate preparation from which most of the
residues; also in preparations of this new polysaccharide
‘lambda fraction had been removed and with the complete
so far examined, the number of 3,6-anhydro structures
absence of milk reactivity found on alkali treatment of a
found is substantially less than is found in kappa-car
rageenan. It is, therefore, indicated that the 3,6-anhydro
sodium lambda-carrageenate preparation from which most
of the kappa fraction had been removed.
D-galactop-yranose residues in said new polysaccharide are
While the foregoing description of the chemical changes
randomly distributed throughout the polysaccharide chain,
involved in and the compounds formed by the alkaline
rather than in the regular alternation with D-galactopyran
hydrolysis of carrageenan and other seaweed mucilages in
ose residues found in kappa-carragecnan. The regular
accordance with the practice of this invention is plausible
50
interspersal of sulfated residues with non-sulfated residues
in the light of presently available evidence and is believed
characteristic of kappa-carrageenan has been suggested as
an explanation of the speci?c tendency of kappascarragee
nan to form gels in the presence of certain cations, not
ably potassium (Bayley, Biochim et. Biophys, Acta, vol.
by me to be essentially correct, the possibility is recog
nized of there being other reaction mechanisms and com
pounds formed thereby which can conceivably be postu
lated to ?t the presently available evidence, and for this
17, pp. ‘194-205 (1955)). An absence of the same reg 55 reason I do not wish that what I claim as my invention,
ular ‘spacing of monoester sulfate groups, plus steric hind
in so ‘far as it applies to the alkaline hydrolysis of sea
rance due to the additional monoester sulfate groups, in
weed mucilages and to the compounds formed thereby,
alkali-modi?ed lambda-carrageenan may well account for
shall be construed as limited to the particular reaction
its failure to possess the gel-forming properties character
mechanism hereinabove set forth and the particular com
60 pounds hereinabove indicated as being produced ‘thereby.
istic of kappa-carrageenan.
In contrast to the pronounced chemical changes ob
Rather, what I wish to claim in this respect are chemical
served in lambda-carrageenan an alkaline hydrolysis in
processes and compounds of such a nature and possessed
accordance with the practice of this invention, no evidence
of such properties ‘as I have established and herein set
of any extensive chemical change is found on like treat
forth.
ment of kappa-carrageenan. This is shown by the an 65
The following techniques may be employed in the
alytical data of Table 1, and by the close similarity of
practice of this invention, it being understood that the
the infrared absorption spectra of normal and alkali
description given herewith of said techniques is intended
modi?ed kappa-carrageenan. Although an increase in
to be illustrative rather than limiting.
both milk reactivity and aqueous rgelsforming ability was
The mucilaginous material to be treated is taken in the
observed on alkali treatment of the preparation of kappa 70 form of an aqueous solution containing, as a matter of
carrageenan studied here, the abovesaid chemical evidence
convenience, one percent or more of mucilaginous ma
has led me to believe that this is due to an association or
terial.
interaction of the essentially unchanged kappa-carragee
extract of the mucilaginous material produced by any
previous process hitherto employed for the manufacture
Such a solution may be one prepared from an
nan with alkali-modi?ed lambda-carrageenan arising
from a small percentage of lambda-carrageenan present 75 of mucilaginous extracts from Irish moss or other sea
3,094,517
14
13
weeds of the class Rhodophyceae. Alternatively, the
solution may be a syrup of mucilaginous material obtained
by ?ltration or other means of separation from the sea
weed in accordance with prior known methods for the
separation of the mucilagino as material from the insoluble
constituents of the seaweed.
Alternatively, as a feature
of preferred practice of this invention ‘the treatment may
be applied to an aqueous ‘mass of the seaweed itself where
,
hereinabove described. The temperature ordinarily em
ployed ranges from about 80° C. to about 150° C., tem
peratures between 90° C. and 130° C. being preferable.
In general, the increase in milk reactivity will be greater
when the higher temperatures within this range are em
ployed. To attain these higher temperatures requires
that the heating be carried out at greater than atmos~
pheric pressure, and accordingly an autoclave or pres
sure cooker must be used. On the other hand, heating
in the mucilaginous material has not been separated from
at 90° C. to 100° C. can be done at atmospheric pres
the insoluble constituents of the seaweed. This latter 10 sure, and from the standpoint of simplicity and initial
technique is advantageous in that it permits the treatment
cost of equipment this temperature range is to be pre
of the mucilaginous material to improve its gel-forming
ierrcd.
properties to be carried out simultaneously with the di
The period of treatment may be varied. In general,
gestion of the seaweed to bring the mucilaginous material
the
increase in milk reactivity will be greater if the treat
into solution whence it can be recovered by ?ltration or 15
ment is prolonged. A period of about three to six hours
other conventional means.
The alkali employed in the preferred practice of this
invention is calcium hydroxide, which is to be preferred
from ‘the standpoints of its eifectiveness in promoting
the desired improvement in milk reactivity of the muci
laginous material, its mildness with respect to degrada
tive attack on the polysaccharide chain of the molecule
of the mucilaginous material, its low solubility and its
low cost. The amount of calcium hydroxide employed
may be considered optimal.
Following the treatment the greater part of the excess
calcium hydroxide may be separated, as aforementioned,
if it is desired to recover it for reuse. Filter aid is then
added to the mixture and ?ltration accomplished by any
suitable type of equipment of which many are well
known, e.g., a ?lter press, rotary ?lter, or the like.
It
is preferable that this ?ltration Fbe carried out on the
may be varied somewhat, with the most effective amount 25 mixture while it is hot, as it is a characteristic of the
mucilaginous material after being subjected to the fore
being from 50% to 125% of the mucilaginous material
going treatment wtih calcium hydroxide that its aqueous
present, though lesser amounts down to about 10% may
solution is highly ?uid when hot so that it can be ?ltered
be used. In general, the larger amount of calcium hy
very readily in this state. It is also preferable that the
droxide produces the greater increase in milk reactivity
of the mucilaginous material. While these amounts of 30 ?ltration he carried out prior to neutralization of the
alkaline mixture so as to remove any remaining solid
calcium hydroxide are in considerable excess of that solu
calcium hydroxide (and thereby to minimize the amount
ble in the amount of water present, it is seemingly, the
of acid subsequently required for neutralization, and,
case, nevertheless, that the excess calcium hydroxide in
further, to take ‘full advantage of the greater stability of
its solid state is an active agent in the improvement of
the milk reactivity of the mucilaginous material. The 35 the mucilaginous material when alkaline to depolymeriza
tion by heat.
The ?ltered alkaline syrup of mucilaginous material is
then neutralized, preferably by addition of a mineral acid
such as sulfuric acid or hydrochloric acid, although any
cium. An excess calcium hydroxide, which may amount 40 other suitable acid may be used.
The foregoing steps accomplish the treatment of the
to 40% to 115% of the weight of the mucilaginous ma
mucilaginous material, to improve its milk reactivity,
terial, seemingly acts catalytically in the sense that while
and the recovery of the treated mucilaginous material.
its presence is necessary to the achievement of a great
For commercial marketing the recovered syrup can be
improvement in the milk reactivity of the mucilaginous
further treated, according to conventional practice, so
material, it is not consumed thereby. Thus the excess
as to produce the mucilaginous material in dry form.
calcium hydroxide remains unchanged at the end of the
For this one may employ such operations as drum or
treatment, and, being in the form of solid particles of
spray drying, coagulation with ‘alcohol, etc, as may be
high density, may be separated ‘from the aqueous mass
regarded as convenient.
of digested seaweed by decantation, centrifugation, or
The following examples offer speci?c illustrations of
other means, and largely recovered for reuse.
the practice of this invention and the nature of the mud
Alkalies other than calcium hydroxide may be em—
laginous materials obtained thereby. It is to be under
played in the practice of this invention and thus are
calcium hydroxide is consumed, in the amount of about
10% of the weight of mucilaginous material present, by
reaction with the mucilaginous material to replace the
cations associated with the mucilaginous material by cal
stood that they are intended only to illustrate and not
understood to come within the scope of this invention,
to limit the scope of this invention.
for it is seemingly the rationale of this invention that an
alkaline hydrolysis is employed to loosen the bond be 55
Example 1
tween the monoester sulfate groups and the polysacchar
Portions
of
a
?ltered
extract of Irish moss, said extract
ide chains of the mucilaginous material whereby said
containing 1.66% of mucil-aginous material, were heated
monoester sulfate groups may either be split off entirely
with calcium hydroxide in the amount of 120% of the
from the molecule of the mucilaginous material or be
enabled to re-esterify in new positions on the polysac 60 weight of mucil-aginous material in the portion taken.
The heating was maintained for six hours at various
charidc chains of the molecule of mucilaginous material.
temperatures, as shown in ‘Table 3. Each portion after
The alkali employed need not be sparingly soluble nor
heating was ?ltered to remove excess calcium hydroxide.
be present in the solid form to be effective in the ractice
The ?ltrates were neutralized with hydrochloric acid
of this invention, and mild ialkalies which are highly
soluble, such as sodium carbonate or trisodium, phosphate 65 and the mucilaginous materials precipitated therefrom
by the addition of isopropyl alcohol. After further de
can
used.
The conversion of the mucilaginous material possessing
a normal degree of milk reactivity, that is, capable of
forming with milk a gel whose strength lies ordinarily
hydration with isopropyl alcohol the precipitated muci
of increased milk reactivity is accomplished by heating
the aqueous mixture containing mucilaginous material
?ltered Irish moss'extract were heated under conditions
laginous materials were dried at 65° C. The dried muci
laginous materials were tested for their milk reactivity,
the range from uni-measurably low strength up to 70 aqueous gel-forming power, and viscosity in aqueous
solution.
a strength of 70 grams as measured by my aforemen
For comparison, other portions from the same lot of
tioned standard procedure, into mucilaginous material
similar to the foregoing, except that no calcium hydroxide
and alkali prepared in accordance with the conditions 75 or other alkali was present.
After heating, these por
3,094,517
15
16
tions were worked up as in the foregoing procedure to
ion so associated with the alkali-treated products cited
in this example is calcuim, which is not a strongly gel
forming cation with respect to the mucilaginous material
of Irish moss. Thus the aqueous gel strengths shown in
yield the dried mucilaginous materials therefrom, and
these were also tested.
A specimen of the mucilaginous material precursive to
the above preparations of this example was prepared by 5 Table 3 could have been greatly increased by the intro
precipitatmg with isopropyl alcohol a portion of the origiduction of other cations, notably potassium. Instances of
nal ?ltered extract of Irish moss, omitting both the calthe aqueous gel strengths thus attainable will be cited in
cium hydroxide and the six-hour heating period. The
a subsequent example.
precipitate was further dehydrated with isopropyl alcohol
Moreover, it is to be observed that the results presented
and dr1ed at 65° C.
.
|
10 in this example, having been obtained by treatment of a
‘Data on all of the preparations of this example are
given In Table 3.
?ltered extract of mucilaginous material entirely sepa
rated from the less soluble constituents of the Irish moss,
TABLE 3
With 120% CB-(OH):
Without alkali
Temperature
of treatment, Treat° C.
Milk
Aqueous Viscos- 'l‘reat-
mcnt
reactlv-
gel
pH 1
ity "
strength 3
12. 0
12. 1
12. 0
12. 0
11. 9
105. 0
140. s
139. 4
143. a
156. 5
19. 0
40. 1
41. 2
31. 9
32. 5
ityl
Milk
Aqueous Viscos
merit
reactlv-
gel
pH 1
ity I
strength I
485
485
434
365
270
7. 0
e. s
6.7
e. s
6. 2
Precursive material (from untreated extract) ______________ ._
ity 4
41. 0
40. 4
32.6
25. 2
(t)
(a)
(n)
(v)
(6)
(d)
435
292
109
4o
u
41. 0
(a)
856
1 pH at mixture after heating and before ?ltratlon and neutralization.
9 Strength of gel. containing 0.154% mucilaginous material in whole milk, in grams at
10° C. as measured by 21- Bloom gelometer equipped with a 1-inch diameter plunger.
3 Strength of gel, containing 1.5% mucilaginous material in water. in grams at 10° C.
as measured by a Bloom gelomcter equipped with a 0.5-inch diameter plunger.
‘ Viscosity of 1% aqueous solution of mucilaginous material, in oentipoises at 25° C.
as measured by a MacMichael vlscosiructcr.
1! Soft gel, too weak to measure.
0 The prccursive material and the products prepared from it by heating without alkali
contained principally sodium as a cation and hence were not water-gelling materials. The
calcium sult of the prccursive material would have an aqueous gel strength or about 10 grams.
Examination of the data in this table reveals that the
demonstrate clearly that the nature of this invention con
present invention, as illustrated in this example, results
sists in the modi?cation of the normal mucilaginous
in a large increase in the milk reactivity of the mucilag
material of Irish moss into a novel and hitherto unknown
inous material found in Irish moss, said increase being 40 form of improved gel-forming properties, that this im
commonly in a two~fold ‘to fourfold ratio of the milk
proved material is not an additional substance already
reactivity of the improved material over that of its pre
present in the Irish moss, and that the practice of this
cursor. Furthermore, the increase is seen to be greater
invention when applied directly to the whole Irish moss
when the alkali treatment is conducted at higher tem
does not consist merely of a more drastic extraction
peratures, even though some depolymerization of the 45 method aimed at extracting additional substances from
mucilaginous material, as indicated by decreased viscosity,
the seaweed.
occurs at these higher temperatures. This illustrates the
Moreover, a comparison of the alkali treatments with
relative insensitivity of the milk reactivity to the degree of
the control treatments conducted without alkali illustrates
polymerization of the mucilaginous material.
the greater stability toward depolymerization by heat of
Moreover, it may be seen that, as a further feature of 50 the mucilaginous material under alkaline conditions.
this invention, the alkali treatment of the mucilaginous
material not only improves its milk reactivity, but also
enhances its potential ability to form gels with water as
well over. It is seemingly the case that the rearrangement
of structure brought about through the alkali treatment 55
relocates the monoester sulfate groups ‘in a con?guration
which is generally favorable for cross-linkage, whether it
Furthermore, it is seen that the effect of heat alone, in
the absence of alkali, does not result in the improve
ment of the mucilaginous material which is the object
of this invention.
Example 2
Portions of a ?ltered extract of Irish moss, said extract
be that between the monoester sulfate groups and the
containing 1.81% of mucilaginous material, were heated
with various amounts of calcium hydroxide. The tem
carboxyl or ester phosphate groups of casein, as in the
gelling of milk, or that between monoester sulfate groups 60 perature was maintained at 126° C. for three hours. Each
on adjacent polysaccharide chains of the mucilaginous
portion after heating was ?ltered to remove excess cal
cium hydroxide. The ?ltrates were neutralized with by
material, as may be involved in its gelling with water.
drochloric acid and the mucilaginous materials precipi
Furthermore, it may be seen that the increase in aqueous
gel strength roughly parallels the increase in milk re
tated ‘therefrom by the addition of isopropyl alcohol.
activity, with a two-fold to four-fold ratio of the aqueous 65 After further dehydration with isopropyl alcohol the pre
cipitated mucilaginous materials were dried at 65° C.
gel strength of the improved material to that of its pre
cursor being found. The aqueous gel strength, however,
is rather more sensitive to the degree of polymerization
of the mucilaginous material than is the milk reactivity,
A specimen of the mucilaginous material precursive to
the above preparations of this example was prepared by
precipitating with isopropyl alcohol a portion of the origi
and hence tends ?rst to increase as the temperature of 70 nal ?ltered extract of Irish moss, omitting both the cal
cium hydroxide and the three-hour heating period. The
the alkali treatment is raised and then to decrease at
still higher temperatures at which depolymerization of
the mucilaginous material becomes considerable. Also,
precipitate was further dehydrated with isopropyl alcohol
and dried at 65° C.
Data on all of the preparations of this example are
the aqueous gel strength depends on the cations associ
ated with the monoester sulfate groups, whereas the cat 75 given in Table 4.
3,094,517
>
TABLE 4
_
1
Theo
Oa(OH),
Treat-
Milk
mucllaglnous
pH 1
tlvity "
percent of
material
ment,
Aqueous
rear,
gel
Vis-
strengthI eoslty 4
50;,
0a,
per-
per-
cent 1
cent 5
'
retical
0a, per
percent
cent of
a for
0a carra-
geenate 6
48.1
61. 2
98. 4
150. 3
6. 9
47. 8
59. 7
95. 8
556
243
353
262
25. B0
23. 63
23. 91
23. 97
0.37
3. 65
4. 17
4. 42
5. 38
4. 93
4. 99
5. 00
theo
retical
6. 9
74. 0
83. 7
88. 4
1 As in Example 1.
1 As in Example 1.
i As in Example 1.
4 As in Example 1.
i Not corrected for moisture content of mucilag'lnous materia l .
I Calculated from $04 according to theoretical ratio of Ora/2804 for a Ca galactose sulfate.
1 Precursive material, not heated with alkali.
This example'demonstrates that the degree of improve
mcntof the gelling properties of the mucilaginous mate
must be present in a sufficient excess or reserve amount,
but that it is immaterial whether this excess be present
rial of Irish moss can be controlled by varying the amount
in solution or as a solid phase.
of calcium hydroxide employed. Moreover, it illustrates
carbonate is eifective in improving gelling properties of
It further appears from this example that While sodium
the desirability of employing a large excess of alkali in
the mucilaginous material of Irish moss, it is not as de
order to obtain a high degree of improvement.
sirable for this purpose as certain other alkalies, notably
A slight desulfation of the mucilaginous material is ob 25 calcium hydroxide. Not only is the amount of sodium
servedzin this example. This phenomenon appears to
carbonate required greatly in excess of the amount of
be a result of the high temperature at which the alkali
calcium hydroxide required for the same degree of im
treatments were carried out. However, a decrease in sul
provement in gelling properties, but also the employment
fate content is not necessarily attendant upon the im
of sodium carbonate in such excess results in a greater
provement of the mucilaginous material with respect to 30 degree of depolymerization of the mucilaginous material
its gel-forming properties. As will be shown in a subse
than is suffered by the employment of calcium hydroxide.
quent example, the employment of lower temperatures
This example serves further to demonstrate that a sub
for the alkali treatment can effect a substantial improve
stantial improvement in the gelling properties of the mu
ment in the gelling properties of the mucilaginous mate
cilaginous material of Irish moss can be achieved even
rial with negligible change in its sulfate content.
35 though the improved mucilaginous material is evidently
extensively depolymerized by the process employed.
Example 3
The failure of the mucilaginous material obtained in
this example to yield an aqueous gel further demonstrates
the dependence of the aqueous gelling phenomenon on
the cations associated with the mucilaginous material. It
is evident that the treatment of the precursive mucilaginous
material with sodium carbonate in excess had also the
Another portion of the ?ltered extract of Irish moss
employed in Example 2 was heated with sodium carbonate
in the amount of 276% of the weight of mucilaginous
material in the solution. The temperature was main
tained at 126° C. for three hours. The product obtained
thereby was ?ltered to remove calcium carbonate formed
effect of extensively replacing by sodium the calcium
by the reaction of some of the sodium carbonate with
and other cations associated with the prccursive material.
calcium present in the aforementioned Irish moss extract. 45 Thus the mucilaginous material obtained in this cxam~
fl‘hc ?ltrate was at pH 10.4.
It was neutralized with hy
pic was substantially in the form of a sodium salt. It is
well known that the sodium cation does not promote
aqueous gel formation by the mucilaginous material of
Irish moss, and it will be shown by this and subsequent
drochloric acid and the mucilaginous' material precipi
tated therefrom by the addition of isopropyl alcohol.
After further dehydration with isopropyl alcohol the pre
cipitatcd mucilaginous material was dried at 65° C.
examples that the improved mucilaginous material ob
tained by the practice of this invention likewise does not
The following analytical data apply to the product ob
tained thereby:
form an aqueous gel when the cation associated there
with is substantially sodium.
Milk reactivity _________________________ __g__ 111.6
Aqueous gel strength _________________ __ None-?uid
Viscosity _____________________________ __cp__
56
Moreover; for the foregoing reasons, the failure of the
55
mucilaginous material obtained in this example to yield
S04 --_, __________________________ __pcrcent__ 22.93
an aqueous gel does not imply that said material lacks
the potential ability to form an aqueous gel in the pres
These may be compared with the corresponding data
ence of more suitable cations, such as calcium and/or
potassium. Indeed, it does not imply that the aqueous
The present example demonstates that an alkali other 60 gel-forming potential of said material has not in fact
than calcium hydroxide may be used to improve the gel
been improved over that of its precursor. The data of
ling properties of the mucilaginous material of Irish moss.
Example 1 have shown that Where an improvement in
milk reactivity has been effected by the practice of this
‘It further demonstrates that the alkali employed need not
invention, the thus improved mucilaginous material so
necessarily be a slightly water soluble one, such as cal
cium hydroxide, but may be highly soluble in water, as 65 obtained also has an improved potential ability to form
is the case with the alkali of this example. Moreover, it
aqueous gels.
'
Exrzmple 4 '
further demonstrates that alkali in the solid phase need
.not necessarily be present, since in this example the
Portions of a ?ltered extract of Irish moss, said extract
amount of sodium carbonate employed did not exceed
containing 1.81% mucilaginous material, were heated
the amount which was soluble in the amount of water 70 with various amounts of trisodium phosphate. The tem
cited in Example 2.
present, and in fact it was observed in the course of this
experiment that all of the sodium carbonate remained in
_ solution. Itis seemingly the case with respect to the alkali
employed for the improvement of the gelling properties
perature was maintained at 126° C. for three hours. The
products obtained thereby were ?ltered to remove trical~
ciurn phosphate formed by the reaction of some of the
trisodium phosphate with calcium present in the afore
of the mucilaginous material of Irish moss that said alkali 75
3,094,517
19
20
mentioned Irish moss extract. The ?ltrates were neutral
In this example a very mild alkali was employed, and
it is seen that at a high level of usage some improvement
in the milk reactivity of the mucilaginons material was
effected, ‘but that this improvement was slight. This and
ized with hydrochloric acid and the mucilaginons mate
rials precipitated therefrom by the addition of isopropyl
alcohol. After further dehydration with isopropyl alcohol
the precipitated mucilaginons materials were dried at
65° C.
the foregoing examples illustrate that seemingly any
A specimen of the mucilaginons material precursive to
the above preparations of this example was prepared by
precipitating with isopropyl alcohol a portion of the orig
ment in the gelling properties to the mucilaginons mate
rial of Irish moss, but that for optimal results the alkali
alkali is capable of effecting more or less of an improve
inal ?ltered extract of Irish moss, omitting both the tri
should be a mild one, such as calcium hydroxide, but not
so mild as to afford too low a concentration of hydroxyl
sodium phosphate and the three-hour heating period. The
precipitate was further dehydrated with isopropyl alcohol
ions, as in the present example, nor yet so strong that
alkaline hydrolysis can progress to the point of severe
and dried at 65° C.
depolymerization. It is seemingly the case that the modi
Data on all of the preparations of this example are
given in Table 5.
?cation of the mucilaginons material of Irish moss so
15 as to improve its gel-forming properties and according
TABLE 5
to the practice off this invention is optimally e?ected with
Na3P04, percent
Treat-
Milk
of mucilaginous
ment
reactivity 2
material
pH 1
Aqueous
in a range of hydroxyl ion concentration corresponding
to a pH range of 11 to 12. However, the pH may range
‘from about 9.5, as indicated by this example, to about 13,
Viscosity4
gel
strength 3
42. 4
6. 8
105. 3
g‘)
57.9
20 while in ordinary practice the pH does not exceed about
12.5.
669
Example 6
144
5)
15
Portions of a ?ltered extract of Irish moss, said extract
1 As
I As
1 As
I As
in example
in example
in example
in example
containing 1.80% mucilaginons material, were heated
1.
1.
I.
1.
25 with the following organic amines and quaternary am
monium hydroxides:
I Precursive material, not heated with alkali.
‘ Very weak gel.
Triethanolamine
Tetraethanolarnmonium hydroxide
This example again demonstrates the use of a highly
Tetraethylammonium hydroxide
soluble alkali to improve the gelling properties of the 30
Phenyltrimethylammonium hydroxide
mucilaginons material of Irish moss. It further illustrates
that while a relatively strong alkali, such as trisodium
These compounds were employed at various concen
phosphate in the present example, is eifective in produc
trations and in each case the temperature was maintained
ing the aforesaid improvement, it must be cautiously em
at 126° C. for three hours. The products obtained
ployed with respect to ‘the amount used and the condi
thereby were clari?ed by ?ltration and the ?ltrates neu
tions of treatment in order to avoid excessive depolym
tralized with hydrochloric acid. The mucilaginons ma
erization of the mucilaginons material. As can ‘be seen
terials were precipitated from the ?ltrates by the addi
from Table 5, the employment of an excessive amount of
tion of isopropyl alcohol. After further dehydration
trisodium phosphate depolyrnerized the mucilaginous ma
with isopropyl alcohol the precipitated mucilaginons ma
terial to the point where its milk reactivity was adversely
terials were dried at 65 ° C.
atfected.
A specimen of the mucilaginons material precursive to
Example 5
the above preparations of this example was prepared by
precipitating with isopropyl alcohol a portion of the origi
Portions of a ?ltered extract of Irish moss, said ex
nal ?ltered extract of Irish moss, omitting both the or
tract containing 1.89% mucilaginous material, were heated
ganic reagent and the three-hour heating period. The
precipitate was further dehydrated with isopropyl alcohol
with various amounts of sodium metaborate. The tem
perature was maintained at 126° C. for three hours. The
products obtained thereby were ?ltered and the ?ltrates
and dried at 65° C.
Data on all of the preparations of this example are
neutralized with hydrochloric acid. The mucilaginons
materials were precipitated from the ?ltrates by the addi
tion of isopropyl alcohol. After further dehydration with
given in Table 7.
TABLE 7
isopropyl alcohol the precipitated mucilaginons materials
Amt. of
were dried at 65° C.
A specimen of the mucilaginons material precursive
to the above preparations of this example was prepared 55
by precipitating with isopropyl alcohol a portion of the
original ?ltered extract of Irish moss, omitting both the
sodium metaborate and the three-hour heating period.
The precipitate was further dehydrated with isopropyl
Data on all of the preparations of this example are
given in Table 6.
TABLE 6
'l‘reat-
of mucilaginous
ment,
material
pH1
Milk
Aqueous
Vis-
reac~
ge
cosity 4
S0.‘
65
reagent, 'I‘reat- Milk Aqueous
percent of ment, reactgel
Vlscos- 804 B
muci-
laginous
pH 1
ivity i strength 5
ity 4
material
5
alcohol and dried at 65 ° C.
NaBOQ, percent
Reagent
Fluid
498
25.84
(C1H40H)aN.
8. 9
41. 3
Fluid
139
25.73
(CiHlOH) N.
. _ _ .. _ . _ _ ___. _ . _ __
. _ _ _ _ _-
9. 2
29. 5
Fluid
9. 6
10.0
10.9
11.2
s. a
40.8
50. 7
73. 1
87. 5
53. 9
Fluid
Fluid
Fluid
Fluid
Fluid
(CuHlOH) 3N.
__
(C;H40H)4N0H- _(CQHlOHMNOH- .(OBH4OH>4NOH_ _.
(C5 niNoH _____ _-
I12
28
56
112
5. s
(CsHs) iNOH _____ _-
28
(CHahCeHgNOH.-(
ahceHtN
_,_
(CHQsColhNOH---
5. 6
56
46. 2
5i ____ .
154
278
281
364
341
24. 64
27.07
25. 70
25. 27
2s. 3s
11. 8
80.8
Fluid
359
26. 05
8. 6
ll. 8
48. 2
67. 4
Fluid
Fluid
376
422
28. 48
26. 39
12. 1
102. 7
Fluid
336
25. 40
tivity 1 strength 3
39. 3
8. 1
561
25. 39
43. 1
Fluid- _ _
275
25. 40
5t]. 3
Fluid-.-
257
25. 16
1 As in Example 1.
2 As in Example 1.
5 As in Example 1.
4 As in Example 1.
I Not corrected for moisture content of mucilaginons material.
0 Precursive material, not heated with alkali.
70
1 As in Example 1.
1 As in Example 1.
I As in Example 1.
4 As in Example 1.
5 Not corrected for moisture content of mucilaginons material.
'1 Preeursive material, not treated.
This example demonstrates that the alkali employed in
the practice of this invention may be an organic one
and further demonstrates that any alkali, inorganic or
75 organic, may be ‘thus employed, provided it is suf?ciently
8,094,517
21
22
precipitating with isopropyl alcohol a portion of the
original ?ltered extract of Irish moss, omitting both the
alkalies and the three-hour heating period. The precipi
strong to a?ford a sufficient concentration of hydroxyl
By here employing successively stronger organic
ions.
alkalies, a progression is obtained from the feebly alkaline
"triethanolamine which is practically inelfective in improv
tate was further dehydrated with isopropyl alcohol and
ing the gel-forming properties of the inuciiaginous mate- 5 dried at 65° C.
_
rial to the strongly alkaline unsubstituted tetraalkyl- or
Data on all of the preparations of this example are
aryltrialkylammonium hydroxides. The latter, as is well
‘given in Table '8.
TABLE 8
anon)“
NaOH,
percent percent of
0t
mncilaglnous 111a-
mucilaginons
material
Treatment,
Milk
pH 1
reactivity 2
Aqueous
g
strength 8
Viscosity 4
SO, '
terlal
(6)
61
s1
e1
(ii
______________ ._
121
121
121
121
ans
24.53
0
6. 1
30. a
61
12. 1
12. 2
12. 5
12. s
134. s
14s. 6
117. 9
as. 1
23. 50
2s. 11
29. 41
27. 17
o
a. 1
30.3
01
12. 2
12. a
12. 5
12. s
15s. 3
150. 5
111. 3
36. a
28. as
27.14
29. as
27. 23
1 As in Example 1.
i As in Example 1.
8 As in Example 1. e
a
‘
1 As in Example 1.
I Not corrected for moisture content of mucllaglnons material.
I! Precurslve material, not treated.
known, approach in strength the alkalimetal hydroxides,
and it is here seen that they are thereby capahle'of effect
This example demonstrates that the forti?cation of a
mild alkali, such as calcium hydroxide, with a strong
alkali, such as sodium hydroxide, is generally disadvan
ing an improvement in the gel-forming properties of the
tageous for the alkali treatment of the mncilaginous
'mucil'aginous material of the order attainable with cal 30 ' material of Irish moss. The tendency of the strong
cium hydroxide. 'Being stronger than calcium hydroxide,
alkali to depolymerize the mucilaginous material more
they are effective at lower concentrations. Moreover, at
than offsets any enhancement it might afford to the
"such concentrations they exhibit a relatively slight tend
action of the calcium hydroxide to improve the gel-form
ency to depolymerize the mncilaginous material. In this
ing
properties of the mucilaginous material.
35
respect they are in marked contrast ‘to the strong alkali
metal hydroxides, such as sodium hydroxide or potassium
Example 8
hydroxide, whose tendency to depolymerize the mucilagi
A ?ltered extract of Irish moss, said extract containing
1.80% of mucilaginous material, was heated with an
nous material is so severe as to render them disadvan
tageous for the practice of this invention.
The rela
tively small quantities required of these strong organic
alkalies and their relatively mild degradative effect on
the mucilaginous material would render their use ad—
,vantageous for the practice of this invention were it not
for their present high cost which renders their employ
anion-exchange resin. Amberlite IRA-400, in the amount
of 1110% of the weight of mucilaginous material in the
solution. The temperature was maintained at 95° C.
for ten hours. The solution had apH value of H9 at
the end of this heating period. The resin was then re
ment economically prohibitive. A further disadvantage 45 moved from the solution by decantation and ?ltration.
The ?ltrate was neutralized by hydrochloric tcid and
of these reagents would be the presence in the product
the mucilaginous material precipitated therefrom by the
of possibly toxic quaternary ammonium salts such as
addition of isopropyl alcohol. After further dehydration
with isopropyl alcohol the precipitated mucilaginous
would render the improved rnucilaginous material un?t
for use in food products.
‘ A forth-er observation with regard to this example is 50 material was dried at 65° C.
A specimen of the mucilaginous material precursive to
that the improved mucilaginous materials show no de
the above preparation of this example was prepared by
precipitating with isopropyl alcohol a portion of the
original ?ltered extract of Irish moss, omitting both the
‘with the practice of this invention may be attended by 55 anion-exchange resin and the ten-hour heating -period.
crease in sulfa-tecontent from that of the precursive
material. "Although 'mprovement of the mucilaginous
material of 'lrish'mos's 'by'alkaii treatment in accordance
more or less cleavage and removal of sulfate, the present
example demonstrates“ that such removal of sulfate is not
necessarily a concomitant of said improvement.
Example 7
The precipitate was ‘further dehydrated with isopropyl
alcohol and dried at 65° C.
Data on the preparations of this example are given
in Table 9.
60
TABLE 9
‘Portions of a’?ltered extract of Irish moss, said extract
containing 1.65% mucilaginous material, were heated
Product
with calcinmih'ydroxide'both alone and with the addition
of
magmas, The heating was maintained at
7 "rec hours. Each portion after heating 65 ePrecurslve'm-aterial ________ __
I26" ‘C. ‘for th
Reslntreated material _____ _‘wasi'iilteredto remove excess calcium hydroxide. The
Milk
reactlvlty!
A ueous
Viscos
qgel
lty 8
strength I
45.5
Fluid
5B 7
72.3
Fluid
as;
SO; 4
"?ltrates were neutralized with hydrochloric acid and the
mucilaginous materials precipitated therefrom 'by the
addition of isopropyl alcohol. After further dehydration
1 As'ln Example 1.
i As in Example}.
with isopropyl alcohol the precipitated mucilaginous 70'
4 Not corrected for moisture content of muellaglnous material.
materials were dried at 165°C. The dried mncilaginous
I As inrExample ,1.
,
V
This example further illustrates that any reagent capable
of affording a su?icient concentration of hydroxyl ions
gelifor'ining power, and‘vis‘c'osit-y in aqueous solution.’
W111 be e?ectivc in improving the gel-forming power of
A specimen of the mucilag'inous material precursive to
the mucilaginous material of Irish moss.
75
the above preparations of this example was prepared by
, materials were tested ‘for their milk reactivity, aqueous
3,094,517
23
The employment of an anion-exchange resin as a source
of hydroxyl ions, here cited as an extreme instance of the
general principle involved in the practice of this invention,
24
groups, as in this example, can be accomplished while the
alkali also acts concomitantly to effect a very substantial
improvement in the gel-forming properties of the result
is not highly practical at the present time since anion~ex
ant mucilaginous material even though it has been par
change resins in their present state of development are not
tially desulfated in the process.
highly stable to heat and suffer deterioration at the tem
Example 10
peratures required in said practice of the invention. Were
it not for this disability, the use of an anion-exchange
A quantity of commercial dried unbleached Irish moss
resin might be attractive, since it might then be recovered
was pulverized and blended to uniformity. Portions were
and regenerated to be used repeatedly.
10 macerated with 60° C. water to which had been added
calcium hydroxide in the amount of 50% of the weight
Example 9
of dry, pulverized Irish moss taken. The macerations
Portions of a ?ltered extract of Irish moss, said extract
were completed by milling the resulting pulps in a Premier
containing 1.67% of mucilaginous material, were heated
colloid mill to produce viscous pastes wherein the weight
with various amounts of strontium hydroxide. The tem- 15 of dry, pulverized moss incorporated therein amounted
perature was maintained at 126° C. for three hours. The
to 3.6% of the ?nal weight of paste. These pastes were
products obtained thereby were ?ltered to remove stron
then heated at various temperatures, with the period of
tium sulfate formed by hydrolytic cleavage of a portion
heating in each case being six hours. Following the heat
of the monoester sulfate groups of the mucilaginous ma
ing, each paste was mixed with a ?lter aid of the diatoma
terial, and the ?ltrates were neutralized with hydrochloric 20 ceous earth type and ?ltered by suction to produce a ?l
acid. The mucilaginous materials were precipitated from
tered extract of alkali-treated mucilaginous material.
the ?ltrates by the addition of isopropyl alcohol. After
These extracts were neutralized with hydrochloric acid and
further dehydration with isopropyl alcohol the precipi
the mucilaginous material then precipitated therefrom by
tated mucilaginous materials were dried at 65° C.
the addition of isopropyl alcohol. The precipitates were
A specimen of the mucilaginous material precursive to 25 further dehydrated with isopropyl alcohol and dried at
the above preparations of this example was prepared by
65° C. Data on these preparations are given in Table 11.
TABLE 11
Temp. 0!
Treat-
treatment,
ment,
° C,
pH 1
Milk
Yield 3
43. 4
43. 8
44. 1
Aqueous
Viscos-
reactl-
ge
ity 0
vity I
strength ‘
76. 2
114.7
139. 6
33 4
50 0
67 5
S04,
Ca,
percent I percent 0
11B
212
124
22 93
22 95
23 20
Theo.
percent
Ca, per
Ca for
cent 01‘
Ca carra~
gcenete 1
thco.
3. 26
4.32
4.88
4. 76
4. 77
4. B3
68. 5
90. 5
99. 0
I As in Example 1.
1 Percent of Irish moss used.
a As in Example 1.
4 As in Example 1.
A As in Example 1.
0 Not corrected for moisture content oi’ mucilaginous material.
'1 Calculated from 80¢ according to theoretical ratio of Ca: 250‘ for a Cu galactose sulfate.
precipitating with isopropyl alcohol a portion of the orig- 45
This example illustrates the application of my invention
inal ?ltered extract of Irish moss, omitting both the stron
to the treatment of the whole seaweed so that the improve
tium hydroxide and the three-hour heating period. The
precipitate was further dehydrated with isopropyl alcohol
ment of the gelling properties of the mucilaginous material
therein is effected simultaneously with the digestion of the
and dried at 65° C.
seaweed and extraction therefrom of the mucilaginous ma
Data on all of the preparations of this example are 50 terial in its improved form. It further con?rms that alkali
given in Table 10.
treatment at the higher temperatures within the range I
TABLE 10
have found to be optimal for the practice of this inven
Sr OH) , percent
oémucilaginous
ment,
Treat-
reactiv-
Milk
Aqueous
material
pH i
ity 2
strength 8
41. 0
73. 1
150. l
gel
11.1
25. 4
104. 7
Viscos
ity 4
283
186
100
S0‘ 6
55
25. 77
22. 97
16. 08
_
5 Not corrected for moisture content of mucilaginous material.
6 Precursive material, not heated with alkali.
‘I Approximate determination by "Hydrion" indicator paper.
The alkaline reagent employed in this example is one
which is also effective in bringing about the hydrolytic
at lower temperatures. Moreover the observation that
the yield of mucilaginous material from Irish moss re
mains substantially the same as the different temperatures
of treatment and regardless of the degree of improvement
in gelling properties effected on the mucilaginous material
con?rms that said improvement represents a fundamental
change in the nature of the mucilaginous material and is
1 As in Example 1.
I As in Example 1.
B As in Example 1.
4 As in Example 1.
tion results in a greater degree of improvement in gelling
properties of the mucilaginous material than is obtained
65
not due merely to extraction of other, more strongly
gelling constituents of the Irish moss, as might be the case
if an increase in yield were found for the more highly
improved mucilaginous material. Nor can said improve
ment be due to the degradation and elimination of Weakly
gelling components of the ‘Irish moss to leave as recover
cleavage of monoester sulfate from the molecule of mu
able only a strongly-gelling component, as might be the
cilaginous material by removing said sulfate as the in
case if a decrease in yield were found for the more highly
soluble strontium sulfate. Although one would expect 70 improved mucilaginous material.
that a very extensive elimination of monoester sulfate
groups from the mucilaginous material would be destruc
tive of its gel-forming properties insofar as these depend
on cross-linkage through said groups, it is seemingly the
Example 11
Portions of a ?ltered extract of Irish moss were heated
case that removal of a moderate proportion of these 75 with calcium hydroxide in the amount of about 120%
3,094,517
26
25
of the weight of mucilaginous material in the portion
carrageenate was replaced by potassium. The resulting
taken. The heating was maintained for six hours at
various temperatures as shown in Table 12. Each por
coagulum was then pressed into a moist cake containing
13% of dry solids. Portions of this cake were further
treated with an aqueous solution containing 50% by
tion after heating was ?ltered to remove excess calcium
hydroxide. Each ?ltrate was then passed, in accordance
with known techniques, through a column containing a
weight of isop'ropyl alcohol and ‘various percentages by
Another portion from the same lot of ?ltered extract
of Irish moss was passed directly through a cation-ex
ride.
Data on all of the preparations of this example are
weight of potassium chloride, as shown in Table 13. The
ratio taken of this solution to the moist cake was Sal by
cation-exchange resin, Amberlite IR-d‘20, in the sodium
weight; the temperature and duration of the treatment
form. The purpose of this operation was to convert the
were 20° C. and 30 minutes, respectively. ‘The excess
mncilaginous material in the ?ltrate into its sodium salt.
Said sodium salt of each mucilaginous material was pre 10 solution was separated from the cake by draining and
pressing, and the cake was dried at 65° C. The‘resulting
cipitated from the e?luent solution from the ion-exchange
products consisted essentially of potassium calcium salts
column by the addition of isopropyl alcohol. After fur
of the alkali-modi?ed carrageenan with the ratio of po
ther- dehydration with isopropyl alcohol the precipitated
tassium to calcium therein being greater for those which
‘sodium salt of each mucilaginous material was dried at
15 had been treated with larger amounts of potassium chlo
65° C.
given in Table 13.
change column as in the foregoing procedure but with
omission of the prior heating with the calcium hydroxide.
The effluent solution was precipitated with isopropyl alco 20
hol, further dehydrated with isopropyl alcohol, and dried
TABLE 13
at 65’ C. ‘to yield the sodium salt of the mucilaginous
material precursive to the above preparations of this
example.
Data on all of the preparations of this example are 25
given in Table 12.
K01 percent in 50% isopropyl
alcohol treatment solution
TABLE 12
'
Treat-
Milk re-
Vis-
alkali treatment,
ment,
activity 2
cosity 3
‘’ 0.
pH 1
Not treated _______________ __
99 _______________ __
12. 3
115 ______________ .12.1
61. 9
126. 8
180.1
1022
385
126 ______________ __
219. 7
Ca,
SO‘,
strength i
0. 21
O. 39
0. S9
1. 88
t}. 20
131. 5
269. 9
357. I
358. 2
290. 6
287. 8
385
ll. (11
0. 01
0.01
29. 10
29. 25
29.00
185
0. 01
27. 84
t as in Example 1.
Milk re
activity *
103. 0
95. 0
81. 3
78. 8
76. 2
67. B
1 Percent of product.
2 As in Example 1.
a As in Example 1.
percent * percent ‘l
1 As in Example 1.
8 As in Exam
product 1
8. 94
Temperature of
l2. 2
Excess KCl Aqueous
retained in
gel
35
This example illustrates the degree of aqueous gelling
ability attainable with carrageenates which have been
40 subjected to alkali treatment in accordance with the prac
tice of my invention when the potential aqueous gel
e 1.
4 Percent ofmoisture-free product.
forming ability induced thereby is activated by associa
tion of the alkali-modi?ed carrageenate with the proper
In this example the precu-rsive mucilaginous material
was of high quality with respect to milk reactivity and
‘degree of polymerization. This is re?ected in the ex
45
cations. It is further evident that the gelling effect ob
served in this example arises through introduction of
potassium as a counter ion to the alkali-modi?ed car
rageenate anion and not to any desolubilizing or “salt
ing-out" e?ect due to the presence in the product of
tremely high degree of milk reactivity attained upon its
excess potassium chloride. In fact, it is seen that the
improvement in accordance with the practice of my in
vention. Moreover, this example illustrates that the 50 presence of potassium chloride in substantial excess has
a deleterious effect on the aqueous gel-forming ability of
mucilaginous material retains the property of milk re
the product.
activity when it is in the form of a salt, such as the
'sodium salt, which is known'not to form a gel with water.
Example 13
Furthermore, this example shows that treatment of the
Portions were taken from a well-mixed lot of dried
mucilaginous material, in accordance with the practice of 55 seaweed
of the Eucheuma species which is harvested on
my invention, with an alkali, such as calcium hydroxide,
which does not form a highly insoluble sulfate, does not
the southeast coast of Africa and known to the trade by
such names as Zanzibar weed, thick type Gracilaria, and
eliminate sulfate from the mocilaginous material through
Eucheuma cottonii. These portions were macerated with
hydrolytic cleavage, unless the treatment be carried out
at a relatively high temperature, in which case a small 60 60° C. water to which had been added various amounts
of calcium hydroxide. The macerations were completed
amount of sulfate is round to be thus eliminated. It pro
by milling the resulting pulps in a Premier colloid mill to
vides a further illustration that the improvement in gell
produce pastes wherein the weight of seaweed incor
ing properties of the muoilaginous material is not neces
porated amounted to 3.4% of the ?nal weight of paste.
sarily attended by elimination of sulfate therefrom.
Each paste was divided into three portions, each of which
65
Example 12
was heated for three hours at 98° C., 115° C. and 126°
A neutral solution containing about 1.6% of alkali
modi?ed calcium carrageenate, which had been produced
C., respectively. Following the heating, each portion of
paste was mixed with a ?lter aid of the diatomaceous
earth type and ?ltered by suction to produce 'a'?ltere'd ex
tice of this invention, was coagulated by the addition of 70 tract of alkali-treated seaweed mucilage. These extracts
were neutralized with hydrochloric acid and the mucilagi
isopropyl alcohol’ containing potassium chloride in the
nous material precipitated therefrom by the addition of
amount of 70% of the weight of calcium carrageenate
isopropyl alcohol. The precipitates were further dehy
present in the solution. This potassium salt acted on
drated with isopropyl alcohol and dried at 65° C. Data
the coagulum of calcium carrageenate to effect an ion
exchange whereby a portion of the calcium of the calcium .75 on these preparations are given in Table 14.
by treatment of Irish moss in accordance with the prac
3,094,517
TABLE 14
Temp.
Treat-
percent 01
Oa(OH) 1,
of
ment,
seaweed l
treat-
pH I
Milk
Yield I
reactivity 4
Aqueous
Ca,
g
Vis-
strength 5
S04,
coslty '1
a,
percent 1 percent 7
percent
of thee.8
ment, "0
98
115
126
7. 9
8. 1
8. 2
44. 7
44. 3
44. 6
24. 2
22. 6
22.0
34. 7
27. 9
22. 2
278
162
56
25. 28
26.09
25. 40
0.37
0.39
0. 45
7. 2
7. 7
8. 7
98
116
126
8. 9
8. B
8. 9
45. 3
44. 2
46. 3
23. 1
24. 5
22. 1
39. 5
37. 7
36. 1
08
85
62
26. 80
27.66
27. 04
1. 54
1. 57
1. 65
27. 4
27. 4
27. 4
98
115
126
10. 6
10.1
9. 5
43. 9
44. 9
46. 1
34. 9
35.1
33. 6
104. 8
103.7
91. 9
246
212
163
26. 98
26.88
27. 10
l. 96
2.00
2.02
36. 1
36. 6
35. 6
98
116
126
11.8
11.8
11.9
42. 3
39. 7
42. 3
90.1
164.6
192. 6
239. 6
395. 7
670. 2
333
367
431
26.12
25.83
26. 01
3.38
3. 68
3. 43
62.0
68.3
63. 5
98
116
126
12. 3
12.3
12.2
42. 9
43.3
41.0
162.0
203. 6
211. 4
431. 8
551. 6
645. 7
293
276
333
26. 30
26. 46
26.59
4. 43
4. 32
4. 32
80. B
78. 4
78.4
98
116
126
12.3
12.2
12.2
43. 7
44. 8
42.3
181. 6
208.1
210. 0
443. 8
573. 4
618. 6
287
316
431
26. 00
26.48
26. 85
4. 20
4. 04
4. 20
77. 9
73.1
75.0
98
115
126
12. 0
11.9
11.7
41.6
41.4
40.9
164. 3
217.0
241. 0
398. 5
616.6
641.7
465
373
402
25. 73
25. 72
26.11
4. 28
4.10
4.11
79. 9
77.0
76.0
98
115
126
12. 3
12.3
40. 1
155. 2
39. 8
40.2
160. 5
200. 1
395. 3
537. 3
12.2
630. 1
333
26. 70
4. 12
74. 0
499
436
26. 67
27.39
4. 06
4.16
78. 1
72. 1
I Based on dried seaweed containing 19% moisture.
9 As in Example 1.
4 Percent of moisture-tree product based on moisture-free seaweed.
4 As in Example 1.
I As in Example 1.
I As in Example 1.
7 Based on moisture-free product.
5 Observed ratio of Cato S04 calculated as percent of theoretical ratio Ca: 2S04=0.208 for a Ca hexose sulfate
This example illustrates the unusually high capability 35 monoester sulfate groups of the mucilaginous material
combine with calcium in the course of the treatment with
of the mucilaginous material of Zanzibar weed for im
calcium hydroxide. Presumably the remaining monoestcr
provemcnt of its gelling properties in accordance with the
sulfate groups remain in combination with potassium and
practice of my invention. As much as a tenfold increase
other cations present in the prccursive mucilaginous ma
in milk reactivity and a twenty-fold increase in aqueous
gel strength are seen to be attainable thereby. This un 40 terial.
By way of contrast to this behavior, one can cite the
carrageenan of Irish moss which, as it naturally occurs,
appears to contain less than an optimal amount of po
tassium, so that forti?cation of carrageenan, either as it
found to be effective for the modi?cation of the car 45 naturally occurs or as it is improved by the practice of
this invention, with potassium ions enhances its aqueous
rageenan of Irish moss.
usual susceptibility of the Zanzibar weed mucilage to
the type of alkaline hydrolysis which is the subject of
my invention is further shown by its response to treat
ment by lower concentrations of alkali than have been
Moreover, I have found, and illustrated in this example,
that modi?cation of the naturally-occurring mucilage of
gel-forming ability to the maximum permitted by its poly
saccharide structure. For carragcenan as it naturally oc
curs this maximum appears to be about the same as that
Zanzibar weed, in accordance with certain ways of prac
ticing my invention, affords directly a mucilaginous ma 50 for the naturally-occurring mucilage of Zanzibar weed.
The maximum which I have been able to attain with
terial capable of forming extremely strong gels with ‘water,
alkali-modi?ed carrageenan, however, is less than I have
no further treatment of said mucilaginous material to as—
achieved with the alkali-modi?ed mucilage of Zanzibar
sociate more potassium ions therewith being required. In
weed.
fact, it is found that the addition of more potassium ions
Examination of the yeld data of Table 14 indicates that
thereto produces no further enhancement of aqueous gel 55
the improvement in gelling properties of Zanzibar weed
strength. While potassium ions appear ‘to be involved in
mucilage cannot be due to extraction from the weed of
the usual formation of aqueous gels by the naturally
additional, strongly-gelling components already present
occurring mucilage of Zanzibar weed as ‘well as by said
therein, nor to destruction of feebly-gelling components
mucilage after improvement according to the practice of
this invention, it is seemingly the case that said mucilagc 60 therein. Thus the improvement of the gelling properties
of the mucilaginous material of Zanzibar weed, in accord
contains an amount of potassium which is optimal for
aqueous gel formation within the limits imposed by the
ance with the practice of this invention, appears to be due
structure of the naturally-occurring polysaccharide. It
to chemical changes in the mucilaginous material and not
further appears that said polysaccharide structure is one
to extraction of different substances from the weed. In
which tcnaciously retains potassium ions. Modi?cation 66 this respect, the result I have obtained with the mucilagi
of the polysaccharide structure by alkaline hydrolysis in
nous material of Zanzibar weed is similar to that with
accordance with the practice of this invention improves
the carrageenan of Irish moss.
its potential ability to form aqueous gels, and when this
The data of this example further show that the chemi
invention is practiced in certain ways, ‘as illustrated by
cal changes which take place on alkaline hydrolysis of
this example, the improved mucilaginous material still 70
the polysaccharide of Zanzibar weed, in accordance with
retains an optimal amount of potassium and hence aque
the
practice of this invention, do not necessarily result in
ous gels prepared therefrom are not further improved by
the elimination of monoester sulfate groups from said
the addition of more potassium ions.
polysaccharide. Here again the behavior of Zanzibar
Further evidence for this surmise is found in this ex
weed
polysaccharide is similar to that of canrageenan.
ample wherein it is found that only about 80% of the 76
3,094,517
r
:29
30"
whose improvement is an object of this invention. It is
seen that the behavior of Zanzibar weed mucilage is simi
lar to carrageenan in these respects.
The polysaccharide of Zanzibar weed has not been sub
jected to extensive investigation of the sort which has
been devoted to carrageenan. ,Hence little, is known of
its structure. My'investigations show that it closely re
sembles kappa-carrageenan in its content of 3,6-anhydro
galactose residues and monoester sulfate groups, and in
Example 15
Portions were taken from a well mixed lot of dried
Gignrtina radula and macerated with 60° C. water to
which had been added various amounts of calcium hy
its infrared absorption spectrum. None of these char
acteristics change signi?cantly on alkaline hydrolysis.
'I‘his absence ‘of readily detectable chemical distinctions
droxide. The maoerations were completed by milling the
among kappa-carrageenan and the natural and alkali 10 resulting pulps in a Premier colloid mill to produce pastes
wherein the weight of Gigartina radula incorporated
modi?ed Zanzibar weed polysaccharides offers no clue as
amounted to about 3 % of the weight of paste. Each paste
to why Zanzibar weed polysaccharidc should exhibit spec
was then'heated for three hours at 98° C. Following the
tacular changes in its gelling'properties on alkaline hy
heating, each paste was mixed with a '?lter aid of the
drolysis while kappa-cari'agcenan does not. Nor does it
afford any insight into whatever chemical changes alka 15 diatornaceous earth type and ?ltered by suction to produce
a ?ltered extract of alkali-treated mucilage of Gig'artina
line hydrolysis effects on Zanzibar weed polysaccharide.
radula. These extracts were neutralized with hydrochlo
One may conjecture'that alkaline hydrolysis as applied to
ric acid and the mucilaginous material precipitated there
this polysaccharide produces rearrangement of monocster
from by the addition of isopropyl alcohol. The precipi
sulfate groups therein in a manner similar to that postu
tlated hcrcinabove from canrageenan, but without exten 20 tates were further dehydrated with isopropyl alcohol and
dried at 65° C. Data on these preparations are given in
sive formation of 3,6-anhydro rings or alterations in
glycosidic linkages.
Table 16.
Example 14
A neutralized ?ltrate, of alkali-modi?ed mucilage of 25
Zanzibar weed which had been prepared by treatment of
the weed with 13% of its weight of calcium hydroxide at
98° (3., in the manner described in Example 13,.was
divided into two portions. One portion was precipitated
TABLE 16
Ca(0H)1, percent of Gigartina
Milk
radttla 1
reactivity 1*
l*)
E5)
34. 9
36. 0
53. l
with isopropyl alcohol and thegprecipitate further dehy
drated with isopropyl alcohol and dried at 65“ C. to yield
Viscosity 1
GB, per
cent *
333
0. an
727
671
689
4. 62
5. ‘i9
8. 66
442
2. 53
the potassium calcium salt of the alkali-modi?ed mucilage
of Zanzibar weed. The other portion was subjected to
cation exchange with the sodium form of Amberlitc
‘IR-120 resin as in Example 11, and the ion-exchanged 35
‘solution precipitated with isopropyl alcohol. The precipi
tate was further dehydrated with isopropyl alcohol and
dried at 65 ° C. to yield the sodium salt of the alkali~modi
1 Based on commercial dried Gigariina mdula containing about 30%
moisture.
1' As in Example 1.
3 As in Example 1.
4 Percent of inoisture'trec product.
Thisexample demonstrates that alkaline hydrolysis, ac
cording to the practice of this invention, is also applicable
A neutralized?ltratc of a more extensively alkali-modi 40 to the mucilage of Gigartina radala, although it appears
that this mucilage is less susceptible to improvement of its
lied mucilage of Zanzibar weed which had been prepared
gel-forming properties thereby than is the carrageenan of
by treatment of the weed with 13% of its weight of cal
'fied mucilage of Zanzibar weed.
Irish moss or the mucila‘ge of the Eucheuma species here
inabove referred to as Zanzibar weed.
cium hydroxide at 126° C. in the manner described ‘in
Example 13, was divided into two portions. These por
tions were then worked up as in the foregoing procedures
‘of the present example to yield, respectively, the potas
sium calcium'salt and the sodium salt of a Zanzibar weed
mucilage which had been subjected to more extensive
alkaline hydrolysis than had the foregoing one of this
example.
Data on the preparations of this example are given in
Table 15.
TABLE 15
Aqueous
80!,
Ca,
Ca,
CutOH); treat- mucllaga reacge
ment, ‘’ C.
inous
tivlty 1 Strength2
Temp. of
Salt of
Milk
per.
cent 5
percent 3
por
cent of
material
As a concomitant of the increase in milk reactivity ob
- tained by the practice of this invention the improved muci
laginous material also has an increased ability .to suspend
cocoa in milk.
50
then.‘
K Ca
Na
161.8
388. 4
26.13
161. B
(5)
26. 60
3.92
<0. 01
72 1
K Ca
209. 4
615. 4
Na
198. 6
(5)
26. 29
3. 88
70. 9
26. 59
<0. 01
0
0
1 As in Example 1.
2 As in Example I.
' Percent oi moisture-free product.
4 Observed ratio of Ca to 504 calculated as percent of theoretical ratio 65
Ca :2SO4=0.208 for a Ca hexose sulfate.
1 Completely ?uid.
The amount of mucilaginous material re
quired to suspend a given amount of cocoa in milk is in
versely related to the milk reactivity of said material, and
by employing mucilaginous materials improved according
to the practice of this invention said suspension of cocoa
can be accomplished with 90% or less of the amount
which would be required of the precursivc, unimproved
material.
It is apparent from the foregoing that the present in
vention permits the production from a certain class of
seaweeds, as hereinabove de?ned, of mucilaginous mate
rials of an improved nature which are novel and useful
products in that they possess severalifold greater gelling
ability for both water and milk than do the mucilaginous
materials precursive to said improved mucilaginous ma
terials, as said precursive materials ordinarily occur in the
aforesaid seaweeds and as they are extracted therefrom
by prior known methods. Moreover, these improved mu
cilaginous materials may be produced by simple and in
expensive methods of such a nature as can be combined
with and simultaneously carried out during processes for
This example establishes that the milk reactivity of the
the
extraction and recovery of the mucilaginous materials
alkali-modi?ed mucilage of Zanzibar weed is virtually
independent of the cations associated with said mucilage. 70 from the aforesaid seaweeds. Moreover, the aforesaid
improved mucilaginous materials, by extending by sev
It further establishes that the ability of said mucilage to
eral fold the range of water and milk-gelling abilities
form aqueous gels depends on the cations associated there
hitherto obtainable in mucilaginons materials extracted
with and is completely suppressed when the cation so as
from seaweeds, extend the usefulness and scope of appli
sociated is one, such as sodium, which is not conducive to
aqueous gel formation by seaweed mucilages of the types 75 cation of mucilaginous materials extracted from seaweeds.
3,094,517
31
I claim:
1. A process for the treatment of a polysaccharide of
seaweeds of the Gigartinaceae and Solieriaeeae families
containing ester sulfate groups within the range of about
5% to about 13% sulfur, which comprises heating the
polysaccharide at a temperature of from about 80° C. to
about 150° C. in an aqueous medium containing calcium
hydroxide in an amount that is over 10% of the weight
32
provided by at least one of said hydroxides which is un
dissolved in said medium.
9. A process according to claim 6 wherein said tem
perature of from about 80° C. to about 150° C. is main
tained for a period of about three to six hours.
10. A process for the treatment of a polysaccharide
of seaweeds of the Gigartinaceae and Solieriaceae fam
ilies, said polysaccharide containing ester sulfate groups
within the range of about 5% sulfur to about 13% sulfur
of the polysaccharide.
2. A pnocess according to claim 1 wherein said poly 10 which comprises subjecting the polysaccharide to alkaline
saccharide is contained in seaweed and said treatment is
carried out during extraction of the polysaccharide from
said seaweed.
3. A process according to claim 2 wherein said heating
treatment of the polysaccharide is carried out for about
three hours to about six hours while the alkaline s01uti0n
containing extracted polysaccharide remains unseparated
from the seaweed, separating said solution while it is
hydrolysis in an aqueous medium at a pH between about
9.5 and about 13 at a temperature between about 80° C.
and about 150° C., said aqueous medium containing a
compound selected from the group consisting of barium
hydroxide and strontium hydroxide which is reactive with
said ester sulfate group to form a sulfate which is insolu~
ble in said aqueous medium.
11. A process for the treatment of a polysaocharide of
seaweeds of the Gigartinaceae and Solieriaceae families,
insoluble materials, and thereafter neutralizing the sep 20 said polysaccharide containing ester sulfate groups within
the range of about 5% to about 13% sulfur, which proc
arated solution.
ess comprises subjecting the polysaccharide to alkaline
4. A process according to claim 1 which comprises
hydrolysis in an aqueous medium at a pH between about
beating the polysaccharide at a pH between about 11 and
within said temperature range and at an alkaline pH from
about 12.5 for a period of about three to six hours.
5. A process according to claim 1 wherein the amount
of calcium hydroxide is at least about 50% by dry weight
of the polysaccharide.
6. A process for the treatment of sulfated polysaccha
ride ‘of seaweeds of the Gigartinaceae and Solieriaceae
families, which comprises subjecting said polysaccharide
to substantial alkaline hydrolysis in an aqueous medium
containing alkaline material consisting substantially en_
9.5 and about 13 at a temperature between about 80° C.
and about 150° C., said aqueous medium containing ca
tions selected from the group consisting of barium and
strontium which are reactive with said ester sulfate group
to form sulfates insoluble in said aqueous medium.
12. A polysaccharide obtained by the process of claim
1 from a precursive polysaccbaride of the Eucheuma
species of seaweed known as Eucheuma cottonii, Zanzibar
weed and ‘thick type Gracilaria.
tirely of alkaline material selected from the group con
sisting of the hydroxides of calcium, of barium and of
strontium, sodium carbonate, trisodium phosphate and
sodium metaborate at a sustained pH between about 9.5
and about 13 and at a temperature of from about 80“ C.
to about 150° C., said ‘alkaline material being substantially
in excess of the amount thereof consumed during said
alkaline hydrolysis and the total amount of said alkaline 40
material being at least 10% of the dry weight of said
polysaccharide.
7. A process according to claim 6 wherein said hy
dnolysis is effected until the content of anhydrosugar 45
residues is increased in an amount at least 10% greater
that that of the precursive polysaccharide.
8. A process according to claim 6 wherein said excess is
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,382,286
Blihovde ____________ __ Aug. 14, 1945
2,427,594
Frieden _____________ __ Sept. 16, 1947
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Byrne _______________ __ Apr. 20, 1948
Le Gloahec __________ __ June 12, 1951
McCormack __________ _- Apr. 22, 1952
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Moe ________________ __ June 10,
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