The interaction of the inorganic nanoparticles (GdYVO4:Eu, d 2 nm) and organic carbocyanine dye
3,3’ -diethyloxa-carbocyanine iodide (DiOC2) has been studied spectrophotometrically. The formation of
complexes of dye molecules with spherical nanoparticles GdYVO4:Eu in aqueous solutions of cationic dye
DiOC2 was found. It is shown that nanoparticle GdYVO4:Eu can form a complex with 5-10 molecules of the
cationic dye DiOC2 which leads to the decrease in the intensity of the absorption and luminescence spectra
of the dye in aqueous solution.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3500

Klochkov, V.K.

Malyukin, Yu.V.

Sorokin, A.V.

Tkacheva, T.N.

Yefimova, S.L.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 1 No 2, 02NNBM20(2pp) (2012)   2304-1862/2012/1(2)02NNBM20(2) 02NNBM20-1  2012 Sumy State University Spectroscopic Study of Cationic Carbocyanine Dye Binding to GdYVO4:Eu Nanoparticles   T.N. Tkacheva*, S.L. Yefimova, V.K. Klochkov, A.V. Sorokin, Yu.V. Malyukin  Institute for Scintillation Materials National Academy of Sciences of Ukraine, 60 Lenin Ave.,  61001 Kharkov, Ukraine  (Received 18 June 2012; published online 22 August 2012)  The interaction of the inorganic nanoparticles (GdYVO4:Eu, d  2 nm) and  organic carbocyanine dye 3,3’ -diethyloxa-carbocyanine iodide (DiOC2) has been studied spectrophotometrically. The formation of complexes of dye molecules with spherical nanoparticles GdYVO4:Eu  in aqueous solutions of cationic dye DiOC2 was found. It is shown that nanoparticle GdYVO4:Eu can form a complex with 5-10 molecules of the cationic dye DiOC2 which leads to the decrease in the intensity of the absorption and luminescence spectra of the dye in aqueous solution.  Keywords: Dye, Nanoparticle, Complex «inorganic nanoparticle - organic molecule».    PACS number: 78.67.Bf   ______________ * tkacheva@isma.kharkov.ua 1. INTRODUCTION  Modern scientific and technical progress is related to the development of new materials. In focus of new quick-ly developing scientific direction, which was nucleated on the joint of physics, chemistry, biology, electronic and computer technique and it is known under the name «nanotechnology», so-called, nano-scale objects are of specific interest. Recently, significant advances have led to a large variety of labeling reagents based on nano-materials, such as quantum dots, magnetic nanoparti-cles, lanthanide doped-compounds, fluorophore-tagged latex/silica nanoparticles, fluorophore–labeled polymeric nanospheres etc. Strong interest in such objects is dic-tated also by the fact that nanoparticles have the poten-tial to revolutionize the diagnosis and treatment of many diseases, for example cancer and infectious diseases.  In the work [1] it was shown that spheric nanoparti-cles GdYVO4:Eu of 2 nm diameter have a tendency  to be accumulated in the nucleus of living cell, that makes them very attractive for the use as nanocontainer for delivery of different substances inside of nucleus includ-ing for photodynamic therapy of the malignant tumor. The interaction of the nonorganic nanoparticles (GdYVO4:Eu, d  2 nm) and the organic carbocyanine dye 3,3’ -diethyloxa-carbocyanine iodide (DiOC2), which was used as a model system of active compounde, has been studied spectrophotometrically.     Fig. 1 – Structural formula of dye DiOC2  2. MATERIALS AND METHODS  The carbocyanine dye DiOC2 and nanoparticles GdYVO4:Eu were synthesized in Institute for Scintilla-tion Materials National Academy of Sciences of Ukraine. Chloroform (Sigma Aldrich) used to prepare stock solu-tion of the dye was a spectroscopic grade product. To prepare aqueous solution of the dye with nanoparticles, doubly distilled water was used. The concentration of the dye in the solutions was in the range of 1×10-6–2×10-4 М. The concentration of the nanoparticles in the solutions is varied within the 0,0005 g/l–2,95 g/l range. Visible absorption spectra were recorded using spec-trophotometer UV-Vis Specord 200 (Analitic, Jena). So-lutions were placed in a quartz cuvette of 2 nm optical path length. Luminescent spectra were recorded using spectrofluorimeter Lumina (Thermo Scientific, USA).  3. RESULTS AND DISCUSSION  The process of co-operation of molecules of dye with nanoparticles can be described with a balanced reaction:    nD+NPs  D(NPs)n,   where D, NPs and DNPs – dye, nanoparticle and com-plex of dye with nanoparticle respectively. As we can see from the structural formula, DiOC2 relates to salt dyes, so in polar solvents it dissociates with formation of cation and anion. Moreover, analysis of absorption spectra DiOC2 in the range of concentra-tions from 1×10-6 to 2×10-4 М shows, that Bouguer-Lambert-Beer law is satisfied and the dye is situated in water solution in monomeric form. Maximum of ab-sorption band is centered at 480 nm, luminescence maximum, at 498 nm. At the investigation of process of complex formation of the system «nanoparticle-dye molecule» two ap-proaches have been used. It is known that binding of dye molecules to the par-ticles is accompanied by changes in the absorption and luminescence spectrums [2]. In this paper we studied the effect of changes in DiOC2 dye optical density as a func-tion of GdYVO4:Eu nanoparticles concentration in aque-ous solutions. DiOC2 concentration in solutions remained constant (1,5×10-5 М), the concentration of nanoparticles varied in the range of 0,0005 –2,95 g/l. It was found that the addition of nanoparticles to the solution leads to the changes in optical density of the solution, measured at the main at maximum. (Fig. 2). It is seen that in the con-centration range 0,001 – 0,01 g/l occurs drop in the ab-sorption intensity of the dye, which is associated with the interaction of the dye with the nanoparticle and the  T.N. TKACHEVA , S.L. YEFIMOVA, V.K. KLOCHKOV ET AL. PROC. NAP 1, 02NNBM20 (2012)   02NNBM20-2 formation of complex «inorganic nanoparticle — organic molecule» [3]. In the absorption spectrum of the dye Di-OC2 is not observed the appearance of new bands, which suggests that the addition of nanoparticles does not lead to the dye aggregation on nanoparticle’s surface. Further increase in the concentration of nanoparticles, as shown in Fig. 2, leads to a gradual increase in dye’s optical den-sity. At high concentrations of nanoparticles in the solu-tion, the optical density of the solution does not change (Fig. 2). At the same time the addition of nanoparticles to the dye solution causes the same changes in the lumi-nescence spectra (Fig. 3).   0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,40,91,01,11,21,31,41,51,61,7   [NPs], g/lD0,01 g/l  Fig. 2 – Changes in DiOC2 optical density as a function of NPs concentration   0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,425003000350040004500Luminescence Intensity, arb. un.[NP], g/l      Fig. 3 – Dependence of the luminescence intensity of DiOC2 dye on NPs concentration   In the range of low concentrations of nanoparticles in solution (0,002 – 0,01 g/l) there is a reduction of the luminescence intensity of the dye measured at the main maximum. Further increase in nanoparticles con-centration does not affect the intensity of the dye lumi-nescence. Increasing the intensity of the absorption of DiOC2 dye after a certain concentration of nanoparti-cles in solution (0,01 g/l) can be explained by agglomer-ation of the nanoparticles, increase due to their concen-tration in the solution and the release of dye molecules. However, this fact requires further study. However, the concentration of nanoparticles GdYVO4:Eu 0,01 g/l can be taken as a kind of optimal concentration at which the formation of complexes «inorganic nanoparticle — organic molecule» with a maximum number of dye molecules per nanoparticle is observed. Using the mass of nanoparticles GdYVO4:Eu which equal 9,6×10-21 g [4], and the ratio of amounts of substances in solution, we obtain the composition 1:9. As a second approach to the study «inorganic nano-particle — organic molecule» complexes formation we have study the «sorption capacity» of the nanoparticles by varying the concentration of the DiOC2 dye in the concentration range (1×10-6 — 2×10-4 M) in constant con-centration of nanoparticles (0,01 g/l) (Fig. 4).   0,0 4,0x10-58,0x10-51,2x10-41,6x10-42,0x10-40,000,010,020,030,040,050,060,070,080,090,10   D:Np = 5:1D0-D1C0, M   Fig. 4 – Dependence D0-D1 from the dye concentration (where D0 and D1 – optical density of the solution without and with NPs)  The change in optical density of dye solutions with and without nanoparticles with increasing total concen-tration of the dye has been studied. As seen in Fig. 4, increasing concentrations of DiOC2 leads to a gradual increase in the part of dye associated with the nanopar-ticle, followed by the saturation region. The point of in-tersection of two tangents, as shown in Fig. 4, give us the concentration at which the binding of the dye with nano-particles is maximal (8×10-5 M). At this concentration DiOC2 about 10% of the dye molecules bound to nano-particles GdYVO4:Eu, which corresponds to the concen-tration of 7,4×10-6 M. Taking into account the weight of one nanoparticle which equal to 9,6×1021 g, the ratio of nanoparticle:dye molecule is  1:5.   4. CONCLUSION  Thus, using two approaches, the process of complex formation in the system «inorganic nanoparticle – organ-ic molecule» has been studied spectrophotometrically. The formation of complexes of dye molecules with spher-ical nanoparticles GdYVO4:Eu (d  2 nm) in aqueous solutions of cationic dye DiOC2 was found. It is shown that nanoparticle GdYVO4:Eu can form a complex with 5-10 molecules of the cationic dye DiOC2 which leads to the decrease in the intensity of the absorption and lumi-nescence spectra of the dye in aqueous solution.   REFERENCES  1.  V.K.Klochkov, N.S.Kavok, Yu.V.Malyukin, et al., National Academy of Sciences of Ukraine 10, 81 (2010).  2. B. Saha, S. Das, J. Saikia, et al., J. Phys. Chem. C 115, 8024 (2011). 3. I-Im.S.Lim, F.Goroleski, D.Mott, et al., J. Phys. Chem. B 110, 6673 (2006). 

Spectroscopic Study of Cationic Carbocyanine Dye Binding to GdYVO4:Eu Nanoparticles

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 1 No 2, 02NNBM20(2pp) (2012) 
 
 
2304-1862/2012/1(2)02NNBM20(2) 02NNBM20-1  2012 Sumy State University 
Spectroscopic Study of Cationic Carbocyanine Dye Binding to GdYVO4:Eu Nanoparticles  
 
T.N. Tkacheva*, S.L. Yefimova, V.K. Klochkov, A.V. Sorokin, Yu.V. Malyukin 
 
Institute for Scintillation Materials National Academy of Sciences of Ukraine, 60 Lenin Ave.,  
61001 Kharkov, Ukraine 
 
(Received 18 June 2012; published online 22 August 2012) 
 
The interaction of the inorganic nanoparticles (GdYVO4:Eu, d  2 nm) and  organic carbocyanine dye 
3,3’ -diethyloxa-carbocyanine iodide (DiOC2) has been studied spectrophotometrically. The formation of 
complexes of dye molecules with spherical nanoparticles GdYVO4:Eu  in aqueous solutions of cationic dye 
DiOC2 was found. It is shown that nanoparticle GdYVO4:Eu can form a complex with 5-10 molecules of the 
cationic dye DiOC2 which leads to the decrease in the intensity of the absorption and luminescence spectra 
of the dye in aqueous solution. 
 
Keywords: Dye, Nanoparticle, Complex «inorganic nanoparticle - organic molecule». 
 
  PACS number: 78.67.Bf 
 
 
______________ 
*
 tkacheva@isma.kharkov.ua 
1. INTRODUCTION 
 
Modern scientific and technical progress is related to 
the development of new materials. In focus of new quick-
ly developing scientific direction, which was nucleated on 
the joint of physics, chemistry, biology, electronic and 
computer technique and it is known under the name 
«nanotechnology», so-called, nano-scale objects are of 
specific interest. Recently, significant advances have led 
to a large variety of labeling reagents based on nano-
materials, such as quantum dots, magnetic nanoparti-
cles, lanthanide doped-compounds, fluorophore-tagged 
latex/silica nanoparticles, fluorophore–labeled polymeric 
nanospheres etc. Strong interest in such objects is dic-
tated also by the fact that nanoparticles have the poten-
tial to revolutionize the diagnosis and treatment of many 
diseases, for example cancer and infectious diseases.  
In the work [1] it was shown that spheric nanoparti-
cles GdYVO4:Eu of 2 nm diameter have a tendency  to be 
accumulated in the nucleus of living cell, that makes 
them very attractive for the use as nanocontainer for 
delivery of different substances inside of nucleus includ-
ing for photodynamic therapy of the malignant tumor. 
The interaction of the nonorganic nanoparticles 
(GdYVO4:Eu, d  2 nm) and the organic carbocyanine 
dye 3,3’ -diethyloxa-carbocyanine iodide (DiOC2), which 
was used as a model system of active compounde, has 
been studied spectrophotometrically.  
 
 
 
Fig. 1 – Structural formula of dye DiOC2 
 
2. MATERIALS AND METHODS 
 
The carbocyanine dye DiOC2 and nanoparticles 
GdYVO4:Eu were synthesized in Institute for Scintilla-
tion Materials National Academy of Sciences of Ukraine. 
Chloroform (Sigma Aldrich) used to prepare stock solu-
tion of the dye was a spectroscopic grade product. To 
prepare aqueous solution of the dye with nanoparticles, 
doubly distilled water was used. The concentration of the 
dye in the solutions was in the range of 1×10-6–2×10-4 М. 
The concentration of the nanoparticles in the solutions is 
varied within the 0,0005 g/l–2,95 g/l range. 
Visible absorption spectra were recorded using spec-
trophotometer UV-Vis Specord 200 (Analitic, Jena). So-
lutions were placed in a quartz cuvette of 2 nm optical 
path length. Luminescent spectra were recorded using 
spectrofluorimeter Lumina (Thermo Scientific, USA). 
 
3. RESULTS AND DISCUSSION 
 
The process of co-operation of molecules of dye with 
nanoparticles can be described with a balanced reaction:  
 
 nD+NPs  D(NPs)n,  
 
where D, NPs and DNPs – dye, nanoparticle and com-
plex of dye with nanoparticle respectively. 
As we can see from the structural formula, DiOC2 
relates to salt dyes, so in polar solvents it dissociates 
with formation of cation and anion. Moreover, analysis 
of absorption spectra DiOC2 in the range of concentra-
tions from 1×10-6 to 2×10-4 М shows, that Bouguer-
Lambert-Beer law is satisfied and the dye is situated in 
water solution in monomeric form. Maximum of ab-
sorption band is centered at 480 nm, luminescence 
maximum, at 498 nm. 
At the investigation of process of complex formation 
of the system «nanoparticle-dye molecule» two ap-
proaches have been used. 
It is known that binding of dye molecules to the par-
ticles is accompanied by changes in the absorption and 
luminescence spectrums [2]. In this paper we studied the 
effect of changes in DiOC2 dye optical density as a func-
tion of GdYVO4:Eu nanoparticles concentration in aque-
ous solutions. DiOC2 concentration in solutions remained 
constant (1,5×10-5 М), the concentration of nanoparticles 
varied in the range of 0,0005 –2,95 g/l. It was found that 
the addition of nanoparticles to the solution leads to the 
changes in optical density of the solution, measured at 
the main at maximum. (Fig. 2). It is seen that in the con-
centration range 0,001 – 0,01 g/l occurs drop in the ab-
sorption intensity of the dye, which is associated with 
the interaction of the dye with the nanoparticle and the 
 
T.N. TKACHEVA , S.L. YEFIMOVA, V.K. KLOCHKOV ET AL. PROC. NAP 1, 02NNBM20 (2012) 
 
 
02NNBM20-2 
formation of complex «inorganic nanoparticle — organic 
molecule» [3]. In the absorption spectrum of the dye Di-
OC2 is not observed the appearance of new bands, which 
suggests that the addition of nanoparticles does not lead 
to the dye aggregation on nanoparticle’s surface. Further 
increase in the concentration of nanoparticles, as shown 
in Fig. 2, leads to a gradual increase in dye’s optical den-
sity. At high concentrations of nanoparticles in the solu-
tion, the optical density of the solution does not change 
(Fig. 2). At the same time the addition of nanoparticles 
to the dye solution causes the same changes in the lumi-
nescence spectra (Fig. 3).  
 
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4
0,9
1,0
1,1
1,2
1,3
1,4
1,5
1,6
1,7
 
 
 
[NPs], g/l
D
0,01 g/l
 
 
Fig. 2 – Changes in DiOC2 optical density as a function of 
NPs concentration  
 
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4
2500
3000
3500
4000
4500
L
u
m
in
e
s
c
e
n
c
e
 I
n
te
n
s
it
y
, 
a
rb
. 
u
n
.
[NP], g/l
 
 
 
  
 
Fig. 3 – Dependence of the luminescence intensity of DiOC2 
dye on NPs concentration  
 
In the range of low concentrations of nanoparticles 
in solution (0,002 – 0,01 g/l) there is a reduction of the 
luminescence intensity of the dye measured at the 
main maximum. Further increase in nanoparticles con-
centration does not affect the intensity of the dye lumi-
nescence. Increasing the intensity of the absorption of 
DiOC2 dye after a certain concentration of nanoparti-
cles in solution (0,01 g/l) can be explained by agglomer-
ation of the nanoparticles, increase due to their concen-
tration in the solution and the release of dye molecules. 
However, this fact requires further study. However, the 
concentration of nanoparticles GdYVO4:Eu 0,01 g/l can 
be taken as a kind of optimal concentration at which 
the formation of complexes «inorganic nanoparticle —
 organic molecule» with a maximum number of dye 
molecules per nanoparticle is observed. Using the mass 
of nanoparticles GdYVO4:Eu which equal 9,6×10-21 g 
[4], and the ratio of amounts of substances in solution, 
we obtain the composition 1:9. 
As a second approach to the study «inorganic nano-
particle — organic molecule» complexes formation we 
have study the «sorption capacity» of the nanoparticles 
by varying the concentration of the DiOC2 dye in the 
concentration range (1×10-6 — 2×10-4 M) in constant con-
centration of nanoparticles (0,01 g/l) (Fig. 4).  
 
0,0 4,0x10
-5
8,0x10
-5
1,2x10
-4
1,6x10
-4
2,0x10
-4
0,00
0,01
0,02
0,03
0,04
0,05
0,06
0,07
0,08
0,09
0,10
 
 
 
D:Np = 5:1
D
0
-D
1
C
0
, M  
 
Fig. 4 – Dependence D0-D1 from the dye concentration (where D0 
and D1 – optical density of the solution without and with NPs) 
 
The change in optical density of dye solutions with 
and without nanoparticles with increasing total concen-
tration of the dye has been studied. As seen in Fig. 4, 
increasing concentrations of DiOC2 leads to a gradual 
increase in the part of dye associated with the nanopar-
ticle, followed by the saturation region. The point of in-
tersection of two tangents, as shown in Fig. 4, give us the 
concentration at which the binding of the dye with nano-
particles is maximal (8×10-5 M). At this concentration 
DiOC2 about 10% of the dye molecules bound to nano-
particles GdYVO4:Eu, which corresponds to the concen-
tration of 7,4×10-6 M. Taking into account the weight of 
one nanoparticle which equal to 9,6×1021 g, the ratio of 
nanoparticle:dye molecule is  1:5.  
 
4. CONCLUSION 
 
Thus, using two approaches, the process of complex 
formation in the system «inorganic nanoparticle – organ-
ic molecule» has been studied spectrophotometrically. 
The formation of complexes of dye molecules with spher-
ical nanoparticles GdYVO4:Eu (d  2 nm) in aqueous 
solutions of cationic dye DiOC2 was found. It is shown 
that nanoparticle GdYVO4:Eu can form a complex with 
5-10 molecules of the cationic dye DiOC2 which leads to 
the decrease in the intensity of the absorption and lumi-
nescence spectra of the dye in aqueous solution.  
 
REFERENCES 
 
1.  V.K.Klochkov, N.S.Kavok, Yu.V.Malyukin, et al., National 
Academy of Sciences of Ukraine 10, 81 (2010).  
2. B. Saha, S. Das, J. Saikia, et al., J. Phys. Chem. C 115, 
8024 (2011). 
3. I-Im.S.Lim, F.Goroleski, D.Mott, et al., J. Phys. Chem. B 
110, 6673 (2006). 


English

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Spectroscopic Study of Cationic Carbocyanine Dye Binding to GdYVO4:Eu Nanoparticles

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