Journal of Luminescence 176 (2016) 65–70

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Full Length Article

Influence of electric field on the properties of the polymer stabilized

luminescent quantum dots in aqueous solutions
Irina S. Zharkova a, Natalia E. Markina a, Alexey V. Markin a,n, Daniil D. Drozd a,
Elena S. Speranskaya a, Irina Yu. Goryacheva a,b
a
Saratov State University, Astrakhanskaya 83, 410012 Saratov, Russia
b
Saint-Petersburg State University, Universitetskii pr. 26, 198504 Petrodvorets, Saint-Petersburg, Russia

art ic l e i nf o a b s t r a c t

Article history: The application of external electric field for verification of quantum dots (QDs) stability in aqueous
Received 19 June 2015 medium was proposed. Hydrophilic CdSe core-shell nanocrystals were synthesized and used with three
Received in revised form polymer-based organic stabilizers, two of which contain PEG chains. An increasing of the stability under
15 February 2016
applied electric field (EF) was shown for stabilizer containing higher amount of PEG chains and terminal
Accepted 13 March 2016
Available online 18 March 2016
amino-groups: introduction of additional PEG chains allowed reducing degradation of luminescence
intensity for about 60%. The changes of QDs solutions after EF treatment were examined by dynamic light
Keywords: scattering measurements, luminescence and absorbance spectroscopy, and conductivity measurements
Quantum dots and explained by decreasing of quantum yield of the samples due to degradation of stabilizer coating.
Electric field
& 2016 Elsevier B.V. All rights reserved.
Luminescence
Colloidal stability
Aqueous medium

1. Introduction sensitized solar cells is more favorable due their electron-donor

Quantum dots (QDs) are nanomaterials with unique spectral
characteristics and a wide range of possible applications in medicine,
biological research, analytical chemistry and fabrication of electronic
devices (solar cells, light emitted diodes, etc.). High brightness, narrow
peaks of luminescence, and small size of QDs allow their application
as an alternative to molecular dyes for sensitive analytical tools, e.g.
for bioimaging [1], in vitro diagnostics [2,3] and food analysis [4,5].
QDs are widely used for solar cells and LED fabrication due their
tunable light absorption, broad excitation spectra, good photostability,
and high extinction coefficient [6,7].
However, QDs like any other nanoparticles have very high surface
area and reactivity. In order to provide stability (chemical and col-
loidal) under ambient conditions, QDs must be protected by stabi-
lizers with structure and composition depending on environment
conditions and supposed applications. Moreover, intrinsic parameters
of QDs such as profile of absorption and luminescence spectra,
quantum yield, and lifetime depend on environment composition and
can be tuned by selecting appropriate stabilizer [8]. For example, Tan
et al. [9] have shown that application of aromatic compounds (e.g.
4-dimethilaminobenzthiol) as QDs stabilizers for fabrication of QDs
n
Corresponding author. Present address: Education and Research Institute of
Nanostructures and Biosystems, Saratov State University, Astrakhanskaya 83, Sar-
atov 410012, Russia. Fax: þ7 8452 511527.
E-mail address: av_markin@mail.ru (A.V. Markin).
properties which provide faster hole transfer from QDs to stabilizer
molecule that enhances photochemical stability of QDs under ambi-
ent conditions, especially in the presence of liquid water or at high
level of humidity.
On the other hand, in vivo and in vitro sensing and imaging
require application of stabilizers with low electron (hole) accept-
ing properties in order to decrease quenching, maximize quantum
yield, and fluorescence lifetime. Additionally, bright luminescent
QDs obtained by high-temperature synthesis in organic solvents
[10,11] are usually hydrophobic and their further applications for
biological and medical purposes require hydrophilization step in
order to allow operating in aqueous media. Application of
amphiphilic brush polymers with poly(ethylene glycol) (PEG)
moieties for QDs stabilization provides appropriate colloidal sta-
bility in water while hydrophobic part (hydrocarbon chains) binds
with initially hydrophobic QDs [11–13]. Such stabilizers allow
keeping high quantum yield of hydrophilized QDs and provide
stability in wide range of pH and ionic strength. Moreover, appli-
cation of PEG-containing polymers for in vivo experiments
decreases immune system response and increases QDs blood cir-
culation time, thus making them perfectly suited for application as
stabilizers for QDs-based biomarkers.
Finally, application of QDs as components of electrochemical
sensors (e.g. as signal amplifier [14]) meets additional requirements
caused by presence of electric field and current [15,16]. For example,
Amelia et al [16] provide a thorough review of electrochemical

http://dx.doi.org/10.1016/j.jlumin.2016.03.018
0022-2313/& 2016 Elsevier B.V. All rights reserved.
66 I.S. Zharkova et al. / Journal of Luminescence 176 (2016) 65–70
properties of CdSe and CdTe QDs (both in solid and liquid states) and
methods of their investigations (cyclic voltammetry, electro-
luminescence, etc.). They are also describe the conditions (electrode
potentials, ambient conditions, etc.) at which QDs experienced elec-
trochemical changes (reduction or oxidation) accompanied by tem-
porary or permanent luminescence quenching. However, systematic
investigations of an influence of structure and chemical composition
of stabilizer coatings on the stability of QDs under external electric
field (especially in water) are actual and still required. Therefore, in
this paper we have investigated an influence of the stabilizer com-
position on CdSe/CdS/CdZnS/ZnS QDs colloidal and chemical stability
in water. The three types of amphiphilic brush polymers with and
without PEG moieties were used in order to stabilize QDs in aqueous
solutions and their protective properties against electric field of low
strength (10 V/cm) were verified.
2. Materials and methods
2.1. Reagents
Cadmium oxide (99.99%), selenium powder (99.99%), sulfur
powder (99%), zinc acetate (Zn(OAc)2, 99.99%), oleic acid (90%), 1-
octadecene (ODE, 90%), oleylamine (70%), octadecylamine (ODA,
90%), poly(maleic anhydride-alt-1-octadecene) (PMAO, M  30–
50 kDa), sodium bicarbonate anhydrous (NaHCO3, Z99.7%) were
purchased from Sigma-Aldrich (Bornem, Belgium). Jeffamine M-
1000 (  1000 g/mol) and Jeffamine ED-600 (  600 g/mol) were
kindly provided by Huntsman (Belgium) [17]. Deionized water
(15 MΩ) for all experiments was prepared in three-stage pur-
ification system (CJSC "RPC Mediana-Filter").
2.2. Synthesis of QDs
Synthesis of CdSe cores and CdSe/CdS/CdZnS/ZnS core-shell
QDs were performed via hot injection method in octadecene
according to established procedure [18]. Briefly, 5 mL of selenium
solution (0.1 M in ODE) were quickly injected into the reaction
flask containing 18 mL of cadmium oxide and oleic acid solution
(1:8 M ratios, 0.1 M of CdO) in ODE. CdSe QDs growth was carried
out at 235 °C. QDs cores purification was performed by precipita-
tion of QDs with ethanol, centrifugation of precipitate (2700 g,
5 min) and further dissolution of residue in toluene. Purification
procedure was carried out twice and then toluene solution of QDs
was flushed with Ar and stored at 4 °C.
For the typical synthesis of CdSe/CdS/CdZnS/ZnS QDs, toluene
solution containing 3  10  7 mol of CdSe cores was added to the
100 mL flask containing 10 mL of ODE and 3.5 g of octadecylamine
and heated under Ar flushing. The sulfur precursor (0.1 M in ODE)
and Cd precursor (described above) were added consecutively
(10 min between each injections) via syringe to the reaction flask
with CdSe cores. Then the Zn precursor solution (11 mL of ODE,
0.275 g of Zn(OAc)2 and 4 mL of oleylamine) were added to the
mixture and the temperature was increased to 260 °C and the
reaction mixture was annealed for 1 h in order to reduce degree of
crystalline lattice defects on the surface of QDs.
The mixture was cooled down to 70 °C after the end of
reaction and was mixed with chloroform at 5:1 ratio (v/v) in order
to prevent solidification of amine. Then the QDs were precipitated
by acetone and centrifuged (2700 g, 7 min). Finally, the precipitate
was dissolved in toluene and stored at 4 °C.
2.3. Water-solubilization of QDs
Water-solubilization of QDs was achieved by coating QDs
with various amphiphilic polymeric stabilizers; we have used
3 different polymers in this work: (i) PMAO, (ii) PMAO con-
jugated with polyoxyethylene/polyoxypropylene block-
copolymer (Jeffamine M-1000) (PMAO/Jeffamine M-1000),
and (iii) PMAO conjugated with two polyoxyethylene/poly-
oxypropylene block-copolymers (Jeffamine M-1000 and Jeffa-
mine ED-600) (PMAO/Jeffamine M-1000/Jeffamine ED-600).
The second and third stabilizers were specifically synthesized
via reaction of maleic anhydride groups in PMAO with amino
groups of Jeffamine M-1000 and Jeffamine ED-600. Jeffamine
M-1000 contains one primary amino group, where as Jeffamine
ED-600 contains primary amino groups on both ends of the
molecular chain. The stabilizer with Jeffamine M-1000 was
synthesized by dissolving Jeffamine M-1000 in chloroform
with further addition of PMAO powder, and then the mixture
was left to stir overnight. Because all primary amino groups of
Jeffamine M-1000 were used for the reaction with maleic
anhydride, only carboxyl functional groups of the stabilizer
remained active. In order to synthesize stabilizer with both
Jeffamine M-1000 and Jeffamine ED-600, the stabilizer with
Jeffamine M-1000 was modified by Jeffamine ED-600 through
binding remaining active carboxyl groups of PMAO with
terminal amino group of Jeffamine ED-600 via EDC method
[11]. Despite the presence of carboxylic groups of PMAO, the
resulting stabilizer contains free amino groups at the ends of
PEG chains.
For encapsulation, QDs and the polymeric stabilizers (PMAO
with binded Jeffamine M-1000 or Jeffamine M-1000 þJeffamine
ED-600) were mixed in chloroform and stirred overnight at room
temperature (molar ratio of QDs/polymer was  1/40). Finally, QDs
were transferred to water by reverse-phase evaporation of QDs
(chloroform)-NaHCO3 (water) mixture with further purification
from excess of stabilizer.
2.4. Methods of characterization
Luminescence spectra of toluene and water solutions of QDs
samples were measured in 1 cm quartz cuvette on Cary Eclipse
Fluorescence spectrophotometer (Agilent Technologies, US). Shi-
madzu UV-1800 spectrophotometer (Shimadzu, Japan) was used
for UV-visible absorbance measurements of the samples. Trans-
mission electron microscopy measurements of QDs samples were
performed with Libra-120 (Carl Zeiss, Germany).
Registration of hydrodynamic diameter (HDD) and surface
charge (zeta-potential) of QDs as well as conductivity of QDs
solutions were performed on Zetasizer Nano (Malvern, UK).
Sample solutions of 1 mL volume were used for all measurements.
We have also used the count rate parameter (at fixed laser
attenuation) in order to estimate concentration changes before
and after EF treatment. The value of count rate displays the
number of photons detected per second in kcps (kilo counts
per second) by the detector and this is a useful parameter for
determining both the sample quality and QDs concentration
before the start of a DLS measurement.
2.5. Electric field treatment of QDs solutions
Zetasizer Nano was also used for EF treatment of the QDs
samples and the mode for zeta-potential (ZP) measurements was
used for this purpose. Universal dip cell for ZP measurement with
palladium electrodes was used. The EF treatments were carried
out in cycles and combination of alternate and direct currents was
used. 5 V potential was applied for all measurements with EF
strength fixed at 10 V/cm. The typical voltage-time and current-
time curve of a single cycle (standard current treatment procedure
at ZP measurements on Zetasizer Nano) is shown in Fig. 1.
 I.S. Zharkova et al. / Journal of Luminescence 176 (2016) 65–70
Any new series of measurements was performed with freshly
prepared QDs solution which was divided in eleven parts with
one part serving as a reference to take into account possible side
processes effecting colloidal stability of QDs overtime; duration
of one series of measurements was approximate to 1 h.
Remaining ten parts were treated by electric field for 1–10 cycles.
For measurements, 1 mL of QDs solution was placed into the
polystyrene cuvette, the electrodes were dipped into the sample
and ZP measurements were performed. The electrodes were
removed and cleaned (rinsed with water and sonicated) from the
treated sample after every cycle. Measurements of HDD and
luminescence spectra were performed before and after every EF
Fig. 1. Voltage-time and current-time curves of a single electric field treatment
cycle applied to the QDs aqueous solutions.
Fig. 2. Schematic illustration of QDs samples with various structure of stabilizer coating; abbreviations for the samples are in parentheses. ODA stabilized QDs (QD0) are
dissolved in toluene, while all other samples (QD1–QD3) are dissolved in water. Inset: TEM image of the QDs sample stabilized by ODA (QD0) and ODA/PMAO/Jeffamine
M-1000 (QD2).
67
treatment cycle. Absorbance spectra were measured before and
after 10 cycles of EF treatments.
3. Results and discussions
3.1. Characterization of QDs samples
Initial QDs coated with ODA (QD0, Fig. 2) and dissolved in
toluene were prepared via hot injection method (synthesis
description is provided in Section 2.2) and were used for further
synthesis of QDs with three types of various hydrophilic stabilizers
based on PMAO with and without attached polyoxyethylene/
polyoxypropylene block-copolymer; these three types of samples
were designated as QD1, QD2, and QD3 (Fig. 2), correspondingly.
All synthesized hydrophilic samples (QD1–QD3) have negative
charge of the QDs surface (ZP from  40 to  20 mV; section 3.2)
due to COO‒ groups of PMAO.
It was found that both emission and absorbance spectra pro-
files of the samples in aqueous solutions do not depend on sta-
bilizer composition and they are similar to the spectra of QDs
stabilized by ODA in toluene solution. In order to select appro-
priate concentration of QDs for further EF experiments we have
performed several additional measurements at various con-
centrations (Fig. 3).
We have chosen the QDs concentration at 10  9 M as appro-
priate for the following experiments because this concentration
lies in the linear range of luminescence and absorbance depen-
dence on the QDs concentration (Fig. 3, insets). Moreover, mean ZP
68 I.S. Zharkova et al. / Journal of Luminescence 176 (2016) 65–70
value decreases on 10–15 mV as QDs concentration lowers to
10  10 M which can lead to undesirable side processes such as
aggregation due to reduction of colloidal stability of QDs caused by
decrease in charge repulsion between QDs particles. Therefore, the
QDs solution with 10  9 M concentration was used for further
investigations due to not only suitable luminescence intensity but
better colloidal stability as well.
3.2. Influence of electric field on hydrodynamic radius and zeta-
potential of the QDs
To the best of our knowledge, performing EF treatment with
simultaneous DLS measurements has never been performed
before and, in comparison with other electrochemical approaches
dealing with investigation of QDs (e.g. cyclic voltammetry), is an
advantage because it allows monitoring changes of hydrodynamic
diameter, surface charge, conductivity, and number of the colloidal
particles (via value of count rate) during or just after EF treatment.
We have found that EF treatment do not change the HDD and
the surface charge of QDs systematically. The averaged results of
HDD and ZP measurements are shown in Table 1. An increasing of
HDD and decreasing of ZP from QD1 to QD3 were observed that is
in agreement with the changing of their stabilizer coating struc-
ture (Fig. 2). Negative charge for QDs samples can be explained
differently for different samples: (i) QD1 sample has a negative
charge due to hydrolysis of anhydride groups of PMAO, (ii) special
feature of the conjugation reaction for stabilizer of QD2 samples is
the formation of one carboxylic group after attaching one Jeffa-
mine M-1000 molecule to anhydride group of PMAO, and
(iii) remaining negative charge for QD3 is caused by residuary
carboxylic groups after binding of Jeffamine ED-600 to PMAO-
Jeffamine M-1000.
Besides HDD and ZP, the conductivity of QDs solutions and
mean count rate of DLS signal were measured during EF treatment
procedure as well (Fig. 4). An increase in conductivity was
observed for all water solutions of QDs (Fig. 4a): 6% for QD1, 12%
for QD2, and 19% for QD3. Conductivity of QD0 (solution in
toluene) was approximate to 0.287 0.08 μS/cm and did not
Table 1
Mean hydrodynamic diameter (HDD) and zeta-potential (ZP) of the QDs samples
(n¼30).
Sample HDD, (nm)
QD0 ‒  9 78
QD1 5.4 7 0.3
QD2 5.5 7 1.0
QD3 6.5 7 1.3
Fig. 3. Luminescence (λex ¼ 380 nm) (a) and absorbance (b) spectra of QD2 sample at various concentrations (0.25–10 nM). Insets: dependence of (a) luminescence intensity
at 620 nm and optical density at 350 nm (b) on QD2 concentration; concentration marked with hollow circle is the working concentration for follow experiments.
change systematically during EF treatments. Mean count rate is
changed similar to conductivity tendencies (Fig. 4b); count rate for
QD1 stays almost the same compared to QD2 and QD3 whose
count rate has changed to 25% and 42%, correspondingly.
We connect observed changes (increase in both conductivity and
count rate) with two possible processes: (i) charging of QDs without
their decomposition and (ii) disintegration of QDs stabilizer coating
with formation supports of charge. In our opinion, the first mechan-
ism is more appropriate for the case of QD1 sample, while the second
describes the processes which occur in samples QD2 and QD3.
3.3. Influence of electric field on luminescence of QDs solution
Finally, we investigated an influence of EF treatment on lumines-
cence of QDs samples. Permanent decrease in QDs luminescence after
EF treatment was observed for all samples (Fig. 5); the stability to EF
increases in the following order: QD2, QD1, QD3, QD0.
Relative decrease in luminescence intensity for all samples
after 10 cycles of EF treatment is shown in Table 2. Reference
measurements of QDs stability over time for QD2 (lowest stability
to the EF) show that without EF treatment decrease in lumines-
cence is insignificant.
We proposed two possible causes of decreases in luminescence
intensity: (i) decrease in concentration of QDs particles and/or
(ii) reduction of QDs quantum yield caused by redox reactions near
the electrode surfaces. Decrease in QDs concentration can occur
due to sedimentation of QDs or their sorption on a surface (e.g.
walls of cuvette or electrodes), while changes of quantum yield are
usually observed after surface changes of QDs such as degradation
of the stabilizer coating or oxidation that lead to formation of
surface defects which facilitate non-radiative relaxation of exci-
tons [16]. Changes in QDs concentration in the samples were
controlled via absorbance measurements before and after EF
treatments with 10 cycles. It was found that the absorbance (at
350 nm) changes much lower after EF treatment than in the case
of luminescence (Table 2) and this can be caused by errors of the
sample preparation or the absorbance measurements, because we
operate with very dilute samples with low absorbance. This result
proves that quantum yield decreasing mechanism is much more
likely than decrease in QDs concentration during EF treatment.
On the other hand, comparison of the luminescence results with
results of conductivity and count rate measurements allows us to
ZP, (mV)
conclude that samples QD2 and QD3 experienced degradation of
the stabilizer coatings (increase of total concentration of particles in
 35 76 the solutions, Fig. 4) that leads to the quenching of luminescence
 30 76
due to formation of surface defects via redox reactions. Gooding et
 25 76
al [19] reported that their CdSe/CdS/ZnS QDs (assembled as 2D
 I.S. Zharkova et al. / Journal of Luminescence 176 (2016) 65–70 69

Fig. 4. Influence of number of applied cycles of electric field on conductivity (a) and count rate (from DLS measurements) (b) of QDs solutions.

Fig. 5. Luminescence intensity vs. number of electrical field treatment cycles for the QDs samples, n ¼5. Part of QD2 sample was used as a reference sample without
treatment by electric field (marked as QD2’); the luminescence measurements for this sample were performed at the same periods of time as for other samples.

repulsion between particles and (ii) better redox protective ability

Table 2 due to electron-donor properties.
Relative luminescence changing (RLC) and relative absor-
bance changing (RAC) of QDs solution before and after EF
treatments for 10 cycles.
4. Conclusions
Sample RLC, (%) RAC, (%)

QD0 87 6 ‒ Therefore, in this article we performed the EF treatment (10 V/cm)

QD1 66 7 8 18 of QDs aqueous solutions in order to evaluate comparative stability of
QD2 737 4 13 QDs samples with various structures of stabilizer coatings. Zetasizer
QD3 407 1 12
QD2’a 27 3 ‒
Nano, standard laboratory equipment for dynamic light scattering
measurements, was used as a source of voltage for the treatment of
a
This sample was used as referent and not treated by QDs samples with EF. To the best of our knowledge, this is a first
EF (luminescence decrease was registered after periods of experimental combination of simultaneous DLS measurements toge-
time equal to other samples).
ther with EF treatment and further luminescent measurements. This
combination allows obtaining additional information about colloidal,
monolayer) are completely and irreversibly quenched under posi-
electrochemical and luminescence stability of QDs solutions and can
tive potentials below 1.5 V in the presence of air oxygen and we
be widely used in the future as a very powerful tool for investigation of
have used 5 V that is more than enough for permanent oxidation of
surface properties of QDs solutions and protective properties of their
our QDs samples. Therefore we can conclude that application of stabilizers.
QDs with high densely packed stabilizer coating (QD3) provides Analysis of results have shown that the QDs remain colloidal
better preserving properties against EF treatment than the other stability, hydrodynamic radius and ZP value after EF treatments,
kinds of used stabilizers. However, QD1 have surprisingly high but irreversible luminescence quenching was observed for the all
chemical stability compare to QD2, despite it do not contain PEG samples in aqueous solutions. Irreversibility of the quenching we
moieties at all. We explain this fact with high negative surface explained by permanent redox changes of the QDs cores with
charge and densely packed coating that provides (i) higher charge consequent decreasing quantum yield during EF treatment. We
70 I.S. Zharkova et al. / Journal of Luminescence 176 (2016) 65–70
have found that stabilizers with higher PEG content preserve QDs
from quenching better compare to the sample lower thickness of
the PEG layer.
Acknowledgments
The work was supported by Russian Science Foundation (pro-
ject 14-13-00229).
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