close

Вход

Забыли?

вход по аккаунту

?

j.jlumin.2018.08.050

код для вставкиСкачать
Author’s Accepted Manuscript
Y2O3:Nd3+
nanocrystals
as
ratiometric
luminescence thermal sensors operating in the
optical windows of biological tissues
I.E. Kolesnikov, A.A. Kalinichev, M.A.
Kurochkin, D.V. Mamonova, E.Yu. Kolesnikov,
A.V. Kurochkin, E. Lähderanta, M.D. Mikhailov
PII:
DOI:
Reference:
www.elsevier.com/locate/jlumin
S0022-2313(18)30788-9
https://doi.org/10.1016/j.jlumin.2018.08.050
LUMIN15848
To appear in: Journal of Luminescence
Received date: 2 May 2018
Revised date: 12 August 2018
Accepted date: 15 August 2018
Cite this article as: I.E. Kolesnikov, A.A. Kalinichev, M.A. Kurochkin, D.V.
Mamonova, E.Yu. Kolesnikov, A.V. Kurochkin, E. Lähderanta and M.D.
Mikhailov, Y 2O3:Nd3+ nanocrystals as ratiometric luminescence thermal sensors
operating in the optical windows of biological tissues, Journal of Luminescence,
https://doi.org/10.1016/j.jlumin.2018.08.050
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
could affect the content, and all legal disclaimers that apply to the journal pertain.
Y2O3:Nd3+ nanocrystals as ratiometric luminescence thermal sensors operating in the
optical windows of biological tissues
I.E. Kolesnikov*,a,b, A.A. Kalinicheva, M.A. Kurochkina, D.V. Mamonovac, E.Yu. Kolesnikovd,
A.V. Kurochkina, E. Lähderantab, M.D. Mikhailovc
a
St. Petersburg State University, 7/9 Universitetskaya nab., 199034, St. Petersburg, Russia
Lappeenranta University of Technology LUT, Skinnarilankatu 34, 53850, Lappeenranta,
Finland
c
Scientific and Technological Institute of Optical Material Science, VNTs S. I. Vavilov State
Optical Institute, Babushkina 36-1, 192171, St. Petersburg, Russia
d
Volga State University of Technology, Lenin sqr. 3, 424000, Yoshkar-Ola, Russia
b
Contact information
e-mail address: ie.kolesnikov@gmail.com (I. Kolesnikov)
Abstract
Here, we report Nd3+-doped Y2O3 nanoparticles suitable for luminescence thermal sensing in the
first and second biological windows. The nanoparticles were synthesized via the combined
Pechini-foaming method. A ratiometric approach, based on the relative changes in the intensities
of different emission bands corresponding to the Stark sublevels or excited levels, was applied to
determine local temperature. The evaluated thermal sensitivities differed 5-fold times depending
on the choice of transitions for the luminescence intensity ratio calculation. The temperature
uncertainty was determined to be below 1 oC, which allows to perform sub-degree thermal
sensing. The results of ex vivo experiment indicate that Nd3+-doped Y2O3 nanoparticles are
promising candidates for real biological applications.
Keywords: Nd3+, Y2O3, Luminescence, Thermometry, Biological windows
Introduction
An accurate thermal measurement is highly demanded in many areas from technology to
biomedical field [1–3]. The conventional temperature sensors, such as thermocouples and
thermistors, are unsuitable for remote temperature measurement at the micro and nanoscale [4,5].
Much attention is paid to the development of new classes of non-invasive, non-contact
nanothermometers exhibiting superior spatial and temperature resolution coupled with high
thermal sensitivity [6]. One of the most promising classes of such thermal sensors is
luminescence nanothermometers. Among many different luminescent materials used as noncontact luminescent temperature sensors, inorganic hosts doped with lanthanide ions have
attracted significant interest due to their unique advantages compared to those of the other
luminescent thermometers such as quantum dots, polymers, and organic phosphors. In particular,
these phosphors exhibit high chemical, mechanical, and thermal stability, perfect photostability,
no photo blinking effects, as well as demonstrate wide usable temperature sensitivity range [7,8].
Real-time temperature sensing during hyperthermia treatment is of crucial importance to reduce
the overheating side effects. To perform in vivo thermal sensing, excitation and emission bands
of luminescent thermometer have to lie in spectral region where transparency of living tissues is
high due to low optical absorption [9,10]. There are three such regions, so-called biological
optical transparency windows (BW): 750-950 nm (I-BW), 1000-1350 nm (II-BW), 15001
1800 nm (III-BW), which contributes to the deep tissue imaging prospects in a different way
[11,12]. In terms of imaging, the I-BW can suffer from the interference of tissue
autofluorescence [13,14] nevertheless the exceptional tissue penetration properties of the I-BW
are commonly exploited for effective NIR laser excitation [15]. The II-BW and III-BW are
significantly better suited for NIR imaging at greater tissue depths [16], due to extremely
reduced NIR light scattering [17,18]. Thus, ideal luminescent nanothermometer should be
excited in the I-BW and emit light in the II-BW or III-BW [19].
Nd3+ ions perfectly fit aforementioned requirements having shielded ladder-like intra-4f levels.
Nd3+-doped nanoparticles (NPs) can be effectively excited with NIR light of around 800 nm
wavelength, which avoids undesired heating of the surrounding [20,21] and subsequent faulty
temperature readout. Additionally, Nd3+-doped NPs demonstrate quite intensive emission lines
situated in all three BW, which broaden possible application in deep tissue in vivo imaging and
nanothermometry [15,22,23].
Usually manuscripts devoted to the ratiometric Nd3+-doped thermometers are focused on the
single temperature dependent parameter [24–26]. In this work, we report Y2O3:Nd3+ NPs to
demonstrate luminescent temperature sensing in the first and second biological windows upon
NIR excitation using various luminescence intensity ratios. The important parameters for
nanothermometry such as thermal sensitivity and temperature uncertainty have been calculated
and compared with other Nd3+-doped sensors. The potential in vivo application of Y2O3:Nd3+
NPs has been explored by carrying out ex vivo experiments.
Experimental
Nd3+-doped Y2O3 nanoparticles was synthesized by the combined Pechini-foaming
method. Unlike previously developed modified Pechini technique [27,28], this method
also reduces agglomeration of derived particles but does not require second calcination
procedure in molten salt. The main part of modification in the combined Pechini-foaming
method is implementation of foaming agent into polymer gel matrix in order to prevent
strong agglomeration of synthesized samples. The foaming agent is mixture of aluminium
nitrate and potassium chloride.
Synthesis of Eu3+ and Nd3+-doped oxides using the combined Pechini-foaming method
were described in details in our previous papers [29–31]. Therefore, only short
description of Y2O3:Nd3+ 1 at.% nanocrystalline phosphors synthesis is presented.
Briefly, aluminium nitrate was added to the yttrium and neodymium nitrates in molar
ratio Al(NO3)3:Y(NO3)3=5:3. Then saturated solution of citric acid in distilled water
(volume ratio 1:1) and potassium chloride powder were successively added to the
abovementioned solution. The resultant mixture was heated up to 150–200 oC leading to
the chelate complexes formation. The acid excess reacts with the salt, which results in the
potassium dihydrogen citrate formation; oxidized, it forms potassium carbonate. Adding
the ethylene glycol in the solution leads to the etherification reaction with formation of
the polymer gel as a result. The polymer gel contains aluminium, yttrium and europium
ions which are uniformly distributed in polymer network and potassium carbonate which
are situated in polymer cells. In order to remove organic components, the gel is calcinated
at 1000 oC for 2 hours. Uniformly distributed aluminium oxide reacts with potassium
carbonate, which results in formation of KAlO2 accompanied by intense gas release. Y2O3
nanoparticles with homogeneously distributed Nd3+ ions are obtained, whereas reaction
2
byproducts are removed by washing in distilled water. The synthesized nanoparticles
were collected by centrifugation at 2800 rpm for 5 min and then dried naturally.
X-ray diffraction patterns were registered with the powder diffractometer UltimaIV (Rigaku) in
Bregg-Bretano geometry with CuKα1 radiation (λ = 1.54059 Å) in the 2θ range from 10o to 80o.
Electron micrograph images were obtained with SUPRA 40VP WDS scanning electron
microscope (resolution 4 nm). Particle size was measured with laser diffraction particle size
analyzer Mastersizer 3000 using static light scattering technique. Fluorescence characterization
was performed with fluorescence spectrometer Fluorolog-3 and T64000 Raman Spectrometer.
Nd3+-doped Y2O3 NPs was optically excited with a 808 nm single mode laser Coherent MBR110 (5 mW) and 532 nm solid state laser Thorus 532 (1 mW). The laser beam was focused into
the sample by using a 4x long working distance microscope objective (NA 0.1). The
fluorescence was collected by using the same microscope objective and was spectrally analyzed
by single spectrometer and a liquid nitrogen cooled Symphony II CCD detector. Thermal
sensitivity and uncertainty experiments were carried out using heating stage controlled with
ThorLabs TC200 with a resolution of 0.1 °C. Sub-tissue temperature sensing was performed with
chicken breast as a phantom of human tissue. 50 µl of aqueous colloidal solution of Nd3+-doped
Y2O3 NPs (5 mg mL−1) was injected in fresh chicken breast at the different depths. The colloidal
solution was prepared by dispersing powder particles in deionized water with further sonification
for 5 min.
Results and discussion
Fig. 1a presents XRD pattern of Y2O3:Nd3+ 1 at.% nanocrystalline phosphors which
demonstrates presence of Y2O3 as a single phase without any impurities. All diffraction patterns
coincide with cubic phase of Y2O3 (JCPDS 41-1105). Fig. 1b shows scanning electron
microphotograph of the synthesized Y2O3:Nd3+ 1 at.% powder. As seen from the micrograph, the
powder consists of weakly agglomerated nanoparticles with average size about 40–50 nm. The
particle size distribution of Y2O3:Nd3+ 1 at.% powder determined using static light scattering
(SLS) technique demonstrates the mean size at about 54 nm (Fig. 1c), which indicates a good
correlation between SLS and SEM data.
Figure 1. (a) XRD pattern of Y2O3:Nd3+ 1 at.% and standard card of Y2O3 (JSPDS 41-1105);
(b) SEM image of Y2O3:Nd3+ 1 at.% nanoparticles with particle size distribution as insert; (c)
particle size distribution in aqueous solution of Y2O3:Nd3+ 1 at.% determined using static light
scattering.
Excitation spectrum of Y2O3:Nd3+ 1 at.% NPs is shown in Fig. 2a. Spectrum measured in the
spectral range 350–850 nm consists of intra-configurational f-f transitions from ground level 4I9/2
to excited levels in Nd3+ ion. During scanning excitation wavelength luminescence signal was
3
monitored at the prominent transition 4F3/2 – 4I11/2 (λem=1079.4 nm). Excitation bands were
observed at 350–382, 420–445, 455–495, 500–557, 560–642, 665–705, 710–780, 780–850 nm.
They were ascribed to the transitions of 4I9/2 – 4D3/2+ 4D1/2, 4I9/2 – 2D5/2, 4I9/2 – 4G9/2+4G11/2+2K15/2,
4
I9/2 – 4G7/2+4G9/2+2K13/2, 4I9/2 – 4G5/2+4G7/2+2H11/2, 4I9/2 – 4F9/2, 4I9/2 – 4F7/2+4S3/2, 4I9/2 – 4F5/2+4H9/2
respectively [32]. In this paper, luminescence of Y2O3:Nd3+ NPs was excited by 808 and 532 nm,
which is schematically shown in Fig. 2a.
Emission spectrum of nanocrystalline Y2O3:Nd3+ powder upon 808 nm is presented in Fig. 2b. It
should be noted that all emission spectra presented in this work were not corrected for the
detector response. Measured spectrum consisted of characteristic narrow lines attributed to the
transitions from excited 4F3/2 to the lower 4IJ levels: 4F3/2 – 4I9/2 (870–985 nm) and 4F3/2 – 4I11/2
(1042–1160 nm). Each transition consists of several lines corresponding to the Stark splitting of
excited and ground levels due to crystal field. Emission spectrum is dominated by 4F3/2(1) –
4
I11/2(2) transition centered at 1079.4 nm. However, it should be noted that intensive
luminescence bands were observed in both I-BW and II-BW.
Figure 2. (a) Excitation and (b) emission spectra of Y2O3:Nd3+ 1 at.% nanoparticles.
Nowadays, ratiometric Nd3+ based NPs provide two different methods for thermal sensing. The
first one is based on the analysis of emission bands corresponding to the transitions between
Stark sublevels of 4F3/2(Ri) and 4I9/2(Xj) or 4I11/2(Yk) energy levels.
Detailed emission spectra of Y2O3:Nd3+ 1 at.% NPs at different temperatures (26.5 and 58.5 oC)
measured in the spectral range of 870–922 nm (I-BW) are presented in Fig. 3a. The
luminescence intensity ratio between 4F3/2(2) – 4I9/2(3) and 4F3/2(1) – 4I9/2(3) (hereafter denoted as
1 ) and between 4F3/2(2) – 4I9/2(1) and 4F3/2(1) – 4I9/2(1) (hereafter denoted as 2 ) were chosen for
nanothermometry (Fig. 3b), because they should have temperature dependence in biological
range due to the value of energy gap between Stark sublevels. As can be seen, the emission lines
used for thermal sensing are well resolved, so deconvolution analysis is not required. According
to previous study, luminescence intensity ratio (LIR) was calculated using integral intensities
(integration width was about FWHM) instead of peak intensities, resulting in the better thermal
sensitivity and temperature uncertainties [33]. Both obtained LIRs demonstrated monotonous
pseudo-linear trend within studied temperature range (Fig. 3c, 3d).
4
Figure 3. (a) Emission spectra of Y2O3:Nd3+ 1 at.% nanoparticles obtained at two different
temperatures (λex=808 nm); (b) energy levels scheme of transition 4F3/2(Ri) – 4I9/2(Xj) for Nd3+
ion in the Y2O3 host; (c), (d) luminescence intensity ratios 1 and 2 as a function of
temperature. Red lines correspond to the best fitting.
Thermal sensing using Y2O3:Nd3+ 1 at.% NPs was performed also in the II-BW. Detailed
emission spectra at different temperatures (26.5 and 58.5 oC) measured in the spectral range of
1040–1090 nm are presented in Fig. 4a. Nanothermometry was based on the luminescence
intensity ratio between 4F3/2(2) – 4I11/2(1) and 4F3/2(1) – 4I11/2(1) (hereafter denoted as 1 ) and
between 4F3/2(2) – 4I9/2(2) and 4F3/2(1) – 4I11/2(2) (hereafter denoted as 2 ) (Fig. 4b). Fig. 4c and
4d showed aforementioned LIRs as a function of temperature from which a pseudo-linear
behavior was observed.
5
Figure 4. (a) Emission spectra of Y2O3:Nd3+ 1 at.% nanoparticles obtained at different
temperatures (λex=808 nm); (b) energy levels scheme of transition 4F3/2(Ri) – 4I11/2(Yk) for
Nd3+ion in the Y2O3 host; (c), (d) luminescence intensity ratios 1 and 2 as a function of
temperature. Red lines correspond to the best fitting.
It should be noted that the adjusted R2 were found to be 0.99 for all luminescence intensity ratios
in both I-BW and II-BW. So, the obtained thermal calibrations could provide information about
local temperature around Y2O3:Nd3+ NPs.
Besides thermal sensing using 4F3/2(Ri) – 4I9/2(Xj) or 4F3/2(Ri) – 4I11/2(Yk) Stark components, an
alternative method relies on LIR between 4F5/2(4) – 4I9/2(3) (820 nm) and 4F3/2(1) – 4I9/2(1)

(892 nm) transitions (532
) (Fig. 5a). Due to the higher energy difference between excited levels
used for nanothermometry, significant enhancement of the relative thermal sensitivity should be
observed. Moreover, this LIR can be potentially used for thermal sensing at high temperature. In
this case the luminescence of Y2O3:Nd3+ 1 at.% NPs was excited with 532 nm radiation (Fig.
5b). Emission spectra consist of narrow lines attributed to the following transitions: 4F5/2(4) –
4
I9/2(3) (820.4 nm), 4F5/2(2) – 4I9/2(3) (829 nm),4F5/2(3) – 4I9/2(4) (838.4 nm), 4F3/2(2) – 4I9/2(1)
(876.7 nm), 4F3/2(2) – 4I9/2(2) (878.8 nm), 4F3/2(1) – 4I9/2(1) (892.3 nm), 4F3/2(1) – 4I9/2(2)
(894.6 nm), 4F3/2(2) – 4I9/2(3) (897.4 nm), 4F3/2(1) – 4I9/2(3) (913.8 nm), 4F3/2(2) – 4I9/2(5)
(929.4 nm), 4F3/2(1) – 4I9/2(5) (946.4 nm). It should be noted that luminescence intensity of
emission lines assigned to the transitions from 4F5/2 level is much lower than from 4F3/2 one and
the corresponding part of spectrum is multiplied by 20. As it can be seen, the intensity of 4F5/2 –
4
I9/2 transitions increased with temperature increase, whereas the intensity of 4F3/2 – 4I9/2
transitions reduced. Dependence of LIR on the temperature within biological range is shown in
6
Fig. 5c. The thermal calibration was fitted with linear function similar to other luminescence
intensity ratios.
Figure 5. (a) Energy levels scheme of transition 4F5/2 – 4I9/2 and 4F3/2 – 4I9/2 for Nd3+ion in the
Y2O3 host; (b) emission spectra of Y2O3:Nd3+ 1 at.% nanoparticles obtained at different

temperatures (λex=532 nm); (c) luminescence intensity ratios 532
as a function of temperature.
Red line corresponds to the best fitting.
An absolute thermal sensitivity expresses the suitability of the luminescent thermometer for
temperature sensing. However, in order to compare the thermal performances between different
nanothermometers irrespective of their nature, it is very useful to evaluate the relative thermal
sensitivity Srel, which can be expresses as follows:
  =
1 
 
∙ 100%
(1)
where R is obtained LIR. The relative thermal sensitivities of Y2O3:Nd3+ 1 at.% NPs calculated
for Stark sublevels and 4F5/2, 4F3/2 levels LIRs are listed in Table 1. Table 1 includes also the
relative thermal sensitivities of different Nd3+-based NPs as well as excitation wavelength, LIR
transition and thermal sensing range. Careful examination of Table leads to conclusion that
among NIR-to-NIR nanothermometers Y2O3:Nd3+ nanophosphor demonstrates the best relative
thermal sensitivity. It should be noted that thermal sensitivity in the I-BW showed lower value
than in the II-BW. Thermal sensing based on LIR between 4F5/2 – 4I9/2 and 4F3/2 – 4I9/2 transitions
7
demonstrates almost 5-fold enhancement of sensitivity compared with Stark sublevels. The
obtained value of 1.59 % oC-1 is close to the maximum relative sensitivities 1.75±0.04 % oC-1 and
1.8 % oC-1 attained for Gd2O3:Nd3+ [34] and YAlO3:Nd3+ NPs [35], respectively. However, it
should be emphasized that emission of Gd2O3:Nd3+ NPs was measured with R928
photomultiplier, whereas in this work a simple charge coupled device (CCD) InGaAs-based
detector was used.
Table 1. Comparison of Nd3+-doped nanoparticles as ratiometric thermometers.
Host
λex
LIR transitions
Temperature Srel, (% oC-1)
(nm)
range (oC)
Y2O3
808 4F3/2 – 4I9/2 (Stark sublevels, 1 )
25–60
0.23
4
4

25–60
0.31
F3/2 – I9/2 (Stark sublevels, 2 )
4
4
25–60
0.43
F3/2 – I11/2 (Stark sublevels, 1 )
4
4

25–60
0.37
F3/2 – I11/2 (Stark sublevels, 2 )
4
4
4

532
25–60
1.59
F5/2, F3/2 – I9/2 (532 )
4
4
NaYF4
830
F3/2 – I9/2 (Stark sublevels)
0–150
0.12
4
4
-196–100
0.11
NaYF4
808
F3/2 – I9/2 (Stark sublevels)
4
4
YAG
808
F3/2 – I9/2 (Stark sublevels)
10–70
0.15
4
4
YNbO4
752
F3/2 – I9/2 (Stark sublevels)
30–200
0.28
4
4
LaF3
808
F3/2 – I9/2 (Stark sublevels)
30–70
0.26
4
4
LaF3
808
F3/2 – I9/2 (Stark sublevels)
20–60
0.48
4
4
YVO4
808
F3/2 – I9/2 (Stark sublevels)
25–60
0.19
4
4
YVO4
808
F3/2 – I11/2 (Stark sublevels)
25–60
0.25
4
4
KGd(WO4)2 808
F3/2 – I9/2 (Stark sublevels)
25–60
0.12
4
4
F3/2 – I11/2 (Stark sublevels)
25–60
0.17
4
4
4
4
CaF2
808
F3/2 – I11/2 / F3/2 – I9/2
21–65
0.12
(Stark sublevels)
Gd2O3
580 4F5/2, 4F3/2 – 4I9/2
15–50
1.75
4
4
4
YAlO3
532
F5/2, F3/2 – I9/2
20–337
1.80
4
4
4
YVO4
532
F5/2, F3/2 – I9/2
-150–600
1.50
Ref
This
work
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[34]
[35]
[46]
If the relative sensitivity is used to compare the performance of different thermometers, the
temperature uncertainty, ΔT, defines the accuracy of temperature evaluation using
nanothermometer and specific experimental setup. As it was shown in our previous paper [33],
the temperature uncertainty can be calculated with various methods. Here, it was obtained from
acquisition of several consecutive emission spectra at a fixed temperature. 50 emission spectra of
Y2O3:Nd3+ 1 at.% NPs were measured at heating stage with controlled temperature (30 oC). The
statistical distributions of temperature determined from luminescence thermometry were fitted
by Gauss function and FWHM was used as an estimation of the temperature uncertainty. The

temperature uncertainties were calculated for LIRs with the highest thermal sensitivities (532
,
1 and 2 ), and the obtained results are presented in Fig. 6. The temperature uncertainties are
below 1 oC, which makes Nd3+-doped Y2O3 NPs perspective candidates for thermal sensing with
sub-degree resolution.
8
Figure 6. Statistical distributions calculated from various luminescence intensity ratios
(Theater = 30 oC).
It should be noted that the temperature uncertainty can be decreased by improving signal-tonoise ratio by increasing acquisition time and/or by averaging consecutive measurements of the
emission spectrum. Usually thermal sensing in real applications requires fast measurement, so
one must have a compromise between decreasing the acquisition time and lowering the
temperature uncertainty. If acquisition time in certain type of measurement should not be
minimized, the minimum achievable temperature uncertainty is defined by the uncertainty of the
experimental setup, in the order of ∼0.0001% for the case of a laboratory-grade
spectrofluorimeter [34].
To probe the potential use of Nd3+-doped Y2O3 NPs for temperature changes investigation in
biological systems, simple ex vivo experiment has been carried out. We injected 50 µl of aqueous
colloidal solution of Y2O3:Nd3+ 1 at.% NPs (5 mg mL−1) in fresh chicken breast at the different
depths. Chicken breast was used to mimic optical properties of human tissue. Experimental setup
is schematically presented in Fig. 7a. Briefly, low intensity 808 nm laser beam excited emission
of NPs through chicken breast. Laser intensity was kept minimal (5 mW) to avoid induced
heating effects. Optical excitation and subsequent luminescence collection were both performed
by using a single long working distance 4x objective. Spectral analysis and LIR calculation of
the sub-tissue luminescence signal was used to determine the injection’s temperature. Taking
into account extinction coefficient of tissue and thermal sensitivity of studied LIR, sub-tissue
temperature sensing was performed in the II-BW using 1 intensity ratio. The temperatures
obtained for different tissue depths and their errors are presented in Fig. 7b. The average
temperature was found to be 26.3 oC, which is very close to the value measured with
thermocouple (26.5 oC). It should be noted that increasing of tissue depth significantly increases
thermal sensing error. The provided experiments demonstrated the applicability of Nd3+-doped
Y2O3 NPs for temperature determination purposes in ex vivo biomedical studies with a good
thermal resolution.
The carried out study opens an avenue toward controllable photothermal treatment, which is
crucial to reduce collateral damage. Bio-functionalized Nd3+-doped Y2O3 NPs can be utilized to
search temperature singularities in vivo for diagnostic purposes. Noteworthy, along with submicrometric spatial and sub-degree thermal resolution use of ratiometric luminescence
thermometers and CCD camera as a detector provide real-time sensing, so local temperature can
be defined with sub-second temporal resolution. All these features are of great importance in real
biological and medical applications.
9
Figure 7. (a) Scheme of the experimental setup for ex vivo temperature sensing; (b) calculated
temperature as a function of tissue depth.
Conclusion
In this work, Nd3+-doped Y2O3 nanoparticles have been synthesized by the combined Pechinifoaming method. Single phase Y2O3:Nd3+ 1 at.% phosphor consists of nanoparticles with average
size about 50 nm, which was determined with SEM and SLS measurements. Two different
approaches were applied to provide ratiometric thermal sensing: 1) LIR was based on the
analysis of emission bands corresponding to the transitions between Stark sublevels of 4F3/2(Ri)
and 4I9/2(Xj) or 4I11/2(Yk); 2) LIR was calculated between transitions from different excited
energy levels (4F5/2 – 4I9/2 and 4F3/2 – 4I9/2). The main advantage of the first approach is to have
both excitation and emission lines in the biological windows, which plays crucial role in
biological and medicine applications, whereas the second approach enhances thermal sensitivity
5-fold but requires using 532 nm excitation. The temperature uncertainty obtained from
acquisition of several consecutive emission spectra at fixed temperature was determined to be
below 1 oC. This makes Nd3+-doped Y2O3 NPs perspective candidates for thermal sensing with
sub-degree resolution. Ex vivo measurements conducted with chicken breast proved possibility
of luminescence temperature sensing in the II-BW through 3 mm tissue.
Acknowledgments
This research has been supported by the Russian Science Foundation (№ 17-72-10055).
Experimental investigations were carried out in “Center for Optical and Laser materials
research“, “Research Centre for X-ray Diffraction Studies“, “Interdisciplinary Resource Center
for Nanotechnology”, and “Innovative Technologies of Composite Nanomaterials“ (St.
Petersburg State University).
References
[1]
Jaque D, Vetrone F. Luminescence nanothermometry. Nanoscale 2012;4:4301.
doi:10.1039/c2nr30764b.
[2]
Balabhadra S, Debasu ML, Brites CDS, Rocha J, Carlos LD. Implementing luminescence
thermometry at 1.3μm using (GdNd)2O3 nanoparticles. J Lumin 2016.
doi:10.1016/j.jlumin.2016.07.034.
[3]
Marciniak L, Bednarkiewicz A, Drabik J, Trejgis K, Strek W. Optimization of highly
10
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
sensitive YAG: Cr 3+, Nd 3+ nanocrystal-based luminescent thermometer operating in an
optical window of biological tissues. Phys Chem Chem Phys 2017;19:7343–51.
Fischer LH, Harms GS, Wolfbeis OS. Upconverting nanoparticles for nanoscale
thermometry. Angew Chemie Int Ed 2011;50:4546–51.
Thyageswaran S. Developments in Thermometry from 1984 to 2011: A Review. Recent
Patents Mech Eng 2012;5:4–44.
McCabe KM, Hernandez M. Molecular thermometry. Pediatr Res 2010;67:469–75.
Jaque D, Jacinto C. Luminescent nanoprobes for thermal bio-sensing: Towards controlled
photo-thermal therapies. J Lumin 2016;169:394–9. doi:10.1016/j.jlumin.2015.03.037.
Brites CDS, Lima PP, Silva NJO, Millán A, Amaral VS, Palacio F, et al. Thermometry at
the nanoscale. Nanoscale 2012;4:4799–829. doi:10.1039/c2nr30663h.
Weissleder R. A clearer vision for in vivo imaging. Nat Biotechnol 2001;19:316.
Smith AM, Mancini MC, Nie S. Second window for in vivo imaging. Nat Nanotechnol
2009;4:710. doi:10.1038/nnano.2009.326.
Hemmer E, Venkatachalam N, Hyodo H, Hattori A, Ebina Y, Kishimoto H, et al.
Upconverting and NIR emitting rare earth based nanostructures for NIR-bioimaging.
Nanoscale 2013;5:11339–61.
Xu J, Murata D, Ueda J, Tanabe S. Near-infrared long persistent luminescence of Er 3+ in
garnet for the third bio-imaging window. J Mater Chem C 2016;4:11096–103.
Alec M, Lomnes SJ, Lee DS, Pietrzykowski M, Ohnishi S, Morgan TG, et al. Tissue-like
phantoms for near-infrared fluorescence imaging system assessment and the training of
surgeons. J Biomed Opt 2006;11:14007.
del Rosal B, Villa I, Jaque D, Sanz‐ Rodríguez F. In vivo autofluorescence in the
biological windows: the role of pigmentation. J Biophotonics 2015.
Skripka A, Benayas A, Marin R, Canton P, Hemmer E, Vetrone F. Double rare-earth
nanothermometer in aqueous media: opening the third optical transparency window to
temperature sensing. Nanoscale 2017;9:3079–85.
Hong G, Diao S, Chang J, Antaris AL, Chen C, Zhang B, et al. Through-skull
fluorescence imaging of the brain in a new near-infrared window. Nat Photonics
2014;8:723–30.
Naczynski DJ, Tan MC, Zevon M, Wall B, Kohl J, Kulesa A, et al. Rare-earth-doped
biological composites as in vivo shortwave infrared reporters. Nat Commun 2013;4.
Wang R, Li X, Zhou L, Zhang F. Epitaxial Seeded Growth of Rare‐ Earth Nanocrystals
with Efficient 800 nm Near‐ Infrared to 1525 nm Short‐ Wavelength Infrared
Downconversion Photoluminescence for In Vivo Bioimaging. Angew Chemie Int Ed
2014;53:12086–90.
Hemmer E, Benayas A, Légaré F, Vetrone F. Exploiting the biological windows: current
perspectives on fluorescent bioprobes emitting above 1000 nm. Nanoscale Horizons
2016;1:168–84.
Xie X, Gao N, Deng R, Sun Q, Xu Q-H, Liu X. Mechanistic investigation of photon
upconversion in Nd3+-sensitized core–shell nanoparticles. J Am Chem Soc
2013;135:12608–11.
kumara gnanasammandhan Jayakumar M, Idris NM, Huang K, Zhang Y. A paradigm shift
in the excitation wavelength of upconversion nanoparticles. Nanoscale 2014;6:8441–3.
Kolesnikov IE, Tolstikova DV, Kurochkin AV, Platonova NV, Pulkin SA, Manshina AA,
et al. Concentration effect on structural and luminescent properties of YVO4:Nd3+
nanophosphors. Mater Res Bull 2015;70:799–803.
doi:10.1016/j.materresbull.2015.06.023.
Suo H, Zhao X, Zhang Z, Guo C. 808 nm light-triggered thermometer–heater
upconverting platform based on Nd3+-sensitized yolk–shell GdOF@ SiO2. ACS Appl
Mater Interfaces 2017;9:43438–48.
Rakov N, Maciel GS. Near-infrared emission and optical temperature sensing
11
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
performance of Nd3+: SrF2 crystal powder prepared by combustion synthesis. J Appl
Phys 2017;121:113103.
Ortgies DH, Teran FJ, Rocha U, de la Cueva L, Salas G, Cabrera D, et al. Optomagnetic
Nanoplatforms for In Situ Controlled Hyperthermia. Adv Funct Mater 2018;28:1704434.
Rocha U, Upendra Kumar K, Jacinto C, Ramiro J, Caamaño AJ, García Solé J, et al. Nd3+
doped LaF3 nanoparticles as self-monitored photo-thermal agents. Appl Phys Lett
2014;104:53703. doi:10.1063/1.4862968.
Dolinskaya YA, Kolesnikov IE, Kurochkin A V., Man’shina AA, Mikhailov MD,
Semencha A V. Sol-gel synthesis and luminescent properties of YVO4 : Eu nanoparticles.
Glas Phys Chem 2013;39:308–10. doi:10.1134/S1087659613030061.
Kolesnikov IE, Povolotskiy A V, Tolstikova D V, Manshina AA, Mikhailov MD.
Luminescence of Y3Al5O12:Eu3+ nanophosphors in blood and organic media. J Phys D
Appl Phys 2015;48:75401. doi:10.1088/0022-3727/48/7/075401.
Kolesnikov I, Povolotskiy A, Mamonova D, Lahderanta E, Manshina A, Mikhailov M.
Photoluminescence Properties of Eu3+ Ions in Yttrium Oxide Nanoparticles: Defect vs
Normal Sites. RSC Adv 2016;6:76533–41. doi:10.1039/C6RA16814K.
Kolesnikov IE, Mamonova DV, Lähderanta E, Kurochkin AV, Mikhailov MD. The
impact of doping concentration on structure and photoluminescence of Lu2O3:Eu3+
nanocrystals. J Lumin 2017;187:26–32. doi:10.1016/j.jlumin.2017.03.006.
Kolesnikov IE, Mamonova D V., Lähderanta E, Kolesnikov EY, Kurochkin A V.,
Mikhailov MD. Synthesis and characterization of Y2O3:Nd3+nanocrystalline powders
and ceramics. Opt Mater (Amst) 2018;75:680–5. doi:10.1016/j.optmat.2017.11.032.
Gruber JB, Sardar DK, Nash KL, Yow RM. Comparative study of the crystal-field
splitting of trivalent neodymium energy levels in polycrystalline ceramic and
nanocrystalline yttrium oxide. J Appl Phys 2007;102:23103.
Kolesnikov IE, Kalinichev AA, Kurochkin MA, Mamonova DV, Kolesnikov EY,
Kurochkin AV, et al. New strategy for thermal sensitivity enhancement of Nd 3+ -based
ratiometric luminescence thermometers. J Lumin 2017;192:40–6.
doi:10.1016/j.jlumin.2017.06.024.
Balabhadra S, Debasu ML, Brites CDS, Nunes LAO, Malta OL, Rocha J, et al. Boosting
the sensitivity of Nd 3+-based luminescent nanothermometers. Nanoscale 2015;7:17261–
7.
Hernández-Rodríguez MA, Lozano-Gorrín AD, Martín IR, Rodríguez-Mendoza UR,
Lavín V. COMPARISON OF THE SENSITIVITY AS OPTICAL TEMPERATURE
SENSOR OF NANO-PEROVSKITE DOPED WITH Nd3+ IONS IN THE FIRST AND
SECOND BIOLOGICAL WINDOWS. Sensors Actuators B Chem 2017.
Wawrzynczyk D, Bednarkiewicz A, Nyk M, Strek W, Samoc M. Neodymium(iii) doped
fluoride nanoparticles as non-contact optical temperature sensors. Nanoscale 2012;4:6959.
doi:10.1039/c2nr32203j.
Marciniak L, Pilch A, Arabasz S, Jin D, Bednarkiewicz A. Heterogeneously Nd 3+ doped
single nanoparticles for NIR-induced heat conversion, luminescence, and thermometry.
Nanoscale 2017;9:8288–97.
Benayas A, del Rosal B, Pérez‐ Delgado A, Santacruz‐ Gómez K, Jaque D, Hirata GAA,
et al. Nd:YAG Near-Infrared Luminescent Nanothermometers. Adv Opt Mater
2015;3:687–94. doi:10.1002/adom.201400484.
Far LĐ, Lukić-Petrović SR, Đorđević V, Vuković K, Glais E, Viana B, et al.
Luminescence temperature sensing in visible and NIR spectral range using Dy 3+ and Nd
3+ doped YNbO 4. Sensors Actuators A Phys 2017.
Carrasco E, del Rosal B, Sanz-Rodríguez F, de la Fuente ÁJ, Gonzalez PH, Rocha U, et
al. Intratumoral Thermal Reading During Photo-Thermal Therapy by Multifunctional
Fluorescent Nanoparticles. Adv Funct Mater 2015;25:615–26.
doi:10.1002/adfm.201403653.
12
[41]
[42]
[43]
[44]
[45]
[46]
Rocha U, Jacinto C, Kumar KU, López FJ, Bravo D, Solé JG, et al. Real-time deep-tissue
thermal sensing with sub-degree resolution by thermally improved Nd3+:LaF3
multifunctional nanoparticles. J Lumin 2016;175:149–57.
doi:http://dx.doi.org/10.1016/j.jlumin.2016.02.034.
Kolesnikov IE, Golyeva EV, Kurochkin MA, Lähderanta E, Mikhailov MD. Nd3+-doped
YVO4 nanoparticles for luminescence nanothermometry in the first and second biological
windows. Sensors Actuators B Chem 2016;235:287–93. doi:10.1016/j.snb.2016.05.095.
Kolesnikov IE, Golyeva E V, Kalinichev AA, Kurochkin MA, Lähderanta E. Nd 3 +
single doped YVO 4 nanoparticles for sub-tissue heating and thermal sensing in the
second biological window. Sensors Actuators B Chem 2017;243:338–45.
doi:10.1016/j.snb.2016.12.005.
Savchuk O, Carvajal JJ, De la Cruz LG, Haro-Gonzalez P, Aguilo M, Diaz F.
Luminescence thermometry and imaging in the second biological window at high
penetration depth with Nd: KGd (WO 4) 2 nanoparticles. J Mater Chem C 2016;4:7397–
405.
Cortelletti P, Facciotti C, Cantarelli IX, Canton P, Quintanilla M, Vetrone F, et al. Nd 3+
activated CaF 2 NPs as colloidal nanothermometers in the biological window. Opt Mater
(Amst) 2016.
Kalinichev AA, Kurochkin MA, Golyeva EV, Kurochkin AV, Lähderanta E, Mikhailov
MD, et al. Near-infrared emitting YVO4:Nd3+ nanoparticles for high sensitive
fluorescence thermometry. J Lumin 2018;195:61–6. doi:10.1016/j.jlumin.2017.11.024.
13
Документ
Категория
Без категории
Просмотров
2
Размер файла
1 671 Кб
Теги
jlumin, 2018, 050
1/--страниц
Пожаловаться на содержимое документа