Cellulose

https://doi.org/10.1007/s10570-018-2065-z (0123456789().,-volV)
(0123456789().,-volV)

ORIGINAL PAPER

Fluorescent CdTe-QD-encoded nanocellulose microspheres

by green spraying method
Qingshun Guan . Ruyuan Song . Weibing Wu . Lei Zhang . Yi Jing .
Hongqi Dai . Guigan Fang

Received: 14 June 2018 / Accepted: 30 September 2018

Ó Springer Nature B.V. 2018

Abstract With water-soluble CdTe quantum Dots
(QDs) as fluorescent labels and TEMPO-oxidized
cellulose nanofibrils (CNF) as matrix, dual-color QD-
encoded microspheres were prepared by mechanical
spraying, freeze-molding and subsequent electrostatic
cross-linking by calcium ion. The entire preparation
process was accomplished in aqueous phase without
any chemical treatment. The nanocellulose micro-
spheres possessed porous structure and were able to be
dispersed stably in water in the form of hydrogels.
CdTe QDs were efficiently fixed in the network of
intertwined nanofibrils via hydrogen bonding with
CNF, making the microspheres to obtain high photo-
luminescence (PL) intensity and identifiable encoding
signals consisting of seven kinds of microsphere
arrays. The crystalline structure and chemical compo-
sition of both CdTe QDs and CNF were not affected
during the preparation process. The comparision of PL
behaviors of CdTe QDs and QD-encoded micro-
spheres in different media indicate that CNF matrix
provided good protection of QDs and improved the PL
intensity and photostability.

Q. Guan
R. Song
W. Wu (&)
Y. Jing
H. Dai

Jiangsu Co-Innovation Center for Efficient Processing and
Utilization of Forest Resources, Jiangsu Provincial Key
Lab of Pulp and Paper Science and Technology, Nanjing
Forestry University, Nanjing 210037, China
e-mail: wbwu@njfu.edu.cn

L. Zhang
Key Laboratory for Organic Electronics and Information,
National Jiangsu, Synergetic Innovation Center for
Advanced Materials (SICAM), Nanjing University of
Posts and Telecommunications, Nanjing 210023, China

G. Fang
Institute of Chemical Industry of Forestry Products,
Chinese Academy of Forestry, Nanjing 210042, China

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Graphical Abstract Dual-color CdTe-encoded
nanocellulose microspheres were prepared via pure
physical process in aqueous phase. The fluorescent
microspheres possessed high photoluminescence
intensity and identifiable seven kinds of encoding
signals. The nanocellulose matrix provided good
protection of CdTe QDs and improved the photolu-
minescence intensity and photostability.
Keywords Quantum dots
Fluorescent
microspheres
Nanocellulose
Fluorescence coding
Introduction
Fluorescence-encoded microspheres are widely used
in biomedical fields such as genetic analysis (Han et al.
2001), immunoassay (Cretich et al. 2013), high-
throughput drug screening (Wilson et al. 2006), and
optical instrument calibration (Gao and Nie 2004), etc.
Generally, there are two main types of fluorescence-
encoded microspheres according to the classification
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Cellulose
of loaded substances: quantum dots (QDs) and organic
dyes (Leng et al. 2015). QDs have some unique
advantages compared with organic dyes (Li and Yeh
2010; Hodlur and Rabinal 2014; Zou et al. 2008): (1)
QDs have stable optical properties as inorganic
nanoparticles; (2) QDs have narrow emission and
wide excitation wavelengths, which make them can be
excited by selecting any wavelength that is 10 nm
smaller than their emission wavelength. In this way,
the same excitation light can be used to excite QDs
with various emission wavelengths; (3) The half-peak
width of QDs is narrow (usually \ 50 nm) and
symmetrically distributed. Thus, the emission spectra
of microspheres are not easy to overlap when fluores-
cence encoding is carried out; (4) The position of the
emission peak of the QDs can be adjusted by
controlling the size and composition of nanoparticles.
In particular, water-soluble QDs with low toxicity and
good biocompatibility can now be synthesized in
aqueous phase (Liu et al. 2009a, b). Therefore, QDs
are the most suitable fluorescent labels for the
preparation of encoded microspheres. Multicolor
Cellulose
QD-encoded polystyrene microspheres have been
widely reported and employed for the detection of a
large number of analytes simultaneously (Ma et al.
2007; Yu et al. 2012). Silica microspheres capped with
QDs were used to serve as the response signal label
(Zou et al. 2016). Other matrices such as In2S3, InVO4,
and BiOI poprous microspheres were also used for the
deposition of QDs (Huang et al. 2016; Liu et al.
2018a, b; Shen et al. 2018).
Surface functional groups of hydroxyl, carboxyl or
amino are usually required for encoded microspheres
to couple probe molecules and detect specific reac-
tions of certain target molecules, such as antibodies,
antigens, nucleic acids, etc. (Dong et al. 2008).
Traditional microsphere materials such as polystyrene
(Liu et al. 2009a, b), silica (Insin et al. 2008),
melamine–formaldehyde (Chen et al. 2015) and
copolyorganosilicone (Rankin et al. 2015) do not
carry effective functional groups themselves. The
introduction of functional groups into microspheres
generally involve the participation of chemical reac-
tions, which is complex and not environmentally
friendly. In addition, biological systems require
microspheres to have good biocompatibility. Thus, it
is necessary to explore natural materials as micro-
sphere substrate. Saito et al. (2006, 2007, 2009)
reported on the preparation of cellulose nanofibrils
(CNF) by oxidizing natural cellulose with 2,2,6,6-
tetramethylpiperidine-1-oxyl radical (TEMPO). The
CNF have a diameter within a dozen nanometers, a
length of several hundred nanometers to several
micrometers, and an aspect ratio of up to 100 or more,
which are very suitable for building various nanocel-
lulose materials by physical winding and hydrogen
bonding. At the same time, carboxyl groups are
introducted on the glucose unit C6 of the cellulose
through the TEMPO-mediated oxidation. The pres-
ence of carboxyl groups not only confers better
reactivity and modifiability to CNF, but also enables
CNF to be stably dispersed and easily processed in
aqueous phase system (Isogai et al. 2011). Therefore,
TEMPO-oxidized CNF are ideal material for prepar-
ing natural polymer microspheres. Recently, Cai et al.
(2014) reported on a simple mechanical method for
preparing aerogel microsphere templates based on
CNF. They used a pressure spray device to process
colloidal CNF into small droplets, which were then
shaped using liquid nitrogen as a coagulation bath.
The results showed that the microspheres had good
porous morphology. However, the structural stability
of microspheres dispersed in water for a long time
could not be guaranteed (Zhang et al. 2017).
In this study, we report a simple and green method
to prepare stable dual-color CdTe QD-encoded micro-
spheres in a pure aqueous system. Water-soluble CdTe
QDs with different wavelengths and CNF were used as
fluorescent labels and microsphere matrix, respec-
tively. A series of encoded fluorescent signals were
obtained by changing the proportion of two types of
CdTe QDs. The photostabilities of QD-encoded
microspheres in different media and upon light
illumination were thoroughly investigated.
Materials and methods
Materials
Bleached softwood pulp (Asia Pacific Senbo (Shan-
dong) Pulp and Paper Co., Ltd., China) was used as an
original material for preparing CNFs. 2,2,6,6-Tetram-
ethylpiperidine 1-oxyl (TEMPO) was purchased from
Sigma Aldrich, USA. Thioglycolic acid (TGA), cad-
mium acetate dihydrate (Cd(CH3COO)2
2H2O) and
potassium tellurite (K2TeO3) were purchased from
Shanghai Macklin Biochemical Co., Ltd. Sodium
borohydride (NaBH4) and sodium hypochlorite
(NaClO) were purchased from Shanghai Aladdin
Reagents Co., Ltd. Calcium chloride anhydrous
(CaCl2) and sodium bromide (NaBr) were purchased
from Nanjing Chemical Reagent Co., Ltd. All reagents
are laboratory grade without further purification.
Preparation of water-soluble CdTe QDs
The synthesis process was carried out according to a
literature method (Wu et al. 2012) with a slight
modification. The molar ratio of Cd(CH3COO)2/TGA/
K2TeO3 was set at 1.0: 1.0: 0.2. In brief, Cd(CH3-
COO)2
2H2O (0.4 mmol, 106.6 mg) and TGA
(0.4 mmol, 30.8 mg) were dissolved in 50 ml deion-
ized water under magnetic stirring, and the pH was
adjusted to 11.0 by dropwise addition of 1 mol/L
NaOH solution. After stirring for 5 min, then K2TeO3
(0.08 mmol, 20.3 mg) dissolved in 50 ml deionized
water was added. Afterward, NaBH4 (0.4 mmol,
150 mg) was added into the precursor solution. After
the reactions proceeded for another 5 min, the mixture
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was transferred to a flask equipped with a condenser
and refluxed at 100 °C without inert gas protection.
CdTe QDs with a series of emission wavelengths were
obtained via controlling the reaction time.
Preparation of cellulose nanofibrils (CNF)
CNF were prepared via TEMPO/NaClO/NaBr oxida-
tion system (Benhamou et al. 2014). Never-dried
bleached softwood pulp (10 g) was suspended in
deionized water (500 ml) containing TEMPO (0.16 g)
and NaBr (1.6 g). An aliquot of 7.6 mM NaClO
solution (120 ml) was added to the cellulose slurry,
and the pH was maintained at 10.5 by adding 0.2 mol/
L NaOH at 25 °C under mechanical agitation. The
reaction was stopped by dilution with deionized water
when no more decrease in pH was observed (Fuku-
zumi et al. 2013). The oxidized pulp was purified via
thoroughly washing with deionized water and finally
ultrasonicated (Ultrasonics FS-300N, Output power:
300 W, Output frequency: 20 kHz) at consistency of
1 wt.% for 5 min at 300 W to obtain the CNF
suspension. The carboxyl content of CNF was deter-
mined by the titration method (Zhang et al. 2012a, b).
Preparation of CdTe-QD-encoded fluorescent
microspheres (QD-FMS)
The molar proportions of two types of CdTe QDs
with emission wavelengths of 530 nm (CdTe-I) and
590 nm (CdTe-II) were set as 0:1, 1:2, 1:1, 2:1, 4:1,
Fig. 1 Absorption spectra (a) and normalized emission spectra (b) of CdTe QDs at different refluxing time. The excitation wavelength
is 405 nm
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Cellulose
6:1 and 1:0, and the total mass ratio of QDs to CNF
was controlled to be 5.0 wt.%. After stirring for
5 min, the CdTe and CNF mixture was placed in an
ultrasonic bath (100 W, 40 kHz) for 10 min. Then
the obtained suspension was transferred to a spraying
device designed by ourselves and sprayed at a certain
speed by controlling the pressure. The sprayed liquid
droplets were rapidly frozen in the coagulation bath
of liquid nitrogen. After the liquid nitrogen volati-
lized, the resulted ice beads were rapidly transferred
to a 0.2 mol/L CaCl2 solution under mild stirring.
The cross-linking process was performed for 15 min.
Then the microspheres were washed with deionized
water several times by centrifugation and finally
dispersed in the water.
Characterization
Fluorescence measurements were carried out using an
optical fiber spectrometer (R4, Shanghai ideal optics co.,
Ltd.) with an excitation wavelength of 405 nm. UV/Vis
absorption spectra were recorded on an ultraviolet
spectrophotometer (TU-1900, Beijing general instrument
co., Ltd.). X-ray diffraction (XRD) measurements were
performed on a combined multifunctional horizontal
X-ray diffractometer (Ultima IV, Japan). For the XRD
characterization of QDs, an aqueous solution of as-
prepared CdTe was diluted with acetone and centrifuged
at 8000 rpm for 5 min. TEM images were obtained using
a high resolution transmission electron microscope (JEM-
2100 UHR, Japan) operating at 200 kV. Micrographs
Cellulose
were obtained using biological microscope (PH100,
Jiangxi Phoenix Optical Technology Co., Ltd.), field
emission scanning electron microscopy (SEM) (JSM-
7600F, Japan) and laser scanning confocal microscope
(FV-1000, Japan), respectively. Attenuated total refrac-
tion Fourier-transform infrared spectroscopy (ATR-
FTIR) was recorded on a FTIR-650 spectrometer (Tianjin
Gangdong Science and Technology Co, Ltd., China).
Results and discussion
The performance of CdTe QDs
Figure 1 shows the absorption spectra (a) and the
normalized emission spectra (b) of the CdTe QD
aqueous solutions which were taken from the refluxing
reaction mixture at different intervals of time. Upon
prolonging refluxing time, both the absorption and
emission wavelengths move toward longer wave-
lengths with an increase in the size of the CdTe QDs as
a consequence of the quantum confinement. There-
fore, CdTe QDs with desired emission wavelength
could be obtained by controlling the refluxing time.
The images of CdTe QDs under daylight lamp and
irradiated ultraviolet lamp are presented in the
inserted picture of Fig. 1a. The change in the
fluorescence color can be clearly observed.
Fig. 2 XRD pattern (a) and TEM image (b) of CdTe QDs. Refluxing time for CdTe QDs: 3 h
The XRD pattern of representative CdTe QDs is
shown in Fig. 2a. Compared to cubic phase CdTe, the
diffraction patterns of the prepared CdTe QDs slightly
shifted to higher angles with peak widths and shapes
being nearly unchanged. Similar shifts were observed
in the diffraction patterns of core–shell ZnS@CdSe
QDs (Dabbousi et al. 1997) The results suggested that
a CdS shell was formed on the surface of the CdTe
core. TGA could produced a small amount of S2- due
to partial hydrolysis during refluxing. The S2- coor-
dinated with Cd2? in aqueous solution to form a CdS
shell, which could effectively passivate the surface
defects of CdTe QDs and improve their quantum yield
and stability (Rogach et al. 2007). TEM images show
that CdTe QDs have obvious lattice structure, as seen
in Fig. 2b. The average sizes of CdTe QDs with
refluxing time of 0.5, 1, 3 and 7 h were 4, 5, 7 and
9 nm, respectively.
Synthesis of QD-FMS
The synthesis route of QD-FMS is shown in
Scheme 1. During the preparation process, freeze-
molding by liquid nitrogen and cross-linking by Ca2?
were critical steps for the formation of stable micro-
spheres. Because of the presence of high content
carboxyl on the surface (1.2 mmol/g), CNF were
electrostatically cross-linked with Ca2? due to the
ionic interactions between divalent cations and
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Scheme 1 Synthesis route of QD-FMS
negatively charged groups (Naseri et al. 2016), leading
to a stable three-dimensional network structure of
CNF in the microspheres (Liu et al. 2018a, b). CdTe
QDs could be effectively fixed in the CNF matrix via
the hydrogen bonding between the carboxyl groups on
the surface of the QDs and the hydroxyl and carboxyl
groups of cellulose molecules (Gong et al. 2005). At
the same time, the aggregation of QDs could be
limited by the three-dimensional network structure of
CNF. Therefore, the microsphere shell provided
protective effect on the loaded CdTe QDs. In addition,
the preparation process of QD-FMS, which was
physically carried out in aqueous system, was simple
and green.
Figure 3a gives the TEM image of TEMPO-
oxidized CNF. The size of CNF was measured to be
in the range of 10–20 nm in width and 0.4–1.6 lm in
length via image software. As illustrated in Fig. 4b,
QD-FMS have highly porous structure from the
intertwining of CNF bundles, which allows the
microspheres to serve as the carrier for targeted drug
delivery. The deposition of CdTe QDs on CNF can be
clearly observed from TEM images (Fig. 3c, d).
Figure 3e presents the photograph of QD-FMS under
an optical microscope. It can be seen that the QD-FMS
exist in the form of hydrogel, which has a good
spherical morphology with the average particle size of
47.5 um and the coefficient of variation (CV) of
9.34%. QD-FMS possess intense fluorescence emis-
sion under a confocal microscope and the boundaries
between individual microspheres are clear and distin-
guishable (Fig. 3f).
123
Cellulose
The FTIR spectra of CNF and QD-FMS are
presented in Fig. 4a. The characteristic peaks
observed for CNF at 3339, 2894 and 1723 cm-1 are
related to O–H stretching, asymmetric C–H stretching
and carboxyl stretching, respectively (Salama et al.
2015). It is noted that there is little difference in the
FTIR spectra between CNF and QD-FMS, which
indicates that the incorporation of CdTe QDs dose not
change the chemical structure of CNF matrix. There-
fore, QD-FMS can be further modified on the active
sites of both –COOH and –OH groups. In addition, the
crystal structure of CNF (cellulose I) and the CdTe
QDs are simultaneously reflected in the X-ray diffrac-
tion patterns of QD-FMS (Fig. 4b), indicating that the
loading of CdTe QDs did not change the crystal
structures of both CNF and QDs. Above all, the
encapsulation of CdTe QDs into nanocellulose micro-
spheres shows no negative effects, which are impor-
tant to guarantee the paintability and fluorescent
performance of QD-FMS.
Dual-color QD-FMS
In order to avoid spectral overlap, two types of QDs
with emission wavelengths of 530 nm (CdTe-I) and
590 nm (CdTe-II) were selected as fluorescent labels.
Figure 5 shows the photographs under the ultraviolet
lamp and the normalized emission spectra of the QD-
FMS with different ratios of CdTe-I and CdTe-II.
Narrow and symmetrical fluorescence emission peak
was observed for QD-FMS loaded with single CdTe-I
or CdTe-II. When two types of QDs were
Cellulose

Fig. 3 Morphology and structure of QD-FMS. a TEM image of CNF. b SEM image of QD-FMS. c, d TEM images of CdTe QD loaded
on CNF. e Optical microscope photograph of QD-FMS. f Fluorescence confocal microscope photograph of QD-FMS

simultaneously loaded, two distinguishable emission II. They are typical fluorescence-encoded signals.
peaks at round 530 nm and 590 nm were recognized. However, there is a remarkable reduction in the PL
Adjustable PL intensity and intensity ratio were intensity at 530 nm of QD-FMS compared to pure
obtained by changing the ratio of CdTe-I and CdTe- CdTe-I. The fluorescence change can be attributed to

123
 Cellulose

Fig. 4 FTIR spectra (a) and XRD patterns (b) of CNF, CdTe QDs and QD-FMS

Fig. 5 Fluorescence-encoded signals of QD-FMS. a Photographs of dual-color QD-FMS illuminated by 365-nm ultraviolet light. b,
c Normalized PL spectra of QD-FMS

the photon reabsorption and Förster resonance energy

transfer (FRET) (Zhang et al. 2012a, b; Fournier- Fig. 6 PL spectra and maximum intensity of the CdTe QDs c
Bidoz et al. 2008). Because of the overlap between dispersed in different solvents with time. a Water, b ethanol,
c acetone, d NaCl solutions (0.02 mol/L)

123
Cellulose

123
 Cellulose

123
 Cellulose
b Fig. 7 PL spectra and maximum intensity of QD-FMS
dispersed in different solvents with time. a Water, b ethanol,
c acetone, d NaCl solutions (0.02 mol/L)
the absorption spectrum of CdTe-II and the emission
spectrum of CdTe-I, FRET can occur between CdTe-
I and CdTe-II QDs which are closely distributed
within 1–10 nm in the microspheres. Despite the
negative effect of FRET, the encoding spectrum of
each type of QD-FMS still has a unique and
recognizable fluorescent signal.
Photostability of QD-FMS
QDs can be directly applied as fluorescent labels in the
biomedical field, but their optical properties are
extremely unstable (Sukhanova and Nabiev 2008).
Figure 6 shows the emission spectra and maximum
fluorescent intensity of CdTe QDs dispersed in water,
ethanol, acetone and NaCl solution (0.02 mol/L) over
time. The inserted pictures are the the digital pho-
tographs of the QD suspensions in above four solvents
after 72 h. It can be seen that the CdTe QDs had
stable fluorescent behavior in water and the PL
intensity remained approximately constant within
72 h. However, the PL intensity of CdTe QDs in
ethanol, acetone and NaCl solution decreased dramat-
ically with time. Besides, the emission peaks of CdTe
QDs showed red-shifts in ethanol, acetone and NaCl
solution compared to water. These changes could be
attributed to the agglomeration of CdTe QDs in above
mediums except water (Erogbogbo et al. 2010). The
thiol groups at one end of the TGA could coordinated
with the metal atom on the surface of the CdTe QDs
and the carboxyl group at the other end could form
hydrogen bond with water, enabling TGA-coated
CdTe QDs to disperse stably in water (Zhou et al.
2011). However, the hydrogen bonding between QDs
and medium molecules were greatly weakened in the
organic solvents with lower polarity than water, such
as ethanol and acetone. Hence, the hydrogen bond
interaction between CdTe QDs themselves induced
their aggregation. On the other hand, CdTe QDs
dispersed in aqueous solution could form electrical
double layers due to the presence of negatively
charged surfaces (Schneider et al. 2009). The addition
of electrolyte such as NaCl produced an electric
neutralization effect and compressed the electrical
Fig. 8 Comparison of the photostability of CdTe QD and QD-
FMS aqueous suspension. The decay curves of PL intensity
were plotted as a function of the time of samples being exposed
under 254-nm ultraviolet illumination from a 100 W ultraviolet
lamp
double layers (Jiang et al. 2009). As a result, the
collision distance between CdTe QDs decreased,
leading to the aggregation of CdTe QDs under van
der waals force. The digital photographs in Fig. 6
clearly illustrate the aggregation of CdTe QDs in
ethanol, acetone and NaCl solution.
In order to investigate the protective effect of
microsphere substrate on the CdTe QDs, the fluores-
cent behaviors of QD-FMS in different solvents were
analyzed. Figure 7 shows the emission spectra of the
QD-FMS dispersed in water, ethanol, acetone and
NaCl solution (0.02 mol/L) over time. It can be seen
that the fluorescent behaviors of the QD-FMS in
ethanol, acetone and NaCl solution were similar to that
in water. The emission peak position remained
unchanged and the PL intensity only decreased
slightly. It proved that the solvent effect had little
effect on the PL performance of the QD-FMS. There
are two main reasons to explain this phenomenon:
First, the microsphere of CNF could protect CdTe QDs
from directly contacting solvents; Second, the fluo-
rescence quenching caused by the aggregation
between CdTe QDs might be limited since they were
fixed in the CNF matrix through hydrogen bond
interaction (Wu et al. 2008). Therefore, the fluorescent
stability and intensity of QD-FMS are remarkably
improved compared with CdTe QDs.
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Photobleaching experiments were also performed
to investigate to the photostability of QD-FMS.
Figure 8 illustrates the decay curves of normalized
maximum PL intensity as a function of exposure time
for CdTe QDs and QD-FMS. The PL intensity of the
CdTe QDs dropped by half after 3 h, while 86% of the
initial value was retained in the case of QD-FMS.
Obviously, encapsulation by CNF microspheres
improved the photostability of CdTe QDs. It can be
explained by that the microsphere matrix pro-
vides good protection of CdTe QDs and reduce the
negative effect of medium outside (Wu et al. 2009).
Conclusion
Dual-color QD-FMS were prepared via a simple and
green spraying method. The QD-FMS, which pos-
sessed porous spherical structure with the average
particle size of 47.5 lm, can be stably dispersed in
aqueous solution in the form of a hydrogel. The
encapsulation of CdTe QDs into microspheres did not
affect the crystal structure of QDs and the surface
groups of CNF. The network matrix of CNF effec-
tively loaded CdTe QDs via hydrogen bonding and
further provided good protection of QDs against
solvent effect, which improved the PL intensity and
photostability. A series of intense and identifiable
encoding fluorescent signals of QD-FMS were
obtained by tuning the ratios of CdTe-I and CdTe-II.
This type of fluorescence-encoded QD-FMS can be
used as multi-functional template and possesses
potential application in the biomedical field.
Acknowledgments The support of this work by the Natural
Science Foundation of Jiangsu Province (BK20171450),
National Key Research and Development Program of China
(2017YFD0601005), and Priority Academic Program
Development of Jiangsu Higher Education Institutions
(PAPD) are gratefully acknowledged.
References
Benhamou K, Dufresne A, Magnin A, Mortha G, Kaddami H
(2014) Control of size and viscoelastic properties of
nanofibrillated cellulose from palm tree by varying the
TEMPO-mediated oxidation time. Carbohydr Polym
99:74–83
Cai HL, Sharma S, Liu WY, Mu W, Liu W, Zhang XD, Deng YL
(2014) Aerogel microspheres from natural cellulose
123
Cellulose
nanofibrils and their application as cell culture scaffold.
Biomacromolecules 15:2540–2547
Chen H, Lin H, Xu J, Wang B, Lin ZB, Zhou JC, Wang YS
(2015) Chromaticity-tunable phosphor-in-glass for long-
lifetime high-power warm w-LEDs. J Mater Chem C
3:8080–8089
Cretich M, Sola L, Gagni P, Chiari M (2013) Novel fluorescent
microarray platforms: a case study in neurodegenerative
disorders. Expert Rev Mol Diagn 13:863–873
Dabbousi B, Rodriguez J, Mikulec F, Heine J, Mattoussi H,
Ober R, Jensen K, Bawendi M, Rodriguez-Viejo J (1997)
(CdSe)ZnS core–shell quantum dots: synthesis and char-
acterization of a size series of highly luminescent
nanocrystallites. J Phys Chem B 101:9463–9475
Dong B, Song H, Qin R, Bai X, Wang F, Fan L, Pan G, Lu S, Ren
X, Zhao H (2008) White luminescence by up-conversion
from thin film made with Ln3?-doped NaYF4 nanoparti-
cles. J Nanosci Nanotechnol 8:1254–1257
Erogbogbo F, Yong KT, Roy I, Hu R, Law WC, Zhao
W, Ding H, Wu F, Kumar R, Swihart MT (2010) In vivo
targeted cancer imaging, sentinel lymph node mapping and
multi-channel imaging with biocompatible silicon
nanocrystals. ACS Nano 5:413–423
Fournier-Bidoz S, Jennings TL, Klostranec JM, Fung W, Rhee
A, Li D, Chan WC (2008) Facile and rapid one-step mass
preparation of quantum-dot barcodes. Angew Chem
120:5659–5663
Fukuzumi H, Saito T, Isogai A (2013) Influence of TEMPO-
oxidized cellulose nanofibril length on film properties.
Carbohydr Polym 93:172–177
Gao XH, Nie SM (2004) Quantum dot-encoded mesoporous
beads with high brightness and uniformity: rapid readout
using flow cytometry. Anal Chem 76:2406–2410
Gong YJ, Gao MY, Wang DY, Möhwald H (2005) Incorporat-
ing fluorescent CdTe nanocrystals into a hydrogel via
hydrogen bonding: toward fluorescent microspheres with
temperature-responsive properties. Chem Mater
17:2648–2653
Han MY, Gao XH, Su JZ, Nie S (2001) Quantum-dot-tagged
microbeads for multiplexed optical coding of biomole-
cules. Nat Biotechnol 19:631
Hodlur RM, Rabinal MK (2014) A new selenium precursor for
the aqueous synthesis of luminescent CdSe quantum dots.
Chem Eng J 244:82–88
Huang C, Hong Y, Yan X, Xiao L, Huang K, Gu W, Liu K, Shi
W (2016) Carbon quantum dot decorated hollow In2S3
microspheres with efficient visible-light-driven photocat-
alytic activities. Rsc Adv 6(46):40137–40146
Insin N, Tracy JB, Lee H, Zimmer JP, Westervelt RM, Bawendi
MG (2008) Incorporation of iron oxide nanoparticles and
quantum dots into silica microspheres. ACS Nano
2:197–202
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cel-
lulose nanofibers. Nanoscale 3:71–85
Jiang J, Oberdörster G, Biswas P (2009) Characterization of
size, surface charge, and agglomeration state of nanopar-
ticle dispersions for toxicological studies. J Nanopart Res
11:77–89
Leng YK, Sun K, Chen XY, Li WW (2015) Suspension arrays
based on nanoparticle-encoded microspheres for high-
Cellulose
throughput multiplexed detection. Chem Soc Rev
44:5552–5595
Li I, Yeh CS (2010) Synthesis of Gd doped CdSe nanoparticles
for potential optical and MR imaging applications. J Mater
Chem 20:2079–2081
Liu JG, Liang JG, Han HY, Sheng ZH (2009a) Facile synthesis
and characterization of CdTe quantum dots–polystyrene
fluorescent composite nanospheres. Mater Lett
63:2224–2226
Liu QH, Liu J, Guo J-C, Yan X-L, Wang D-H, Chen L, F-y Yan,
Chen L-G (2009b) Preparation of polystyrene fluorescent
microspheres based on some fluorescent labels. J Mater
Chem 19:2018–2025
Liu Q, Yin Y, Hao N, Qian J, Li L, You T, Mao H, Wang K
(2018a) Nitrogen functionlized graphene quantum dots/3D
bismuth oxyiodine hybrid hollow microspheres as
remarkable photoelectrode for photoelectrochemical
sensing of chlopyrifos. Sens Actuators B Chem
260:1034–1042
Liu YY, Sui YL, Liu C, Liu CQ, Wu MY, Li B, Li YM (2018b)
A physically crosslinked polydopamine/nanocellulose
hydrogel as potential versatile vehicles for drug delivery
and wound healing. Carbohydr Polym 188:27–36
Ma Q, Wang X, Li Y, Shi Y, Su X (2007) Multicolor quantum
dot-encoded microspheres for the detection of biomole-
cules. Talanta 72:1446–1452
Naseri N, Deepa B, Mathew AP, Oksman K, Girandon L (2016)
Nanocellulose-based interpenetrating polymer network
(IPN) hydrogels for cartilage applications. Biomacro-
molecules 17:3714–3723
Rankin JM, Neelakantan NK, Lundberg KE, Grzincic EM,
Murphy CJ, Suslick KS (2015) Magnetic, fluorescent, and
copolymeric silicone microspheres. Adv Sci 2:1500114
Rogach AL, Franzl T, Klar TA, Feldmann J (2007) Aqueous
synthesis of thiol-capped CdTe nanocrystals: state-of-the-
art. J Phys Chem C 111:14628–14637
Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006)
Homogeneous suspensions of individualized microfibrils
from TEMPO-catalyzed oxidation of native cellulose.
Biomacromolecules 7:1687–1691
Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose
nanofibers prepared by TEMPO-mediated oxidation of
native cellulose. Biomacromolecules 8:2485–2491
Saito T, Hirota M, Tamura N, Kimura S, Fukuzumi H, Heux L,
Isogai A (2009) Individualization of nano-sized plant cel-
lulose fibrils by direct surface carboxylation using TEMPO
catalyst under neutral conditions. Biomacromolecules
10:1992–1996
Salama A, Shukry N, El-Sakhawy M (2015) Carboxymethyl
cellulose-g-poly (2-(dimethylamino) ethyl methacrylate)
hydrogel as adsorbent for dye removal. Int J Biol Macro-
mol 73:72–75
Schneider R, Wolpert C, Guilloteau H, Balan L, Lambert J,
Merlin C (2009) The exposure of bacteria to CdTe-core
quantum dots: the importance of surface chemistry on
cytotoxicity. Nanotechnology 20:225101
Shen Q, You Z, Yu Y, Qin T, Su Y, Wang H, Wu C, Zhang F,
Yang H (2018) A carbon quantum dots/porous InVO4
microsphere composite with enhanced photocatalytic
activity. Eur J Inorg Chem 9:1080–1086
Sukhanova A, Nabiev I (2008) Fluorescent nanocrystal-encoded
microbeads for multiplexed cancer imaging and diagnosis.
Crit Rev Oncol Hematol 68:39–59
Wilson R, Cossins AR, Spiller DG (2006) Encoded microcar-
riers for high-throughput multiplexed detection. Angew
Chem Int Ed 45:6104–6117
Wu W-B, Wang M-L, Sun Y-M, Huang W, Cui Y-P, Xu C-X
(2008) Color-tuned FRET polystyrene microspheres by
single wavelength excitation. Opt Mater
30(12):1803–1809
Wu W-B, Liu C, Wang M-L, Zhou S-R, Jiang W, Sun Y-M, Cui
Y-P, Xu C-X (2009) Uniform silica nanoparticles encap-
sulating two-photon absorbing fluorescent dye. J Solid
State Chem 182(4):862–868
Wu SL, Dou J, Zhang J, Zhang SF (2012) A simple and eco-
nomical one-pot method to synthesize high-quality water
soluble CdTe QDs. J Mater Chem 22:14573–14578
Yu H-Y, Kima IS, Niessner R, Knopp D (2012) Multiplex
competitive microbead-based flow cytometric immunoas-
say using quantum dot fluorescent labels. Anal Chim Acta
750:191–198
Zhang PF, He Y, Ruan Z, Chen FF, Yang J (2012a) Fabrication
of quantum dots-encoded microbeads with a simple cap-
illary fluidic device and their application for biomolecule
detection. J Colloid Interface Sci 385:8–14
Zhang K, Fischer S, Geissler A, Brendler E (2012b) Analysis of
carboxylate groups in oxidized never-dried cellulose II
catalyzed by TEMPO and 4-acetamide-TEMPO. Carbo-
hydr Polym 87:894–900
Zhang F, Ren H, Dou J, Tong GL, Deng YL (2017) Cellulose
nanofibril based-aerogel microreactors: a high efficiency
and easy recoverable W/O/W membrane separation sys-
tem. Sci Rep 7:40096
Zhou D, Lin M, Chen ZL, Sun HZ, Zhang H, Sun HC, Yang B
(2011) Simple synthesis of highly luminescent water-sol-
uble CdTe quantum dots with controllable surface func-
tionality. Chem Mater 23:4857–4862
Zou L, Gu ZY, Zhang N, Zhang YL, Fang Z, Zhu WH, Zhong
XH (2008) Ultrafast synthesis of highly luminescent green-
to near infrared-emitting CdTe nanocrystals in aqueous
phase. J Mater Chem 18:2807–2815
Zou C, Foda MF, Tan X, Shao K, Wu L, Lu Z, Bahlol HS, Han H
(2016) Carbon-dot and quantum-dot-coated dual-Emission
core-satellite silica nanoparticles for ratiometric intracel-
lular Cu2? imaging. Anal Chem 88:7395–7403
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