J Nanopart Res (2017) 19:70

DOI 10.1007/s11051-017-3757-2

RESEARCH PAPER

Tuning optical properties of water-soluble CdTe quantum dots

for biological applications
Anne S. Schulze & Isabella Tavernaro &
Friederike Machka & Olga Dakischew &
Katrin S. Lips & Mathias S. Wickleder

Received: 12 August 2016 / Accepted: 24 January 2017

# Springer Science+Business Media Dordrecht 2017

Abstract In this study, two different synthetic methods in
aqueous solution are presented to tune the optical proper-
ties of CdTe and CdSe semiconductor nanoparticles. Ad-
ditionally, the influence of different temperatures, pres-
sures, precursor ratios, surface ligands, bases, and core
components in the synthesis was investigated with regard
to the particle sizes and optical properties. As a result, a red
shift of the emission and absorption maxima with increas-
ing reaction temperature (100 to 220°C), pressure (1 to
25 bar), and different ratios of core components of alloyed
semiconductor nanoparticles could be observed without a
change of the particle size. An increase in particle size from
2.5 to 5 nm was only achieved by variation of the
mercaptocarboxylic acid ligands in combination with the
reaction time and used base. To get a first hint on the
cytotoxic effects and cell uptake of the synthesized
Anne S. Schulze, Isabella Tavernaro, and Friederike Machka
contributed equally to this work.
A. S. Schulze : I. Tavernaro : F. Machka :
M. S. Wickleder (*)
Institute of Inorganic and Analytical Chemistry,
Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17,
35392 Giessen, Germany
e-mail: mathias.wickleder@anorg.chemie.uni-giessen.de
I. Tavernaro
INM—Leibniz Institute for New Materials, Campus D2 2,
66123 Saarbruecken, Germany
O. Dakischew : K. S. Lips
Laboratory of Experimental Trauma Surgery,
Justus-Liebig-University Giessen, Schubertstraße 81,
35392 Giessen, Germany
quantum dots, in vitro tests mesenchymal stem cells
(MSCs) were carried out.
Keywords Syntheses of CdTe . CdSe and CdTexSex-1 .
Microwave-assisted synthesis . Biocompatibility . Cell
uptake . Cytotoxicity
Introduction
In recent years, the interest in using semiconductor nano-
particles for biological applications has grown steadily, as
they are considered to be a promising new class of
fluorophores for diagnostic and sensor applications
(Bruchez et al. 1998; Chan and Nie 1998; Yeh et al.
2005). Due to their resistance to chemical and metabolic
degradation, outstanding long-term photostability, high
quantum yields, and broad excitation spectra with high
absorption coefficients, they have significant advantages
over conventional organic dyes and fluorescent proteins.
For any biological application, the semiconductor nano-
particles must not only be water-soluble, stable, and non-
toxic but should also possess easily adjustable absorption
and emission maxima for detection. Luminescent spherical
semiconductor nanoparticles are considered to be quasi
zero-dimensional single crystals, called quantum dots
(QDs). Their properties depend on the size, shape, and
composition and differ significantly from those of mole-
cules or bulk materials (Drummen 2010; Kim et al. 2013).
The fluorescence emission is caused by the quantum con-
finement effect: If the particles become smaller than the
exciton Bohr radius, the energy levels become discrete and
70 Page 2 of 16
the band gap increases for smaller particles. If the exciton
recombines, the energy is emitted in form of light and the
wavelength of the light correlates with the band gap;
therefore, the emission undergoes a blue shift for smaller
particles (Alivisatos 1996; Murray et al. 1993).
Compared to common organic dyes, colloidal semicon-
ductor QDs possess unique optical properties making them
preferable to organic fluorophores (He et al. 2008). For this
reason, QDs have a wide range of applications. They can
be used for example in LEDs (Sun et al. 2007), lasers (Lott
et al. 1997), sensors (Zhang et al. 2005), and biolabeling
(Bruchez et al. 1998). In addition, the advances in synthe-
sis, water solubility, and bioconjugation have made them
very appealing for diagnostic and therapy in vitro and
in vivo (Wang et al. 2010). Functionalized cadmium-
based nanoparticles can also be used for binding to specific
targets, like tumors (Yang et al. 2009), blood vessels
(Smith et al. 2007), receptors (Zhou et al. 2007), and
DNA (Dubertret et al. 2002).
QDs have to be stable in aqueous medium to use
them in biological systems. When synthesized in or-
ganic solvents, they are often stabilized with hydro-
phobic ligands like trioctylphosphine oxide, which
make a postsynthetic surface modification by an ex-
change reaction mandatory. However, this is often
critical for the stability and the quantum yields. Thus,
it is preferable to synthesize QDs in an aqueous medi-
um with mercaptocarboxylic acids as ligands. These
ligands possess on one end an anchor for the attach-
ment at the particle surface and on the other end a free
moiety for further functionalization. Furthermore,
high temperatures and instable and highly toxic pre-
cursors like dimethylcadmium are not needed (Parak
et al. 2003; Breus et al. 2007; Zhang et al. 2003;
Gaponik et al. 2002). The cytotoxicity caused by the
leakage of cadmium ions and other heavy metals can
be reduced with a certain degree by using a shell of a
material with a larger band gap like ZnS. Because of
the arrangement of the valence and conduction bands,
the electrons are unable to enter the shell; therefore,
they are forced to recombine in the core and
nonradiative relaxation processes on the surface are
prevented. This is also preferable to increase the sta-
bility and the intensity of the photoluminescence
(Hines and Guyot-Sionnest 1996).
In this study, different methods are described to tune
the optical properties of QDs for a potential use in
biological applications. It was shown that the emission
and absorption maxima can be influenced by the
J Nanopart Res (2017) 19:70
ligands, the reaction time, temperature, and the compo-
sition of the particles without changing the core size.
Results and discussion
CdTe and CdSe QDs were synthesized in aqueous me-
dia following a modified literature known method
(Rogach et al. 1996; Kale et al. 2012; He et al. 2008).
They were prepared by adding oxygen-free NaHX
(X = Se or Te) precursors to an Ar-saturated aqueous
Cd2+/mercaptocarboxylic acid precursor solution at
pH > 10. The high alkaline pH value is needed for the
poor solubility of the complexes formed with cadmium
and the carboxylic acid ligands in aqueous media. The
precursor ratio of Cd2+/NaHX/mercaptocarboxylic acid
was fixed at 2/1/4.8, since previous studies indicated
this ratio as suitable to get high quantum yields (Xu et al.
2011). After the injection of freshly prepared NaHX
precursor solution into the Cd2+-ligand mixture, it was
heated to reflux for 2–24 h to grow the QDs (Fig. 1).
After 1, 3, and 5 h, aliquots were taken to check the
particle growth by UV/Vis and fluorescence emission
measurements.
The UV/Vis absorption spectra of the synthesized CdTe
QDs (Fig. 2) indicate a different particle growth velocity
with different ligands. Mercaptocarboxylic acids with short
alkyl chain lengths like thioglycolic acid (TGA) and
mercaptopropionic acid (MPA) show absorption maxima
at λTGA = 534 nm and λMPA = 529 nm, respectively,
after a reaction time of 3 h, whereas longer alkyl
chain lengths like mercaptohexanoic acid (MHA) and
mercaptoundecanoic acid (MUDA) have a maximum at
λMHA = 450 nm and λMUDA = 440 nm, respectively.
Further ligands with different chain lengths
(mercaptobutanoic acid (MBA) and mercaptopentanoic
acid (MPETA)) were used for the synthesis and also
exhibited the trend discussed. The obtained spectra of the
aliquots after 5 h indicate a sustainable growth of the QDs
with short chain lengths (λTGA = 565 nm; λMPA = 542 nm),
while the ligands with longer alkyl chains show little or no
red shifts (and no particle growth) (S 1). Additionally,
bulky ligands such as mercaptosuccinic acid (S 2) (MSA,
λMSA = 509 nm) appear to slow down the particle growth
(Fang et al. 2012).
The fluorescence emission spectra of the individual
aliquots were measured with an excitation wavelength
of 450 nm. As a result, the previously discussed trend of
the influence of the used mercaptocarboxylic acid on the
J Nanopart Res (2017) 19:70
Fig. 1 Scheme of the QD
synthesis
optical properties can also be seen in the emission
maxima (Fig. 3). QDs coordinated with TGA and
MPA indicate a larger red shift than QDs with MHA
and MUDA. Beside the ligands (Silva et al. 2012), the
choice of base used in the synthesis seems to influence the
particle growth as well. Using tetramethylammonium hy-
droxide (TMAH) instead of NaOH, larger TGA-
coordinated QDs were obtained with an absorption maxi-
mum at 555 nm for the same reaction time (Fig. 4). In
addition, a longer reaction time causes an increase of the
size distribution of the resulting QDs, which is visible by
broader absorption bands (Fig. 4). The explanation of this
phenomenon might be a different adsorption of the bases
on the particle surface followed by different particle
growth.
Fig. 2 Comparison of the UV/
Vis absorption maxima of the
synthesized mercaptocarboxylic
acid-coordinated QDs after a
reaction time of 1, 3, and 5 h.
Normalized absorption spectra of
MSA-coordinated QDs after
different reaction times (inset)
Page 3 of 16 70
The replacement of the core material by CdSe led to a
shift of the absorption maximum and emission maxi-
mum. After an analogous reaction time (3 h), MPA-
coordinated CdSe QDs could be obtained having an
absorption maximum of 485 nm (λCdTe/MPA = 520 nm)
and an emission maximum of 585 nm (λ CdTe/
MPA = 555 nm). To investigate the impact of the core
material on the optical properties in more detail, a ter-
nary system of CdTexSe1-x was synthesized. Compared
to binary compounds like CdTe and CdSe, these ternary
systems are still only little explored. Nevertheless, up to
now, several ternary and quaternary systems have been
synthesized and characterized (Liu et al. 2012; Pons
et al. 2009). In this study, CdTexSe1-x was synthesized
with different molar ratios of tellurium and selenium
70 Page 4 of 16 J Nanopart Res (2017) 19:70

Fig. 3 Comparison of the

fluorescence emission maxima of
the synthesized
mercaptocarboxylic acid-
coordinated QDs after a reaction
time of 1, 3, and 16 h.
Photography of a section of QDs
synthesized in this project under
the UV lamp (inset; λex = 366 nm)
[ligands: MUDA (green), MHA
(yellow), MPA (orange)] (color
figure online)

precursor. For stabilization of the QDs, the short ligand
MPA was chosen. The CdTexSe1-x QDs were prepared
via the conventional synthesis in aqueous solution under
inert conditions. Different molar ratios of NaHTe and
NaHSe were added at the beginning, the reaction tem-
perature and time were held constant at 100°C and 3 h
(Fig. 5). The resulting nanoparticles were purified via
dialysis in water (three times, MWCO 3500).
To determine the structural and optical properties of
the resulting QDs UV/Vis and emission spectroscopy,
TEM measurements, XRD analysis, and EDX spot
analysis were performed. With an increasing percentage
of telluride in the system, the absorption maximum
shifts to higher and the emission maximum shifts to
lower wavelength (Fig. 6). A linear correlation for the
mixed analogs was found (Fig. 6). The values of the
absorption and emission maxima vary between pure
CdSe to CdTe.
XRD patterns of MPA-capped CdTexSe1-x show that
the reflections shift between those of the binary border
compounds CdTe and CdSe. This indicates a solid so-
lution, i.e., a mixed crystal system without miscibility
gap. This is possible due to the fact that both CdTe and
CdSe have the same cubic crystal structure and tellurium

Fig. 4 Normalized UV/Vis

absorption spectra of TGA-
coordinated CdTe-QDs, using
TMAH (gray) or NaOH (black)
as base during synthesis. The
absorption maxima shift from
498 nm (NaOH 1 h) to 527 nm
(TMAH 1 h) [534 nm (NaOH 3 h)
to 555 nm (TMAH 3 h)] using
TMAH
J Nanopart Res (2017) 19:70
Fig. 5 Synthetic procedure for
the mixed crystal system
CdTexSe1-x
and selenium atoms can substitute each other in the
structure. The reflections in the XRD patterns (Fig. 7)
are broadened due to nanosized particles. A mean diam-
eter of 3 nm can be calculated with the Scherrer equation
(Scherrer 1918). TEM measurements show monodis-
perse nanoparticles with 2.8 ± 0.5 nm for all synthesized
particles (S 3).
Hence, the growth mechanism for the QDs is not
depending on the precursor solution. EDX spot analysis
revealed a homogeneous distribution of the constituting
elements within the particles. The values found corre-
spond to the nominal composition of the mixed crystals
(Table 1).
The conventional synthesis with Schlenk technique
allows the synthesis of water-soluble QDs with precisely
tunable absorption maxima and particle sizes by a suitable
choice of the ligand, reaction time, and core material. In
this study, another method for the synthesis was also
applied. Following the idea that microwave irradiation
provides effects like extremely fast heating rates, hot spots,
and temperatures far above the boiling point of the used
solvents (Baghbanzadeh et al. 2011; Bilecka and
Niederberger 2010), further improvements of the obtained
nanoparticles should be possible by using a microwave-
assisted synthesis. In contrast to the conventional synthesis
in aqueous media, the Cd2+/MUDA mixture and the Te
precursor solution were added to a sealed microwave
reaction vessel and heated 10 min to 130°C (Fig. 8). The
influence of the microwave irradiation on the optical prop-
erties was monitored after precipitation with isopropanol
and resuspension in distilled water, using again UV/Vis
absorption spectroscopy and TEM measurements (S 4, S
5). In Fig. 8, the normalized absorption spectra of the QDs
are shown, which were synthesized by the microwave-
assisted synthesis. QDs coordinated with different
mercaptocarboxylic acids were obtained under the de-
scribed reaction terms by the microwave-assisted synthesis
(Table 2). Besides the obvious savings in time, these results
indicate particles with narrower absorption bands and
therefore narrower size distribution. This can be seen as
an advantageous effect of the microwave-assisted
synthesis.
Page 5 of 16 70
Although the reaction time, the alkyl chain length, and
the pH values have an influence on the growth rate of the
particles, there were no changes in the optical properties of
the MUDA-functionalized CdTe QDs and no particle
growth was detectable (Figs. 3 and 8). The time-
dependent evolution of the optical properties monitored
by UV/Vis spectra indicated that the particle growth
stopped after some time at 2.5 nm, as verified by TEM
images and DLS measurements and may be explained by
the steric stabilization of the MUDA ligand. This phenom-
enon was also described (Aldeek et al. 2008) studying the
influence of large ligands on the particle size of QDs. They
demonstrated that the number of carbon atoms in the
thioalkyl chain does have an influence on the particle size,
the fluorescence intensity, and the surface coverage of the
QDs. This leads to small particle sizes and an absorption
maximum around 450 nm for the hydrophobic MUDA
ligand. Nevertheless, they also noticed a small effect of a
shift of few nanometers to longer wavelength using the
hydrothermal synthesis method with higher temperature
and pressure in an autoclave. Due to this, the microwave-
assisted synthesis of the MUDA-capped QDs was used to
investigate the influence of the reaction temperature. The
particles were heated from 120 to 220°C with a micro-
wave, and a redshift in the absorption and emission max-
ima was observed with increasing temperature and
600
Wavelength [nm]
580
560
540
520
500 Absorption
Emission
480
0.0 0.2 0.4 0.6 0.8 1.0
x
Fig. 6 Emission (λex = 350 nm) and absorption maxima of
CdTe x Se 1-x /MPA with x = 0.0 to x = 1. Photography of
CdTexSe1-x/MPA with x = 0.1 to x = 1 under the UV lamp
(λex = 366 nm) (inset)
70 Page 6 of 16 J Nanopart Res (2017) 19:70

Fig. 7 XRD patterns of

CdTexSe1-x/MPA with x = 0.0 to CdTexSe1-x (x=1.0)
CdTexSe1-x (x=0.9)
x = 1.0. Both binary compounds CdTexSe1-x (x=0.8)
CdTe and CdSe are also shown CdTexSe1-x (x=0.7)
for comparison with the mixed CdTexSe1-x (x=0.6)

Intensity [a.u.]
CdTexSe1-x (x=0.5)
crystal system CdTexSe1-x (x=0.4)
CdTexSe1-x (x=0.3)
CdTexSe1-x (x=0.2)
CdTexSe1-x (x=0.1)
CdTexSe1-x (x=0.0)
PDF 01-075-2086 CdTe
PDF 00-019-0191 CdSe

10 20 30 40 50 60 70 80
2Theta [deg]

pressure during the synthesis (Fig. 10). This red shift is not the absorption shifts from 435 nm for CdTe@120°C to
caused by an increase in size as can be seen in the TEM 535 nm for CdTe@210°C and the emission from 545 to
images. The particles size remains nearly the same 617 nm (120–220°C) (Fig. 10). The size of the particles
(~2.4 nm) from 120 to 200°C, only above 200°C that it did not change significantly for these ratios. QDs with
increases slightly. Thus, the shift of the absorption and the composition Cd/Te 1:2 show a constant size for
emission maxima toward longer wavelengths cannot be CdTe@120°C to CdTe@200°C, and particles with a
explained by particle growth. However, a comparison of composition 2:1 do not change from CdTe@120°C to
the photoluminescence intensities reveals an increase for a CdTe@210°C. For higher temperatures, the sizes in-
preparation temperature of 200°C. This result may be crease to ~2.9 nm (1:2) and 4.6 nm (2:1), respectively.
explained by an improved crystallinity at higher tempera- EDX measurement confirmed a slightly higher telluri-
tures. Particles with higher crystallinity show less surface um amount for the particles synthesized with a tellurium
defects; therefore, the excitons undergo less frequently excess. The observed shift is probably a result of the
non-radiative relaxation processes. The higher crystallinity lower tellurium amount that creates vacancies in the
of the CdTe quantum dot samples prepared at high tem- lattice. A similar observation was reported (Wang et al.
peratures can also be confirmed by XRD powder diffrac- 2012) at investigations about the influence of oxygen
tion (Fig. 9). The respective patterns show more distinct vacancies on the absorption properties ZnO. If the
reflections and an enhanced intensity of the characteristic amount of vacancies is big enough, the impurity states
diffraction reflections. Syntheses at temperatures below near the edge of the valance band can delocalize and
140°C led to poor crystallization of the QDs. Due to these
results, the color change of the CdTe QDs may be ex-
Table 1 Overview CdTexSe1-x/MPA QDs: diameter, composition,
plained by a smaller band gap for more highly crystalline absorption, and emission maxima
dots (Rotaru et al. 1999).
For further investigations, CdTe QDs with two dif- x dTEM (nm) EDX Te/Se λAbs (nm) λEm (nm)
ferent Cd/Te ratios were used, namely Cd/Te 1:2 and
0 2.6 ± 0.2 0/1 485 584
2:1, in order to investigate the influence of the compo-
0.1 2.4 ± 0.3 0.13/0.87 487 598
sition on the optical properties (S 6). The redshifts of the
0.2 2.9 ± 0.2 0.24/0.76 486 581
absorption and emission maxima were observed for
0.3 2.3 ± 0.3 0.30/0.70 488 579
both ratios, but if less tellurium was present during the
0.4 2.5 ± 0.2 0.38/0.62 492 573
synthesis, the maxima generally shifted to longer wave-
0.5 2.6 ± 0.2 0.61/0.39 498 567.5
lengths. For the composition Cd/Te 1:2, the absorption
0.6 2.5 ± 0.3 0.68/0.32 500 564
shifts from 420 nm for CdTe@120°C to 480 nm for
0.7 2.3 ± 0.3 0.68/0.32 498 564
C d Te @ 2 0 0 ° C . T h e a b s o r p t i o n m a x i m a f o r
CdTe@210°C and CdTe@220°C cannot be determined. 0.8 2.5 ± 0.2 0.60/0.40 506 560.5
The emission for this composition changes from 536 to 0.9 2.5 ± 0.2 0.88/0.12 518 559
606 nm (120–200°C). For the composition Cd/Te 2:1, 1.0 2.6 ± 0.2 1/0 520 555
J Nanopart Res (2017) 19:70 Page 7 of 16 70

Fig. 8 Reaction scheme of the

microwave-assisted synthesis and
the normalized absorption spectra
of different CdTe QDs (130°C
10 min)

overlap with the valance band edge which leads to a onto the particle surface. For the potential use of QDs in
narrowing of the band gap and to a shift in the absorp- biological systems, the fluorescence quantum yields are
tion and emission maxima. In addition, the described also important characteristics. These were determined by
reaction terms can be used to synthesize QDs coordi- the comparative method of Rhys Williams and Winfield
nated with other ligands like mercaptosulfonic acids or (1983). The microwave-assisted synthesis led to the best
polydentate ligands with multiple attachment sites. In fluorescence quantum yields with 18% for the MUDA-
this study, the ligands 3-mercapto-1-propane sulfonic coordinated QDs and 35% for the TGA-coordinated QDs.
acid (MPSA) and the bidentate dihydrolipoic acid This is a range similar to the water-soluble QDs known in
(DHLA) were used (S 7). Whereas MPSA can enhance literature (Silva et al. 2012).
the stability at lower pH values (Yang et al. 2012), In addition to the determination of the two beneficial
DHLA-coordinated QDs are known for a better factors for the use in biological applications, the number
chemioxidation and thermal stability than those capped of immobilized ligands, and the fluorescence quantum
by TGA or MPA, since the two thiol functions anchor yields, first in vitro cell proliferation and cytotoxicity
simultaneously onto the nanoparticle’s surface (Fang
et al. 2008). Particle characterization with TEM mea- Table 2 Overview of the different mercaptocarboxylic acids-
surements and UV/Vis spectroscopy (S 7, S 8) indicate coordinated QDs synthesized by microwave irradiation
for CdTe/MPSA a size of d = 3.5 ± 0.3 nm with λCdTe/
Coordinated QDs dTEM (nm) dDLS (nm)a λAbs (nm)
MPSA = 565 nm and for CdTe/DHLA d = 3.3 ± 0.2 nm
with λCdTe/DHLA = 545 nm, respectively. TGA 4.7 ± 0.3 7±1 542
Due to their tunable optical properties and their high MPA 3.5 ± 0.3 7±2 512
stability in aqueous media, the synthesized QDs are ideal MSA 3.9 ± 0.2 7±2 522
tools for the multivalent presentation of different bioactive MBA 3.4 ± 0.3 n.d. 494
substances. To determine the potential number of available MPETA 3.2 ± 0.3 6±1 481
ligands on the particle surface, thermogravimetric analyses MHA 3.2 ± 0.2 6±1 470
of the synthesized CdTe QDs were conducted (S 9). MUDA 2.5 ± 0.2 6±1 431
Through the weight loss of the samples, an amount of 60
ligands were calculated for MUDA-coordinated QDs, 350 n.d. not determined
a
ligands for MPA-coordinated QDs, and 450 ligands for The mean hydrodynamic diameter of the particles was deter-
mined, using the Bnumber distribution,^ which is related to pop-
TGA-coordinated QDs, respectively. Thus, these figures ulation or counting of particles and is calculated using the volume
indicate the maximum number of possible bioactive epi- distribution data. It is weighted to the smaller particles in the
topes, which can be immobilized by coupling reactions distribution
70 Page 8 of 16 J Nanopart Res (2017) 19:70

Fig. 9 XRD patterns of CdTe

QDs synthesized at temperatures CdTe (MW) 200 °C
from 120 to 200°C in the CdTe (MW) 190 °C
CdTe (MW) 180 °C
microwave and at 100°C in a CdTe (MW) 170 °C
vessel CdTe (MW) 160 °C

Intensity [a.u.]
CdTe (MW) 150 °C
CdTe (MW)140 °C
CdTe (MW) 130 °C
CdTe (MW) 120 °C
CdTe 100 °C
PDF 01-075-2086 CdTe

10 20 30 40 50 60 70 80
2Theta [deg]

tests were realized in this study. For these tests, the
synthesized QDs were passivated with a ZnS protection
shell. This is necessary, since CdTe and CdSe QDs are
highly cytotoxic (Winnik and Maysinger 2013). It is
well-known that the toxic release of Cd2+ ions can be
reduced by using a protective shell of polymers or ZnS
(Chen et al. 2012; (Soenen et al. 2011). That is why the
freshly prepared QDs were passivated with the conven-
tional synthesis method, using ZnSO4 and Na2S as
precursors and a reaction temperature of 65°C. By var-
iation of the reaction time (t = 0.5–2.5 h), the shell
thickness could be adjusted. A successful passivation
could be detected by a red shift in UV/Vis absorption
spectra (S 10) and by EDX measurements. The EDX
measurements confirm a homogeneous distribution of
zinc, sulfur, cadmium, and tellurium. A relatively large
amounts of zinc (44%) and sulfur (41%) are present and
low concentrations of cadmium (11%) and tellurium
(4%) can be found. The high amount of the shell
material and the large ratio of Zn and S to Cd and Te
indicates the presence of ZnS shell. Furthermore, X-ray
powder diffraction before and after the passivation has
revealed that after the particles were passivated, only
reflexes of the ZnS shell are visible (S 11). This con-
firms the results from the EDX measurement. An in-
crease in stability of the QDs could also be observed.
The QDs without ZnS shell precipitate after 2 weeks in
the refrigerator, while the CdTe/ZnS particles do not
undergo any optical changes over a month.
Cell uptake experiments
To examine the cellular uptake of the synthesized QDs,
samples of CdTe/ZnS/MUDA, CdTe/ZnS/MPA, and
CdTe/MPSA were incubated with mesenchymal stem
cells (MSCs) (Lautenschläger et al. 2015). After an
incubation period of 24 h, 72 h, and 7 days, the cells

Fig. 10 Emission and absorption

maxima of CdTe 2:1 (red) and
CdTe 1:2 (black) in dependence
on the reaction temperature.
Photography of the luminescence
of CdTe (1:2)/MUDA QDs
synthesized in a microwave at
different temperatures
(λex = 366 nm) (inset)
J Nanopart Res (2017) 19:70
were checked by light microscopy. In Fig. 11, light
microscopic images of the incubated cells with
CdTe/ZnS/MPA QDs and a control without QDs are
shown after 3 and 7 days of incubation. At the used
concentration of QDs (c = 20 pmol/L), no significant
change in patterned cell morphology could be detected,
since the spindle/fibroblastoid like morphology with the
long thin cell bodies and large nucleus of MSCs could
be still observed. In another study (Fig. 12), the particle
concentration was changed (14.1, 100, 1 nmol/L) and
the cells were controlled after an incubation period of
1 day. As a result, no significant effects on the cell
vitality by a higher particle concentration could be de-
tected. To control the influence of the protecting ZnS
shell and the sulfated ligands on the morphology and
viability of the cells, the test was repeated with
CdTe/MPSA, which had a similar particle size (S 12).
No influence of the absent ZnS shell and the ligand
could be detected.
In a third study, the cell uptake of the synthesized
QDs into the MSCs was determined. Therefore, the cells
with CdTe/MPSA and CdTe/ZnS/MUDA were incubat-
ed with a concentration of 100 pmol/L and checked
under the confocal laser scanning microscope. The
Fig. 11 Light microscopic
images of MSCs incubated with
CdTe/ZnS/MPA QDs
(c = 14.1 pmol/L) and without
QDs (control) after different days.
a Control (3 days), b 14.1 pmol/L
CdTe/ZnS/MPA QDs (3 days), c
control (7 days), and d 14.1 pmol/
L CdTe/ZnS/MPA QDs (7 days)
Page 9 of 16 70
images of internalized CdTe/MPSA and CdTe/ZnS/
MUDA in MSCs were recorded after incubating the
QDs with cells for 24 h at 37°C (Fig. 13). It is obvious
that the QDs were ingested into the cells and agglomer-
ate around the nucleus without penetrating into it. Ad-
ditionally, it seems that more unsulfated QDs were taken
up into the cells than the sulfated ones. An evidence for
that can be seen in a comparison between Fig. 13a, b.
Many CdTe/ZnS/MUDA QDs are located in the cyto-
plasm, while the number of sulfated CdTe/MPSA QDs
is significantly lower. However, further studies are need-
ed to clarify the mechanisms for the cellular uptake of
the QDs.
Conclusion
Through an appropriate choice of the reaction parame-
ters for an aqueous synthesis of mercaptocarboxylic
acid-coordinated QDs, it was possible to gain CdTe
and CdSe QDs with particle sizes of 2.5 to 5 nm which
have a narrow size distribution and an emission in the
visible range of the optical spectrum. The optical prop-
erties can be influenced through variation of the ligand
70 Page 10 of 16 J Nanopart Res (2017) 19:70

Fig. 12 Light microscopic

images of MSCs incubated with
different concentrations of
CdTe/ZnS/MPA QDs after 24 h. a
(c = 1 nM), b (c = 100 pM), c
(c = 14.1 pM), and d (control
without QDs)

Fig. 13 Fluorescence confocal

microscope images of CdTe/ZnS/
MUDA QDs (a). CdTe/MPSA
QDs (b) incubated MSCs and
controls of the MSCs without
QDs (c, d) after 24 h [nuclear
staining: 4′,6-diamidine-2′-
phenylindole (DAPI); staining
actin filaments: phalloidin-
TRITC (a, c) and phalloidin-
FITC (b, d)]. a Nucleus (blue),
actin filaments (red), QDs
(green). b Nucleus (blue), actin
filaments (green), QDs (orange).
c Nucleus (blue), actin filaments
(red). d Nucleus (blue), actin
filaments (green)
J Nanopart Res (2017) 19:70
chain length, the reaction temperature, the core material,
the ration of cadmium to tellurium, and so on. Because
of their already given water solubility and stability, these
QDs are versatile tools for biological applications such
as cell imaging. First in vitro studies with mesenchymal
stem cells indicated a cell uptake during a period of
1 day by endocytosis, where the nanoparticles started
to agglomerate in the cytoplasm and accumulate around
the nucleus without penetrating it. Also, no cytotoxicity
of the synthesized QDs with and without a protecting
ZnS shell was be observed.
Experimental section All reactions of nanoparticles in
aqueous solution were conducted in purified
Millipore water. All other chemicals were purchased
from commercial sources and used as received with-
out further purification. The syntheses of the QDs
were prepared under argon atmosphere. Cellulose
dialysis membrane having 3500-kDa molecular
weight cutoff (MWCO) was procured from Carl
Roth GmbH (Karlsruhe, Germany). Prior to use, all
glassware was thoroughly cleaned with aqua regia
(3:1 v/v of 37% HCl and 65% HNO3 solutions)
followed by rinsing with deionized water. A part of
the semiconductor quantum dot syntheses were car-
ried out by microwave irradiation experiments using
a Monowave 300 single-mode microwave reactor
(2.45 GHz, 850 W) from Anton Paar GmbH (Graz,
Austria) under temperature control mode, not with
constant power. The reaction temperature was mon-
itored by an external infrared sensor (IR), located in
the sidewalls of the microwave cavity and an inter-
nal fiber-optic (ruby) thermometer. Ten milliliters or
30 mL borosilicate glass reaction vials were used which
were sealed with snap caps and standard
polytetrafluoroethylene (PTFE)-coated silicone septa. All
experiments were performed at a stirring rate of 600 rpm
and simultaneous cooling during the experiments with
compressed air.
Characterization All optical measurements were per-
formed at room temperature under ambient condi-
tions. The UV/Vis spectra were recorded with an
Agilent 8453 spectrophotometer (Agilent Technolo-
gies Inc., Santa Clara, CA, USA). Fluorescence
spectra were obtained with the spectrofluorometer
FP8300 from JASCO (Gross-Umstadt, Germany)
using a xenon lamp and an excitation wavelength
of 350 nm. Samples were placed in an open-sided 1-
Page 11 of 16 70
cm path length quartz cuvette for both fluorescence
and UV/Vis measurements. The quantum yield
values were determined from the equation:
FSample ∙ ARef ∙ n2Sample ∙
QYSample ¼ QYRef
FRef ASample n2Ref
where F, A, and n are the measured fluorescence, the
measured absorbance, and the refractive index of the
solvent, respectively (Rhys Williams and Winfield
1983). To determine the diameters, the morphology,
and the agglomeration state of the nanoparticles, the
samples were additionally analyzed by dynamic light
scattering measurements (DLS) and transmission
electron microscopy (TEM). DLS measurements
were performed either with the StabiSizer PMX
200C from Particlemetrix (Mersbusch, Germany) or
the Nanotrac 250 ultra from Microtrac (Mersbusch,
Germany). TEM measurements were carried out
using a Philips CM30 STEM (300 kV, LaB6-cathode)
equipped with a GATAN digital camera. TEM sam-
ples were prepared by placing a 10-μL drop of the
particle sample dispersion onto a carbon film-
supported copper grid, and then images were recorded
using Digital Micrograph. The average particle core
sizes were determined by measuring at least 75 indi-
vidual particles from recorded TEM images. The
crystal structure of the semiconductor nanoparticles
was verified by X-ray diffraction (XRD) in reflection
mode on a PANalytical ‘X’Pert Pro’ instrument with
Cu Kα radiation (λ = 1.54 nm) at an operating voltage
of 40 kV and a current of 40 mA. A PV9900 from
EDAX (Germany) was used for EDX measurements.
The ZnS shell on the particles was investigated with a
FEI Osiris microscope at 200 kV. For EDX measure-
ments, a Bruker Quantax system (XFlash detector) was
used. The EDX spectra qualification was performed
with the FEI software package BTEM imaging and
analysis.^
Cell culture Biocompatibility and cellular uptake
investigations were performed using human prima-
ry mesenchymal stem cells of two patients without
secondary diseases who declared their consent in
written form after approval and strict compliance
with the local ethic commission (74/09). The cells
were harvested from reaming heads during routine
trauma surgery to stabilize a fracture and to insert
an endoprosthesis, respectively. They were
70 Page 12 of 16
transferred to cell culture medium containing F12K
(Gibco, Life technologies), 20% fetal calf serum
(FCS), 100 U/mL penicillin, and 100 μg/g strep-
tomycin in a 37°C and 5% CO 2 atmosphere
(Wenisch et al. 2005). After reaching confluency,
human marrow stromal cells (hMSCs) were
trypsinized, seeded into cover slips (20,000 cells/
cm2), and covered with F12K medium including
penicillin/streptomycin and only 2% FCS. QDs in
different concentrations were added and incubated
for 1, 3, and 7 days. Cell viability was monitored
during the experiments by inverted light microsco-
py (Type 090-135.002, Leica, Wetzlar, Germany)
equipped with a digital camera (Ds-Fi1, Nikon,
Duesseldorf, Germany). For immunofluorescence
analysis, hMSCs were washed thoroughly with
phosphate-buffered saline (PBS, pH 7.4) and fixed
in 4% phosphate-buffered paraformaldehyde (pH
7.4). After additional rinsing steps, cells were in-
cubated with 5 μg/mL FITC or TRITC-conjugated
phalloidin (Sigma-Aldrich, Steinheim, Germany)
for 40 min in the dark to label the cytoplasmic
actin filaments. After carefully washing, hMSCs
were covered with 2 μg/mL 4′,6-diamidine-
2’phenylindole (DAPI, Carl Roth, Karlsruhe, Ger-
many) for 15 min in the dark to stain the nuclei.
Thereafter, cells were washed in PBS, cover-
slipped with ProLong Gold Antifade Reagent
(Invitrogen, Eugene, Oregon, USA), and stored at
4°C prior to analysis with the confocal laser scan-
ning microscope (TCS SP5, Leica).
Synthesis of the ligands MBA, MPETA, MHA, and
DHLA
MBA Mercaptobutanoic acid (MBA) was synthe-
sized by the reaction of 1.990 g (11.9 mmol) 4-
bromobutanoic acid with 1.190 g (15.6 mmol) thio-
urea in 15 mL ethanol (Yang et al. 2014). Then, the
reaction mixture was refluxed for 3 h. After the
addition of 11 mL NaOH solution (4 M), the mix-
ture was refluxed for another 2 h. Next, the solvent
was evaporated and the residue was extracted three
times with 20 mL of diethyl ether. The pH value of
the aqueous phase was adjusted to 1 with 6 M HCl
and then again extracted with 20 mL diethyl ether.
Finally, the assembled organic phase was dried over
magnesium sulfate and the solvent was removed
under reduced pressure. Yield: 0.750 g (6.24 mmol,
J Nanopart Res (2017) 19:70
52%); NMR: 1H–NMR (200 MHz, CDCl3): δ = 1.30
(t, 1H, SH); 1.88 (t, 2H, CH2-SH); 2.37–2.61 ppm
(m, 4H, CH 2 ); 13 C–NMR (100 MHz, CDCl 3 ):
δ = 23.87 (CH2-SH), 28.66 (CH2), 32.36 (CH 2-
COOH), 179.29 ppm (COOH); IR (film):
2940.5 cm−1 (s, ν(C-H)); 2580.3 cm−1 (w, ν(S-H));
1711.1 cm−1 (s, ν(C = O)); 1413.8 cm−1 (m, δ(C-
H)); 1398.3 cm−1 (m, δ(C-H)); 1309.4 cm−1 (m, δ(C-
H)); 1233.1 cm−1 (m, δ(O-H)); 1198.7 cm−1 (s, ν(C-
O)); 1062.9 cm−1 (w, ν(C-O)).
MPETA The ligand mercaptopentanoic acid (MPETA)
was synthesized by a literature known method (Lu et al.
2008). A 0.700 g (9.1 mmol) thiourea and 1.070 g
(5.9 mmol) 5-bromovaleric acid were solved in 15 mL
ethanol and refluxed overnight. Then, the solvent was
evaporated and the residue was resolved in 15 mL
NaOH solution (7.5 M). The reaction mixture was heat-
ed to 90°C and stirred for 24 h. Then, the mixture was
extracted three times with 50 mL dichloromethane, and
finally, the assembled organic phase was dried over
magnesium sulfate and the solvent was removed under
reduced pressure. Yield: 0.880 g (6.55 mmol, 72%). 1H–
NMR (200 MHz, CDCl3): δ = 1.30 (t, 1H, SH); 1.51–
1.78 (m, 4H, CH2); 2.31 (t, 2H, CH2-COOH); 2.48 ppm
(t, 2H, CH 2-SH); 13C–NMR (100 MHz, CDCl3):
δ = 23.25 (CH2), 24.20 (CH2), 33.23 (CH2-SH), 33.50
(CH 2 -COOH), 179.82 ppm (COOH); IR (film):
2936.5 cm−1 (s, ν(C-H)); 2858.3 cm−1 (s, ν(C-H));
2675.1 cm−1 (w, ν(S-H)); 1709.2 cm−1 (s, ν(C = O));
1413.2 cm−1 (m, δ(C-H)); 1284.6 cm−1 (m, δ(O-H));
1233.2 cm−1 (s, ν(CO)); 1073.4 cm−1 (w, ν(C-O)).
MHA The ligand mercaptohexanoic acid was synthe-
sized by a method described by Chevolot et al. (2001).
The reaction mixture consisting of 13.6 g (120 mmol) ε-
caprolactam, 8.40 g (110 mmol) thiourea, and 6.6 mL
48% bromine (9.80 g, 120 mmol) was heated to 120°C
and stirred 9 h at this temperature. Then, the reaction
mixture was cooled to room temperature and an amount
of NaOH solution was added until the mixture got clear.
The mixture was heated to 100°C and stirred additional
3 h. Then, the pH value was adjusted to 1 with H2SO4
and the clear solution was extracted three times with
20 mL diethyl ether. After this, the assembled organic
phase was washed three times with distilled water, dried
with magnesium sulfate, and the solvent was evaporat-
ed. Finally, the crude product (yellow oil) was distilled
under reduced pressure. Yield: 4.47 g (30.2 mmol,
J Nanopart Res (2017) 19:70
27%). 1H–NMR (400 MHz, DMSO-d6): δ = 1.49 (t, 1H,
SH); 1.59 (m, 2H, CH2), 1.73–1.82 (m, 4H, CH2); 2.49
(t, 2H, CH2COOH); 2.63 ppm (m, 2H, HS-CH2); 13C–
NMR (100 MHz, DMSO-d6): δ = 24.36 (CH2); 24.63
(CH 2 ); 28.77 (CH 2 ); 33.91 (CH 2 ); 34.54 (CH 2 );
176.85 ppm (CO); IR (film): 3443.2 cm−1 (s, ν(O-H));
2935.4 cm−1 (s, ν(C-H)); 2861.0 cm−1 (s, ν(C-H));
2550.0 cm−1 (w, ν(S-H)); 1707.6 cm−1 (s, ν(C = O));
1411.8 cm−1 (m, δ(C-H)); 1309.6 cm−1 (w, δ(C-H));
1269.3 cm−1 (m, δ(O-H)); 1220.5 cm−1 (s, ν(C-O));
1054.4 cm−1 (w, ν(C-O)); 720.5 cm−1 (w, CH2-rocking).
DHLA The synthesis of dihydrolipoic acid (DHLA) was
carried out like described elsewhere (Roux et al. 2005).
A 1.22 g (5.9 mmol) α-lipoic acid was solved in 0.25 M
NaHCO3 solution and cooled and kept at 0°C. Then,
0.9 g (23.8 mmol) NaBH4 was added by small portions
and the reaction mixture was vigorously stirred. After
3 h, the mixture was acidified to pH 1 (9 mL, 6 M HCl).
Then, DHLA was extracted three times from the crude
product by 50 mL of diethyl ether. The assembled
organic phase was dried over magnesium sulfate, and
the solvent was removed under reduced pressure. Yield:
0.983 g (4.72 mmol, 80%). 1H–NMR (400 MHz, D2O):
δ = 1.36–1.71 (m, 6H, CH2); 1.85 (m, 2H, CH2); 2.31 (t,
1H, CH-CO); 2.59 (m, 1H, CH-S); 2.65 ppm (t, 2H,
CH2-S). 13C–NMR (100 MHz, DMSO-d6): δ = 22.31
(CH2-S), 28.61 (CH2), 29.71 (CH2), 33.71 (CH-S);
33.77 (CH 2 ), 34.60 (CH 2 -CO), 42.77 (CH 2 ),
179.21 ppm (CO); IR (film): 2933.9 cm−1 (s, ν(C-H));
2860.6 cm−1 (s, ν(C-H)); 2672.5 cm−1 (m, ν(S-H));
2563.3 cm−1 (m, ν(S-H)); 1706.6 cm−1 (ss, ν(C = O));
1412.6 cm−1 (m, δ(C-H)); 1283.7 cm−1 (m, δ(C-O));
1088.3 cm−1; 936.2 cm−1; 744.6 cm−1.
Synthesis of the tellurium and selenium precursors
(NaHTe and NaHSe) The Te precursor and Se precursor
were prepared by literature known methods
(Schumacher et al. 2009; Gu et al. 2008). For NaHTe,
52 mg Te powder (0.4 mmol, 1 eq.) and 37 mg NaBH4
(1 mmol, 2.5 eq.) were dissolved in 10 mL of degassed
water and under argon atmosphere. It was heated to
75°C for 1 h and then cooled to room temperature giving
a deep red solution. For NaHSe, 34 mg Se powder
(0.4 mmol, 1 eq.) and 37 mg NaBH4 (1 mmol, 2.5 eq.)
were dissolved in 10 mL of degassed water and under
argon atmosphere. It was cooled in an ice bath for 3 h
and then heated up to room temperature giving a color-
less solution.
Page 13 of 16 70
Synthesis of CdTe quantum dots CdTe QDs were syn-
thesized using a standard Schlenk technique. In a
first step, precursor solutions of Te and Cd were
freshly prepared. The Cd precursor was prepared
by dissolving Cd(OAc)2·2H2O (50 mg, 0.188 mmol)
and 0.4 mmol of mercaptocarboxylic acid in 15 mL
of Ar saturated water and setting the pH value of the
mixture above 10 by NaOH or TMAH. Both precur-
sor solutions were mixed in a fixed molar ratio of
1:0.5:2.4 (Cd/Te/mercaptocarboxylic acid) in a two
neck flask under argon atmosphere, and the reaction
mixture was stirred at 100°C for 5–24 h under
reflux. The obtained QDs were purified by precipi-
tation with isopropanol and dispersed in water,
followed by dialysis against water (three times,
MWCO 3500). The particles were characterized
with DLS measurements, TEM measurements, UV/
Vis, and fluorescence emission spectroscopy.
Synthesis of CdTe/ZnS core-shell quantum dots The
ZnS shell was prepared by adding a solution composed
of 0.22 mmol mercaptocarboxylic acid and 34 mg
(0.12 mmol) ZnSO4 in 3 mL of degassed water into
20 mL of prepared 0.025 g (0.10 mmol) CdTe quantum
dot solution. Afterward, under vigorous stirring, a solu-
tion of 9 mg (0.12 mmol) Na2S in 2 mL of degassed
water was added. The pH was adjusted by 1 M NaOH
and the reaction mixture was stirred for 2 h at 60°C
under an argon atmosphere or was treated 5 min at 60°C
with microwave irradiation. The obtained QDs were
purified by precipitation with isopropanol and dispersed
in water, followed by dialysis against water.
Synthesis of MPA-coordinated CdSe quantum dots The
MPA-coordinated CdSe QDs were synthesized accord-
ing to the described CdTe QDs using standard Schlenk
technique. The freshly prepared precursor solutions of
Se and Cd/MPA were mixed and stirred for 5 h under
reflux. The obtained QDs were purified by precipitation
with isopropanol and dispersed in water, followed by
dialysis against water (three times, MWCO 3500).
Synthesis of CdTexSe1-x quantum dots CdTexSe1-x QDs
were synthesized using standard Schlenk technique. The
precursor solutions of NaHTe and NaHSe were freshly
prepared. In the meantime, a third flask was loaded with
54 mg Cd(OAc)2·2H2O (0.2 mmol), 42 μL MPA
(0.48 mmol), and 20 mL of water. NaOH was added
until the solution cleared up. The mixture was heated up
70 Page 14 of 16
to 100°C. Then, both precursor solutions were added
simultaneously in different molar rations (x = 0.1 to 0.9)
and stirred for 3 h. The reaction was quenched with an
ice bath and the particle solution was dialyzed against
water (three times, MWCO 3500). The particles were
characterized with DLS measurements, UV/Vis and
fluorescence spectroscopy, XRD analysis, TEM mea-
surements, and EDX spot analysis.
Microwave-assisted synthesis of CdTe quantum
dots CdTe QDs were also prepared using a
microwave-assisted synthesis. Therefore, the tellurium
precursor was synthesized as described before except
using a volume of 6 mL degassed water. Fifty-six mil-
ligrams (0.21 mmol, 1 eq) Cd(OAc)2·2H2O and 30 mg
(1.4 mmol, 6.7 eq) 11-mercaptoundecanoic acid were
dissolved in 12 mL water. NaOH was used to adjust the
pH value >10. The freshly prepared NaHTe was added
to the cadmium solution in a sealed reaction vial and
heated with microwave irradiation to different tempera-
tures for 10 min. For the series of CdTe QDs with
different mercaptocarboxylic acid ligands, both precur-
sor solutions were mixed in a sealed borosilicate glass
reaction vial with the fixed molar ratio of 1:0.5:2.4 (Cd/
Te/mercaptocarboxylic acid). The mixture was treated
with microwave irradiation for 10 min at 130°C. The
resulting particle solutions were precipitated, washed
three times with isopropanol, dispersed in water, and
were dialyzed against water.
Acknowledgements The authors wish to acknowledge Hans P.
Reisenauer (Institute of Organic Chemistry, Justus-Liebig Univer-
sity at Giessen) for his valuable suggestions and assistance in the
spectrofluorometric determinations and Oliver Falkenbach (Insti-
tute of Inorganic and Analytical Chemistry, Justus-Liebig Univer-
sity at Giessen) for the powder diffraction measurements. We also
want to thank Sabine Schlecht for the initiation of this work.
Furthermore, we want to thank Christian Schöttle and Claus
Feldmann (Institute of Inorganic Chemistry, Karlsruhe Institute
of Technology) for the EDX analysis of the CdTe/ZnS QDs.
Authors’ contribution Anne S. Schulze, Isabella Tavernaro,
and Friederike Machka contributed equally to this work. They
designed the study, performed particle syntheses, and the particle
characterization. Anne S. Schulze synthesized the MUDA-
coordinated CdTe QDs with two different Cd/Te ratios at different
temperature by microwave irradiation. Isabella Tavernaro synthe-
sized the MPA-coordinated CdSe QDs and the CdTe QDs with
different mercaptocarboxylic acids, dihydrolipoic acid, and 3-
mercapto-1-propanesulfonic acid by conventional synthesis and
microwave irradiation. Friederike Machka synthesized the alloyed
J Nanopart Res (2017) 19:70
CdTexSe1-x QDs by conventional synthesis. Katrin S. Lips and
Olga Dakischew designed and performed the cell culture analysis.
Compliance with ethical standards We assure that we have
kept the ethical standards throughout this work.
Conflict of interest The authors declare that they have no con-
flict of interest.
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