Microchimica Acta (2019) 186: 516

https://doi.org/10.1007/s00604-019-3603-6

ORIGINAL PAPER

Organosilane-functionalized carbon quantum dots and their

applications to “on-off-on” fluorometric determination of chromate
and ascorbic acid, and in white light-emitting devices
Yushan Liu 1 & Wei Li 1 & Peng Wu 1 & Chunhui Ma 1 & Xueyun Wu 1 & Sha Luo 1 & Shouxin Liu 1

Received: 22 January 2019 / Accepted: 12 June 2019 / Published online: 6 July 2019
# Springer-Verlag GmbH Austria, part of Springer Nature 2019

Abstract
Organosilane-functionalized carbon quantum dots (Si-CQDs) were synthesized by reacting glucosamine and 3-[2-(2-
aminoethylamino)ethylamino]propyl-trimethoxysilane in acetone. The surface morphology, crystal structure, function-
al groups, elemental composition, and optical properties of the Si-CQDs were characterized using TEM (HRTEM),
XRD, FT-IR, XPS, UV-vis absorption and fluorescence spectroscopy. They show that N-containing groups including
C=N and C-N, and Si-containing groups including Si-O-C and Si-O-Si have been formed on the surface of Si-
CQDs. The element doping and surface functionalization of Si-CQDs endow their novel chemical, physical and
optical properties. The Si-CQDs dispersed in acetone are almost monodisperse with an average particle diameter of
3.6 nm. The Si-CQDs dispersed in acetone display blue fluorescence (excitation/emission maxima of 380/460 nm).
In contrast, the solid-state Si-CQDs exhibited yellow fluorescence (with excitation/emission maxima of 470/595 nm).
The fluorescence emission spectra of acetone-suspended Si-CQDs are concentration-dependent, and the emission
peak becomes red-shifted as the concentration is increased. The Si-CQDs are sensitive and selective fluorescent
“on off on” nanoprobes for chromate [Cr(VI)] and ascorbic acid (AA). Fluorescence is quenched by Cr(VI) via an
inner filter effect from the absorption of Si-CQDs excitation at 380 nm by Cr(VI). Upon addition of AA, fluores-
cence is restored because of reduction of Cr(VI) by AA. Under optimal conditions (excitation/emission wavelength
of 380/460 nm), the response is linear in the 0.4–160 μM Cr(VI) concentration range, and the detection limit is
34 nM. The respective data for AA are 1–80 μM and 84.6 nM. The practical use of the nanoprobe for Cr(VI)
determination in real river water samples is also demonstrated successfully. Their concentration-dependent fluores-
cence, good thermal stability and self-crosslinking behavior also make the Si-CQDs a candidate material for white
light-emitting diodes that displays color conversion and can act as an encapsulation layer in a blue light-emitting
diode (LED) chip.

Keywords Solid-state fluorescence . Concentration-dependent fluorescence . “On off on” nanoprobe . Fluorescence detection .
Detection mechanism . Inner filter effect . Self-cross linking . Good thermal stability . Solvothermal

Electronic supplementary material The online version of this article Introduction

(https://doi.org/10.1007/s00604-019-3603-6) contains supplementary
material, which is available to authorized users.
* Wei Li
liwei19820927@126.com
* Shouxin Liu
liushouxin@126.com
1 CQDs. First, analyte detection requires highly specific
Key laboratory of Bio-based Material Science and Technology of
Ministry of Education, Northeast Forestry University,
Harbin 150040, People’s Republic of China
Carbon quantum dots (CQDs) have luminescent proper-
ties that expand the potential for their use in a range of
fluorescent applications. These include photocatalysis [1,
2], analyte detection [3, 4], light-emitting devices (LED)
[5, 6], bioimaging and drug delivery [7, 8]. However,
various challenges must be overcome to successfully use
interactions between the CQDs and the analytes, and
so the CQDs require specific recognition groups on
516 Page 2 of 13
their surface to distinguish each analyte [9]. Second,
most of the literature on CQDs states that they exhibit
blue to green light emission with low fluorescence
emission in tensity, w hich is not co nduc iv e to
bioimaging. Third, almost all work on CQDs to date
has focused on CQD fluorescence in solution. Despite
some progress on solid-state CQD fluorescence, most of
this work has required the dispersion of the CQDs with-
in a matrix to avoid the aggregation-caused self-
quenching effect (ACQ) when the CQDs are dried to
form films or powders. For example, Moretto et al. em-
bedded CQDs in a polymer to prevent solid state lumi-
nescence quenching [10]. Shen et al. prepared CQD-
based phosphors that emitted efficient blue and green
fluorescence through the effective dispersion of the
CQDs by integrating them with starch particles [11].
Additionally, fluorescent silica xerogel/CQDs composites
have also been reported. However, there are few reports
of pure CQDs that exhibit solid-state fluorescence emis-
sion, which considerably limits their use in solid-state
optoelectronic devices.
Over the last decade of research, surface
functionalization and heteroatom doping has been found
to modify the optical properties of CQDs, which has led
to the development of novel applications [12]. The syn-
thesis of CQDs usually causes the presence of many
carboxyl groups or hydroxyl groups on their surface,
which allows them to be functionalized with polymers
or other organic molecules. For example, polyethylene
glycol (PEG) [13], polyethyleneimine (PEI) [14], N-
carbamoylmaleimide [15] and 4,7,10-trioxa-1,13-
tridecanediamine (TTDDA) [16] have been used to
functionalize the surface of CQDs. Si-CQDs have been
used for analyte detection, bioimaging, and WLEDs [17,
18]. The organosilane serves two purposes: (1) the steric
hindrance induced by the high-density of silane chains
on the surface can prevent ACQ in the solid-state, and
(2) the presence of the Si atom, which is adjacent to C
in the periodic table and so has a similar atomic struc-
ture, means that the efficient modulation of the physi-
cochemical properties of the CQDs after doping is pos-
sible. Doping of Si introduces a diverse range of surface
states, which can facilitate a high yield of electron/holes
pairs to undergo radiative recombination and so in-
creases fluorescence intensity.
The inner filter effect (IFE) is a source of error pres-
ent in spectrofluorometry in which the emitted light is
attenuated through absorption by absorbers present in
the detection system. However, IFE-based fluorescent
assays have been reported because IFE can only occur
effectively if the absorption band of the absorber over-
laps the excitation and/or emission bands of the
fluorophore. CQD-based fluorescence analyte detection
Microchim Acta (2019) 186: 516
based on IFE has been reported. This method was sim-
ple, convenient, fast to implement, and exhibited good
selectivity and high sensitivity. Cr(VI) is a heavy metal
ion that is widely distributed in aquatic environments, is
carcinogenic and extremely harmful to humans [19].
Sensitive, effective, low-cost and rapid detection
methods for Cr (VI) are required. The characteristic ab-
sorption spectrum of Cr(VI) and desirable luminescent
properties of CQDs mean that they may be suitable
powerful absorber and fluorophores, respectively, in
IFE-based fluorescent assays [20–22]AA (2-(1,2-
dihydroxyethyl)-4,5-dihydroxyfuran-3-one) is a water-
soluble vitamin C that possesses antioxidant properties
and exists widely in the human diet, cosmetic products
and pharmaceutical formulation [23, 24]. AA is an es-
sential vitamin that is required to maintain healthy,
physiological function [25]. The fast and simple detec-
tion of AA receives scientific attention across the world
because of its importance. Compared with oxidant titra-
tion [26], capillary electrophoresis [27], liquid chroma-
tography [28], chemiluminescence [29] and electrochem-
ical methods [30], fluorescence detection is a simple
and efficient method. Traditional fluorescent probes are
usually based on organic molecules or heavy metal-
containing quantum dots. In contrast, CQD-based fluo-
rescent probes are effective, have low-toxicity, are read-
ily surface-functionalized, and are stable. As such, their
use for the detection of AA is highly promising
[31–33]. Additionally, its chelation effect and reduction
reaction towards heavy metal ions are beneficial for a
CQD-based fluorescent assay.
Light-emitting devices are solid-state light sources
that can directly convert electrical energy into light.
These devices have various advantages, including
small volume, high luminous efficiency, long lifetime,
and low-energy consumption [34]. In addition, white
light-emitting devices (WLEDs) are widely used in
outdoor lighting, such as street lamps and large screen
displays, and they getting closer to being used as in-
door lighting, which will have significant impact on
both residential and industrial applications [35].
Currently, commercial WLEDs are constructed using
rare-earth-based phosphors for the light conversion
material, which includes Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce),
Li 2 SrSiO 4 :Ce 3 + , Eu 2 + , Sr-α-SiAlON:Eu 2 + , Ca-α-
S i A l O N : E u 2 + , S r 3 S i O 5 : Eu 2 + a n d B a 3 S i O 5 : E u 2 + .
However, these phosphors are usually expensive, toxic
and their optical performance is relatively poor.
Additionally, these phosphors are not compatible with
conventional packaging materials, which restrict their
development in WLEDs. Quantum dots that have ex-
hibited outstanding performance have been reported.
These have used CdSe [36], CdSe/ZnS [37], InP/ZnS/
Microchim Acta (2019) 186: 516
SiO 2 [38] and CuInS 2 /ZnS [39] as nanophosphors.
Nevertheless, these semiconductor and noble metal
quantum dots are potentially harmful to both human
and the environment. Additionally, noble metal quan-
tum dots are relatively expensive. Thus, novel mate-
rials that produce light at low cost and low toxicity
are highly desirable. Si-CQDs show great potential
for use in WLEDs because they have desirable optical
properties, are thermally stabile and can self-cross link
[40–42].
A one-pot solvothermal method for the synthesis of
Si-CQDs is described. The optical properties of the Si-
CQDs acetone solution and solid-states were examined.
The Si -CQDs acetone sol uti on exhibited blue-
fluorescence that was concentration-dependent, while
the solid-state Si-CQDs exhibited yellow-fluorescence.
Using these results, a mechanism for the solid-state
fluorescence emission is proposed. The Si-CQDs were
used as an “on off on” fluorescence nanoprobes for the
detection of Cr(VI) and AA. Additionally, their use as a
WLED color conversion and encapsulation material was
also investigated.
Materials and methods
Materials
Glucosamine, AA, cysteine, tyrosine, glutamic acid, glu-
cose, uric acid, dopamine, tryptophan, valine, phenylal-
anine, glucosamine, lysine, and citric acid were pur-
chased from Lanji Technology Development Co., Ltd.
(Shanghai, China, http://www.shlanji.com/). K2Cr 2O7,
HgCl 2 , ZnCl 2 , NaCl, MnSO 4 , SnCl 2 , FeCl 3 , CoCl 2 ,
AlCl3, CuSO4, CaCO3, Ni(NO3) 2, Cd(NO3) 2, FeSO4,
MgCl 2 , CuCl, AgNO 3 , CrCl 3 , K 2 CO 3 , K 2 SO 4 , KCl,
and KNO 3 were purchased from Kermel Chemical
Reagent Co., Ltd. (Tianjin, China, http://www.
chemreagent.com/). Acetone and dimethyl sulfoxide
(DMSO) were purchased from Guangfu Technology
Development Co., Ltd. (Tianjin, China, http://www.
guangfu.com/). 3-[2-(2-Aminoethylamino)ethylamino]
propyl-trimethoxysilane (NQ-62) was purchased from
Macklin Reagent Co., Ltd. (Shanghai, China, http://
www.macklin.cn/). Phosphate-buffered saline (PBS,
100 mM, pH = 7.4) was purchased from Solarbio
Science and Technology Co., Ltd. (Beijing, China,
http://www.solarbio.com/). All chemical reagents were
of analytical grade and used as received. A blue LED
chip (460 nm) was purchased from Looking Long
Technology Co., Ltd. (Shenzhen, China, https://
ledchips01.cn.china.cn/).
Page 3 of 13 516
Preparation of Si-CQDs
Si-CQDs were prepared via a one-pot solvothermal
treatment using glucosamine and NQ-62 in acetone
(Fig. 1). Typically, glucosamine (0.5 g) and NQ-62
(4 mL) were dissolved in acetone (10 mL) in a glass
beaker with stirring. The mixture was subsequently
transferred to a poly(p-phenylene) autoclave (50 mL)
and heated at 210 °C for 2 h. After that, the autoclave
was cooled to ambient temperature in air. The crude
product was filtered through a nylon filtration mem-
brane filter (0.22 μm), and then subjected to dialysis
in acetone (500 Da molecular weight cut off) for ap-
proximately 24 h. These CQDs were named Si-CQDs.
For comparison, the CQDs were prepared via the same
procedure in acetone with only glucosamine or NQ-62,
named O-CQDs and NQ-62-CQDs, respectively. Si-
CQDs and O-CQDs were also prepared using the same
procedure in aqueous solution, named Si-CQDs-W and
O-CQDs-W, respectively.
Cr(VI) and AA determination
The detection of Cr(VI) was performed in PBS
(100 mM, pH = 7.4). A typical procedure involved
adding varying concentrations of K2Cr 2O 7 to a PBS
solution containing Si-CQDs. The final concentration
of Cr 2 O 7 2− was 0, 0.2, 2, 5, 10, 20, 40, 80, 160,
240, 320, 400, 480, 560, 640, 720, 800 and
1000 μM, respectively. The solutions were allowed to
react for 1 min before the fluorescence measurement
was taken. All samples were excited at 380 nm, and
the fluorescent intensities were recorded at 460 nm.
The selectivity of the detection for Cr(VI) was inves-
tigated by adding different metal ions into the solu-
tions in place of Cr 2 O 7 2 − , the concentration for
Cr 2 O 7 2− was 500 μM, other ions were 1000 μM.
These included Hg2+, Zn2+, Na2+, Mn2+, Sn2+, Fe3+,
Co2+, Al3+, Cu2+, Ca2+, Ni2+, Cd2+, Fe2+, Mg2+, Cu+,
Ag+, Cr3+, CO32−, SO42−, Cl−, and NO3−.
The detection of AA was also performed in PBS
(100 mM, pH = 7.4). A typical procedure involved
adding varying concentrations of AA to a solution that
contained both Si-CQDs and K2Cr2O7. The final con-
centration of AA was 0, 0.5, 2, 5, 10, 20, 40, 80, 160,
240, 320, 400, 480 and 560 μM, respectively. The
solutions were allowed to react for 20 min before the
fluorescence measurement were taken. All samples
were excited at 380 nm, and the fluorescent intensities
were recorded 460 nm. The selectivity of the detection
for AA was investigated by adding various small or-
ganic molecules into the solutions in place of AA, and
516 Page 4 of 13
Fig. 1 Schematic diagram
showing the preparation of the
Si-CQDs
the concentration for AA and other small organic mol-
ecules were 1000 μM. These included cysteine, tyro-
sine, glutamic acid, glucose, uric acid, dopamine, tryp-
tophan, valine, phenylalanine, glucosamine, lysine,
citric acid.
Fabrication of WLEDs
A blue LED chip with a peak emission wavelength
centered at 460 nm was fixed on the bottom of the
LED base and the two threads on the LED were con-
nected to an external power supply. Si-CQD solutions
(25 μL of 50, 100, 120, 200 or 250 g·L−1) were coated
on the chip. The device was dried at 80 °C for 6 h to
solidify and then the electroluminescence was examined
under a driving current of 20 mA.
Characterization methods
Seen from supporting information.
Results and discussion
Structural and optical characterization of the Si-CQDs
Characterization of Si-NCDs were performed by TEM
(HRTEM), XRD, FT-IR and XPS (See the Fig. S1,
S2, S3).
The fluorescence spectra of the Si-CQDs, Si-CQDs-
W, O-CQDs, O-CQDs-W and NQ-62-CQDs, when
Microchim Acta (2019) 186: 516
excited at 380 nm, are shown in Fig. S4(a) and the
UV-absorption spectra of Si-CQDs, O-CQDs and NQ-
62-CQDs are shown in Fig. S4(b). The fluorescence
intensity of the CQDs that were synthesized in acetone
was stronger t han t hose syn thesized in water.
Additionally, the fluorescence emission maximum of
the CQDs synthesized in acetone was red-shifted when
compared with those synthesized in water. This indicat-
ed that the presence if the Si may have altered the
structural network of the CQDs. It is possible that the
large number of silane chains created a new surface
state that facilitated a high yield of radiative recombi-
nation. Furthermore, the fluorescence intensity of the
NQ-62-CQDs was stronger than that of the O-CQDs,
which was consistent with NQ-62 being a primary rea-
son for the improved fluorescence properties of the
CQDs. The UV-vis absorption spectrum of the Si-
CQDs was similar with those of O-CQDs and NQ-62-
CQDs, which was further confirmation that the Si-CQDs
were prepared successfully using the method.
The Si-CQDs acetone solution and solid-states ex-
hibited blue (Fig. S5(a), bottom panel) and yellow
(Fig. S5(b), bottom panel) emission when irradiated
at 365 nm, respectively. Inverted fluorescence micros-
copy images of the solid-state Si-CQDs on a square
plastic container are shown in Fig. S5(c–f). The Si-
CQD powder exhibited yellow and red fluorescence
when excited at 360, 470 and 540 nm, respectively.
The UV-vis absorption and fluorescence spectroscopy
of the Si-CQDs were examined to understand their
optical properties. The absorption spectrum of the
Si-CQDs acetone solution exhibited three obvious
peaks, including two strong, characteristic peaks at
Microchim Acta (2019) 186: 516
241 and 343 nm, and one relatively weak peak at
287 nm, as seen in Fig. S6(a). The peak at 241 nm
was attributed to π-π* transition of C=C bonds [43],
while the adsorption peaks at 287 and 343 nm were
assigned to n-π* transitions of electrons in C=O/N
bonds [44, 45]. Interestingly, the absorption spectrum
of the solid-state Si-CQDs exhibited a wider and more
obvious absorption band when compared with the Si-
CQDs acetone solution, which began from 210 nm
and covered the entire visible light region, as seen
in Fig. S7. This broad absorption band may have
been caused by the diverse aminosilane-
functionalized surface state of the Si-CQDs [46].
The photoluminescence excitation (PLE) spectrum of
the Si-CQDs acetone solution, shown in Fig. S6(a),
was recorded at the photoluminescence emission max-
imum (PL, 460 nm).
The fluorescence emission of the Si-CQDs was in-
vestigated when they were excited at different wave-
lengths. The Si-CQDs acetone solution exhibited
excitation-dependent emission when excited with wave-
length between 360 and 520 nm, as shown in Fig.
S6(b). This behavior was consistent with literature re-
ports [47–49]. As the maximum emission wavelength
was ~460 nm when the excitation wavelength was
~380 nm, a maximum excitation wavelength of
380 nm was used in the following experiments. This
excitation-dependent fluorescence is caused by the
abundance of surface states, and it demonstrated that
CQDs can effectively emit a variety of different colors.
Interestingly, the fluorescence of the solid-state Si-
CQDs was independent of the excitation wavelength,
as evidenced from the emission spectra that were ob-
tained when the excitation wavelength was varied from
280 to 490 nm, as seen in Fig. S6(c). This may have
been because the emission originated from n-σ* and/or
n-π* transitions. This suggestion was supported by the
fluorescence emission at this time being a single tran-
sition process only requiring a certain amount of ener-
gy. The n-π* and/or n-σ* transitions were more likely
to occur in the solid-state Si-CQDs, which resulted in
the fluorescence emission being independent of the ex-
citation wavelength.
To understand the mechanism behind the fluores-
cence from the solid-state Si-CQDs, the excellent
solid-state fluorescence and yellow, rather than the
blue, emission were examined in detail. The emission
maximum of the solid-state Si-CQDs (595 nm) exhib-
ited a significant red shift of 145 nm when compared
with that from a dilute solution (centered at 450 nm),
shown in Fig. S6(d). The red-shifting behavior of the
emission maximum continued from 450 to 500 nm as
the concentration of the Si-CQDs was increased from
Page 5 of 13 516
0.005 to 2 g·L−1, as shown in Fig. S6(d). This caused
a color change from blue to yellow-green with increas-
ing concentration, following excitation at 365 nm (Fig.
S8(a)). Solutions of varying concentration of the Si-
CQDs were easily cast onto clean glass sheets. The
letters “ABC” that were coated on the glass emitted
blue, green and yellow fluorescence when irradiated
at 365 nm, as shown in Fig. S8(b). This experiment
showed that these Si-CQDs can be used as colorful
fluorescence inks.
As the absorption of the solid-state Si-CQDs can
overlap the emission spectra (see Fig. S6(c) and Fig.
S7), it is possible that the observed red-shift in the
solid-state was based on the combination of fluores-
cence reabsorption and the excitation-dependent fluo-
rescence. The fluorescence emission in short wave-
length region can be overlapped quite well with the
absorption (between 210 and 400 nm), which weak-
ened the fluorescence intensity at short wavelengths.
Conversely, the emission at longer wavelengths, which
had less overlap, was stronger. The red-shift mainly
originates from IFE and resonance energy transfer
(RET) effects. In general, concentration-induced fluo-
rescence red-shift mainly results from IFE. The RET
only can occur over small inter-particle distances with-
in (R0) 10 nm. According to pervious reports, CQDs
are one kind of complex mixture composed of
nanodots with different size and multiple surface states,
which can play the roles of both energy donor and
acceptor. The inter-particle distances for Si-CQDs in
solid state was less 10 nm, indicating the RET may
take place between different kinds of Si-CQDs
(nanodots with different size and multiple surface
states). In this cases, the red shift can be explained
by a process in which the fluorescence emission from
smaller Si-CQDs was consecutively absorbed and re-
emitted by larger ones [46, 50].
Fluorescence lifetime is an effective method to dis-
tinguish the IFE and RET. IFE can’t change the fluo-
rescence lifetime, but the RET can. Fluorescence emis-
sion decay curves from the acetone solution and solid-
state Si-CQDs were measured. The average lifetime of
the solid-state Si-CQDs was 4.28 ns (Fig. S9(a)),
which was shorter than that of the Si-CQDs acetone
solution (4.67 ns, Fig. S9(b)). This was a strong indi-
cation that RET was occurring because it can compete
with the radiative recombination process of electron/
hole pairs in Si-CQDs, which shortens the fluorescence
lifetime. Nevertheless, the efficient dispersion of the
Si-CQDs in solution lead to inter particle distances
greater than 10 nm, as seen in Fig. S9(c), which
prevented RET and resulted in blue-fluorescence and
longer lifetimes from the Si-CQDs acetone solution
516 Page 6 of 13
(monomer state) than the solid-state Si-CQDs (aggre-
gate state). In summary, IFE is main reason for
concentration-dependent fluorescence, especially for
Si-CQD acetone solution, but the RET is the one of
the origin for the fluorescence red-shift for solid state
Si-CQDs.
Application in Cr(VI) and AA “on-off-on” nanoprobe
The Si-CQDs acted as a highly sensitive nanoprobe
for Cr(VI) because their fluorescence was quenched
in the presence of the toxic, heavy metal ion Cr(VI)
(Fig. 2(a)). The fluorescence intensity vs. Cr(VI) con-
centration (0.4–160 μM) is shown in Fig. 2(a), and a
linear correlation (R 2 = 0.999) of this plot resulted in
the following equation: F = 8724.61–43.98[Cr 2 O 7 2− ],
as shown in the inset of Fig. 2(b). The limit of de-
tection (LOD) was estimated using the following
equation: LOD = 3σ/m, where σ is the standard
a
c d
Fig. 2 a Fluorescence emission spectra of the Si-CQDs in the presence of
increasing concentrations of Cr2O72− (from top to bottom, 0, 0.2, 2, 5, 10,
20, 40, 80, 160, 240, 320, 400, 480, 560, 640, 720, 800 and 1000 μM. b
Fluorescence emission intensity as a function of Cr2O72− concentration. c
Normalized fluorescence intensity of the Si-CQDs in the presence of a
Microchim Acta (2019) 186: 516
deviation of the blank sample (n = 11) and m is the
slope of the curve fit. The LOD for Cr(VI) was de-
termined to be 33.6 nM. The linear detection range of
the Si-CQDs was wider with a lower LOD than other
CQD-based probes reported for the detection of
Cr(VI) (Table 1). Compared with the semiconductor
quantum dots [20], heavy metal quantum dots [51],
radioactive Ir [52] and noble metal nanoclusters
[58], the CQD-based materials are lower in cost and
safer to use [53–57]. The selectivity of the Si-CQDs
towards Cr(VI) was investigated by measuring the
fluorescence in the presence a range of ions, which
confirmed that the fluorescence quenching effect was
strongest in the presence of Cr(VI), as shown in Fig.
2(c). The fluorescence quenching mechanism of Si-
CQDs by Cr(VI) was examined by plotting the
Stern-Volmer equation:
F0 = F ¼ KSV ½Q þ 1;
b
range of ions showing the selectivity towards Cr(VI) (concentration of the
Cr2O72−was 500 μM, other ions were 1000 μM). d Relationship between
quenching efficiency and Cr2O72− concentration. All of the fluorescence
test conditions were excitation/emission wavelength at 380/460 nm,
respectively
Microchim Acta (2019) 186: 516 Page 7 of 13 516

Table 1 Comparison of the

detection abilities of the Si-CQDs Sensor Linear range (μM) LOD (nM) Ref
for Cr(VI) with other reported
a
nanomaterials CDs 0.5–263 260 [53]
b
DECDs 2–300 400 [54]
c
N, S-CQDs 1–10 200 [55]
d
Co-CDs 5–125 1170 [56]
e
GQD-modified membranes 1–500 190 [57]
f
SiNPs 0.1–200 28 [20]
g
CdTe QDs 0.2–20 154 [51]
h
IrNCs 0.1–100 25 [52]
i
AgNCs@PEI 0.0005–25 0.05 [58]
Si-CQDs 0.4–160 33.6 Current work
a
Carbon dots
b
Dual emissive carbon dots
c
Nitrogen and sulfur co-doped carbon quantum dots
d
Cobalt(II)-doped carbon dots
e
Graphene quantum dot modified membranes
f
Silicon nanoparticles
g
Glutathione-capped CdTe quantum dots
h
Iridium nanoclusters
i
Polyethyleneimine protected silver nanoclusters

where K SV is the Stern-Volmer quenching constant, fluorescent molecules of (1.0–2.0) ×

[Q] is Cr(VI) concentration, and F 0 and F are the
fluorescence intensities of the Si-CQDs at 460 nm in
the absence and presence of Cr(VI), respectively. A
linear relationship between F0 /F and the Cr(VI) con-
centration (0 and 320 μM) was observed with a cor-
relation coefficient of R 2 = 0.987, as shown in Fig.
2(d).
The fluorescence lifetime of the Si-CQDs was de-
termined to be 5.96 ns, as shown in Fig. 3 (a). The
formula K qτ 0 = Ksv yielded a bimolecular annihilation
constant (Kq ) of 1.68 × 10 12 L mol −1 s −1, which was
larger than the typical quenching constant for
10 10 L mol −1 s −1. This implied that the quenching
did not occur via a dynamic quenching mechanism.
The fluorescence lifetime of Si-CQDs in the presence
of Cr(VI) was also measured, which yielded a lifetime
of 5.87 ns (Fig. 3(a)). The small change in fluores-
cence lifetime of the Si-CQDs in the presence and
absence of Cr(VI) indicated that the fluorescence
quenching did not result from an electron-transfer
process. The fluorescence emission/excitation spectra
of Si-CQDs and the UV-vis absorption spectrum of
K 2 Cr 2 O 7 were measured to gain further insight into
the Cr(VI) detection mechanism. The excitation and

a b

Fig. 3 a Fluorescence decay curves of the Si-CQDs and a mixture of Cr(VI) and the Si-CQDs. b UV-vis absorption spectrum of Cr(VI), and the
fluorescence excitation and emission spectra of the Si-CQDs
516 Page 8 of 13
emission spectra of the Si-CQDs overlapped the ab-
sorption spectrum of Cr(VI) quite well, as shown in
Fig. 3(b). The enhanced absorbance of Cr(VI) resulted
in successful quenching of the fluorescence from the
Si-CQDs. Therefore, the fluorescence of Si-CQDs was
likely quenched effectively by Cr(VI) via IFE, rather
than alternative mechanisms.
The feasibility of Si-CQDs for detecting Cr(VI) in
real water samples was validated by river water sam-
ples from the Songhua River of Harbin, Heilongjiang
province, China. The river water sample was filtered
through a 0.22 μm nitrocellulose filters and then cen-
trifuged at 12000 rpm for 15 min. The resultant water
sample was spiked with PBS standard solutions
(100 mM, pH = 7.4) containing different concentra-
tions of Cr(VI), which were 20 μM, 50 μM and
120 μM respectively (Fig. S10, Table S1). displayed
that the real water sample also showed good
a b
c d
Fig. 4 a Normalized fluorescence intensity of the Si-CQD/Cr(VI)
mixture in the presence of a variety of organic molecules highlighting
the selective fluorescence recovery of AA (concentration of the organic
molecules was 1000 μM). b Fluorescence emission spectra of the Si-
CQD/Cr(VI) mixture in the presence of increasing concentrations of
AA (from bottom to top, 0, 0.5, 2, 5, 10, 20, 40, 80, 160, 240, 320,
Microchim Acta (2019) 186: 516
quenching effect to Si-CQDs. The concentration of
Cr(VI) in practical sample was calculated according
to the PL intensity in Fig. S10. It was found that
the concentration of Cr(VI) measured by the fluores-
cence quenching method were 18.9 μM, 48.6 μM and
127.0 μM, respectively, which were comparable to
that of spiked standard solutions. Although, the prac-
tical use of the nanoprobe for Cr(VI) determination in
real river water samples has been successfully, how to
screen off the interferences form UV absorbers and
other fluorescent substance towards the 'on-off-on'
fluorometric determination system is still a non-
negligible problem.
Interestingly, AA was found to recover the fluores-
cence intensity of the Si-CQDs following exposure to
Cr(VI), and possessed excellent selectivity when com-
pared with a range of other organic molecules (i.e.
cysteine, tyrosine, glutamic acid, glucose, uric acid,
400, 480 and 560 μM). c Fluorescence emission intensity as a function
of AA concentration. The equation of the linear fit is shown. (D) UV-vis
absorption spectra of the Si-CQDs, Cr(VI), the Si-CQD/Cr(VI) mixture
and the Si-CQD/Cr(VI)/AA mixture. All of the fluorescence test condi-
tions were excitation/emission wavelength at 380/460 nm, respectively
Microchim Acta (2019) 186: 516 Page 9 of 13 516

Table 2 Comparison of the detection abilities of the Si-CQD/Cr(VI) Cr(III), which would have eliminated the IFE effect
mixture for AA with other reported nanomaterials
and recovered the fluorescence of the Si-CQDs. The
Sensor Linear range (μM) LOD (nM) Ref absorption peak of the Si-CQD/Cr(VI) mixture
(373 nm) decreased and blue-shifted when AA was
a
GQDs 0.5–20 200 [66] added, with the appearance of an accompanying, wide
b
N, S-CQDs/Fe3+ 10–200 4960 [67] absorption band from Cr(III) that was centered at
c
CdTe QDs 10–250 1300 [60] 525 nm. This result confirmed that Cr(VI) was indeed
d
CuInS2 QDs 0.25–200 50 [61] reduced to Cr(III), which was likely caused by an
e
CdTe/CdS/ZnS QDs 0.008–0.1 1.8 [62] oxidation-reduction reaction between Cr(VI) and AA.
f
BSA-AuNCs 1.5–10 200 [64]
g
GSH-AgNCs 2–300 100 [65] Application in WLEDs
h
LaF3:Ce,Tb NPs 8–100 2400 [63]
i
CoOOH-TPNPs – 170 [59] A thermal gravimetric analysis curve of the Si-CQDs under a
Si-CQD/Cr(VI) 1–80 84.6 Current work nitrogen atmosphere showed that they were thermally stable
a
below 180 °C (Fig. S12). The working temperature of an LED
Graphene quantum dots
b
is approximately 150 °C, which indicated that the Si-CQDs
Nitrogen and sulfur co-doped carbon quantum dots ion and Fe3+ mix-
ture system
suitable for use in LEDs. Additionally, the Si-CQDs can form
c monolith, solid-state films while placing for a period of time
CdTe quantum dots
d benefiting from self-cross linking effect, as seen in Fig. S13,
CuInS2 quantum dots
e which resulted from surface abundant methoxysilyl groups.
CdTe/CdS/ZnS core/shell/shell quantum dots
f This indicated that the Si-CQDs can also be used as an encap-
Bovine serum albumin-modified Au nanoclusters
g
sulation layer in LEDs directly. Significantly, the unique opti-
Glutathione-modified Au nanoclusters
h
cal properties of the Si-CQDs, particularly the strong fluores-
LaF3:Ce,Tb nanoparticles
i
cence intensity and the concentration-dependent fluorescence
Cobalt oxyhydroxide (CoOOH) nanoflake-modified two-photon nano-
particles (TPNPs)
emission, means that the Si-CQDs should be suitable for in-
corporation into LEDs.
WLEDs were fabricated using the Si-CQDs as single white
light converter that transformed blue light into white light
dopamine, tryptophan, valine, phenylalanine, glucos- efficiently, as shown in Fig. 5(a). The broad emission spec-
amine, lysine and citric acid) (Fig. 4(a)). Using this trum from the WLEDs spanned almost the entire visible light
fluorescence recovery behavior, a fluorescence “off- region (380–780 nm, Fig. 5(b)). Si-CQD solution of varying
on” AA nanoprobe was constructed, as shown in concentrations were dropped onto the LED chips and then
Fig. S11. The fluorescence intensity of the Si-CQD/ dried into solid films. The concentration-dependent fluores-
Cr(VI) mixture at 460 nm gradually increased as the cence and self-absorption of the Si-CQDs resulted in the emis-
concentration of AA was increased (Fig. 4(b)). A lin- sion spectrum from the WLEDs red-shifting, as shown in Fig.
ear correlation (R 2 = 0.996) was observed for the fluo- 5(b). As the concentration of the Si-CQDs was increased, the
rescence intensity versus AA concentration (1– CIE chromaticity coordinates increased (Table S2, Fig. 5(c)),
80 μM), which resulted in the following equation: while the correlated color temperature (CCT) decreased and
F = 193.72 + 2.05[AA], as shown in Fig. 4(c). The the color rendering index increased gradually. The combina-
LOD for AA was determined to be 84.6 nM. The tion of the fluorescence emission band from the blue chip
Si-CQDs provided a better linear detection range and (460 nm) and the yellow emission centered at 600 nm from
lower LOD than those of reported CQD-based probes the Si-CQDs resulted in a successful WLEDs. The WLED
f o r d e t e c t i n g A A ( Ta b l e 2 ) . I n r e g a r d t o t h e coordinates (0.340, 0.255) were close to those of pure white
nanoprobe used [66–67], the semiconductor nanopar- light (0.330, 0.330). Therefore, the concentration-dependent
ticles [59], heavy metal quantum dots [60–62] and fluorescence of the Si-CQDs shows great potential for opti-
rare earth material LaF 3:Ce, Tb [63] were potentially mizing LEDs for both residential and industrial applications.
harmful to human beings and environment, while no-
ble metal nanoclusters [64, 65] are relatively expen-
sive. The recovery of the fluorescence from the Si- Conclusion
CQD/Cr(VI) mixture in the presence of AA may have
been caused by the functional groups in AA chelating The solid-state Si-CQDs with yellow fluorescence emission
the Cr(VI) from the surface of the Si-CQDs. were synthesized via a one-pot solvothermal method. The
Alternatively, AA may have reduced Cr(VI) into acetone-suspended Si-CQDs exhibited blue fluorescence that
516 Page 10 of 13
Fig. 5 a Schematic diagram showing the fabrication of the WLEDs on a
blue LED chip. b Emission spectra of the Si-CQDs phosphor-based
LEDs that were fabricated using different concentrations of Si-CQDs
red-shifted with increasing concentration because of IFE. The
organosilane chains on the surface of Si-CQDs endow their
novel chemical, optical and electrical properties. Including,
(1) diverse aminosilane surface states were introduced. This
increased the radiative recombination of the electron/hole
pairs, which increased the fluorescence intensity. (2) Steric
hindrance that was induced by the silane chains on the surface
of the Si-CQDs minimized ACQ. (3) The surface
methoxysilyl groups allowed the easily fabrication of pure,
monolith Si-CQD films because of a cross-linking effect,
and (4) the Si-CQDs were thermally stabile because of the
thermal properties of the organosilane surface molecules.
The Si-CQDs were applied for fluorometric determination
of Cr(VI) based on IFE with a LOD of 33.6 nM (0.4–
160 μM). The fluorescence of the Si-CQDs was recovered
by the addition of AA because of its chelation and the reduc-
tion effect towards (VI) and the LOD for AA is 84.6 nM (1–
80 μM). Although, the practical use of the nanoprobe for
Microchim Acta (2019) 186: 516
solution. c CIE chromaticity diagram for the LEDs, the inset shown a
photograph of the LED fabricated using a Si-CQDs concentration of 100
and 250 g·L−1, respectively
Cr(VI) determination in real river water samples has been
successfully, how to screen off the interferences form UV
absorbers and other fluorescent substance towards the on-
off-on fluorometric determination system is still a non-
negligible problem. The Si-CQDs were also used to fabricate
WLEDs as a color conversion and encapsulation layer of blue
LEDs. It is promising that Si-CQDs can be potentially applied
in a wide range of applications for fluorescence detection as-
says and WLEDs.
Acknowledgments This study was supported by the National Nature
Science Foundation of China (Nos. 31890773, 31570567),
Fundamental Research Funds for the Central Universities (Nos.
2572018AB02).
Compliance with ethical standards
Conflict of interest The author(s) declare that they have no competing
interests.
Microchim Acta (2019) 186: 516
References
1. Wang B, Chen YF, Wu YY, Bo W, Liu YS, Chang ML (2016)
Synthesis of nitrogen- and iron-containing carbon dots, and their
application to colorimetric and fluorometric determination of dopa-
mine. Microchim Acta 183(9):2491–2500. https://doi.org/10.1007/
s00604-016-1885-5
2. Ying G, Yang LL, Li WW, Wang XF, Shang YH, Li BX (2016)
Carbon dots doped with nitrogen and sulfur and loaded with
copper(II) as a “turn-on” fluorescent probe for cystein, glutathione
and homocysteine. Microchim Acta 183(4):1409–1416. https://doi.
org/10.1007/s00604-016-1779-6
3. Liu YS, Li W, Wu P, Ma CH, Wu XY, Xu MC, Luo S, Xu Z, Liu SX
(2019) Hydrothermal synthesis of nitrogen and boron co-doped
carbon quantum dots for application in acetone and dopamine sen-
sors and multicolor cellular imaging. Sens Actuators B: Chem 284:
34–43. https://doi.org/10.1016/j.snb.2018.10.075
4. Gui R, Hui J, Wang Y, Jie S (2017) Ions-induced two-photon fluo-
rescence dual-switching for reversible and simultaneous sensing of
Cu2+ and Hg2+ based on dual-emitting carbon dot/carbon dot con-
jugates. Sens Actuators B: Chem 245:386–394. https://doi.org/10.
1016/j.snb.2017.01.166
5. Gao WL, Zhou YM, Xu CG, Guo MX, Qi ZC, Peng XJ, Gao B
(2019) Bright hydrophilic and organophilic fluorescence carbon
dots: one-pot fabrication and multi-functional applications at visu-
alized Au3+ detection in cell and white light-emitting devices. Sens
Actuators B: Chem 281:905–911. https://doi.org/10.1016/j.snb.
2018.11.024
6. Wang XF, Wang GG, Li JB, Liu Z, Zhao WF, Han JC (2018)
Towards high-powered remote WLED based on flexible white-
luminescent polymer composite films containing S, N co-doped
graphene quantum dots. Chem Eng J 336:406–415. https://doi.
org/10.1016/j.cej.2017.12.056
7. Dong J, Wang KQ, Sun LP, Sun BL, Yang MF, Chen HY, Wang Y,
Sun JY, Dong LF (2018) Application of graphene quantum dots for
simultaneous fluorescence imaging and tumor-targeted drug deliv-
ery. Sens Actuator B-Chem 256:616–623. https://doi.org/10.1016/j.
snb.2017.09.200
8. Niu WJ, Li Y, Zhu RH, Shan D, Fan YR, Zhang XJ (2015)
Ethylenediamine-assisted hydrothermal synthesis of nitrogen-
doped carbon quantum dots as fluorescent probes for sensitive bio-
sensing and bioimaging. Sens Actuator B-Chem 218:229–236.
https://doi.org/10.1016/j.snb.2015.05.006
9. Zu FL, Yan FY, Bai ZJ, Xu JX, Wang YY, Huang YC, Zhou XG
(2017) The quenching of the fluorescence of carbon dots: a review
on mechanisms and applications. Microchim Acta 184(7):1899–
1914. https://doi.org/10.1007/s00604-017-2318-9
10. Mosconi D, Mazzier D, Silvestrini S, Privitera A, Marega C, Franco
L, Moretto A (2015) Synthesis and photochemical applications of
Processable polymers enclosing Photoluminescent carbon quantum
dots. ACS Nano 9(4):4156–4164. https://doi.org/10.1021/acsnano.
5b00319
11. Sun MY, Qu SN, Hao ZD, Ji WY, Jing PT, Zhang H, Zhang LG,
Zhao J, Shen DZ (2014) Towards efficient solid-state
photoluminescence based on carbon-nanodots and starch compos-
ites. Nanoscale 6(21):13076–13081. https://doi.org/10.1039/
C4NR04034A
12. Yan FY, Jiang YX, Sun XD, Bai ZJ, Zhang Y, Zhou XG (2018)
Surface modification and chemical functionalization of carbon dots:
a review. Microchim Acta 185(9):424. https://doi.org/10.1007/
s00604-018-2953-9
13. Wang X, Cao L, Yang ST, Lu F, Meziani MJ, Tian L, Sun KW,
Bloodgood MA, Sun YP (2010) Bandgap-like strong fluorescence
in functionalized carbon nanoparticles. Angew Chem-Int Edit
122(31):5438–5442. https://doi.org/10.1002/anie.201000982
Page 11 of 13 516
14. Qu D, Zheng M, Zhang LG, Zhao HF, Xie ZG, Jing XB,
Haddad RE, Fan HY, Sun ZC (2014) Formation mechanism
and optimization of highly luminescent N-doped graphene
quantum dots. Sci Rep 4:5249–5259. https://doi.org/10.
1038/srep05294
15. Xu JJ, Yu CF, Feng T, Liu MY, Li FT, Wang Y, Xu JJ (2018) N-
Carbamoylmaleimide-treated carbon dots: stabilizing the electro-
chemical intermediate and extending it for the ultrasensitive detec-
tion of organophosphate pesticides. Nanoscale 10:19390–19398.
https://doi.org/10.1039/C8NR05098H
16. Zhang Z, Hao JH, Zhang J, Zhang BL, Tang JL (2012) Protein as
the source for synthesizing fluorescent carbon dots by a one-pot
hydrothermal route. RSC Adv 2(23):8599–8601. https://doi.org/
10.1039/c2ra21217j
17. Zhang F, Feng XT, Zhang Y, Yan LP, Yang YZ, Liu XG (2016)
Photoluminescent carbon quantum dots as a directly film-forming
phosphor towards white LEDs. Nanoscale 8(16):8618–8632.
https://doi.org/10.1039/C5NR08838K
18. Zheng JX, Wang YL, Zhang F, Yang YZ, Liu XG, Guo KP, Wang
H, Xu BS (2017) Microwave-assisted hydrothermal synthesis of
solid-state carbon dots with intensive emission for white light-
emitting devices. J Mater Chem C 5:8105–8111. https://doi.org/
10.1039/C7TC01701D
19. Costa M (1997) Toxicity and carcinogenicity of Cr(VI) in animal
models and humans. CRC Crit Rev Toxicol 27(5):431–442. https://
doi.org/10.3109/10408449709078442
20. Zhu LJ, Peng X, Li HT, Zhang YY, Yao SZ (2017) On-off-
on fluorescent silicon nanoparticles for recognition of
chromium(VI) and hydrogen sulfide based on the inner filter
effect. Sens Actuator B-Chem 238:196–203. https://doi.org/
10.1016/j.snb.2016.07.029
21. Liu YS, Chen ZJ, Li W, Ma CH, Wu P, Wu XY, Li SJ, Liu SX
(2018) A nanocomposite probe consisting of carbon quantum dots
and phosphotungstic acid for fluorometric determination of
chromate(VI) with improved selectivity. Microchim Acta 185(10):
10–19. https://doi.org/10.1007/s00604-018-2993-1
22. Gong XJ, Liu Y, Yang ZH, Shuang SM, Zhang Z, Dong C (2017)
An "on-off-on" fluorescent nanoprobe for recognition of
chromium(VI) and ascorbic acid based on phosphorus/nitrogen
dual-doped carbon quantum dot. Anal Chim Acta 968:85–96.
https://doi.org/10.1016/j.aca.2017.02.038
23. André C, Castanheira I, Cruz JM, Paseiro P, Sanchessilva A (2010)
Analytical strategies to evaluate antioxidants in food: a review.
Trends Food Sci Technol 21(5):229–246. https://doi.org/10.1016/
j.tifs.2009.12.003
24. And RDH, Viola† R (2005) Improving the nutritional value of
crops through enhancement of l-ascorbic acid (vitamin C) content:
rationale and biotechnological opportunities. J Agric Food Chem
53(13):5248–5257. https://doi.org/10.1021/jf0503863
25. Padayatty SJ, Katz A, Wang Y, Eck P, Kwon O, Lee JH, Chen S,
Corpe C, Dutta A, Dutta SK (2003) Vitamin C as an antioxidant:
evaluation of its role in disease prevention. J Am Coll Nutr 22(1):
18–35. https://doi.org/10.1080/07315724.2003.10719272
26. Arya SP, Mahajan M, Jain P (2000) Non-spectrophotometric
methods for the determination of vitamin C. Anal Chim Acta
417(1):1–14. https://doi.org/10.1016/S0003-2670(00)00909-0
27. Kim W-S, Dahlgren RL, Moroz LL, Sweedler JV (2002) Ascorbic
acid assays of individual neurons and neuronal tissues using capil-
lary electrophoresis with laser-induced fluorescence detection. Anal
Chem 74(21):5614–5620. https://doi.org/10.1021/ac025917q
28. Koblová P, Sklenářová H, Brabcová I, Solich P (2012)
Development and validation of a rapid HPLC method for the de-
termination of ascorbic acid, phenylephrine, paracetamol and caf-
feine using a monolithic column. Anal Methods 4(6):1588–1591.
https://doi.org/10.1039/c2ay05784k
516 Page 12 of 13
29. Wang ZH, Teng X, Lu C (2012) Carbonate interlayered
hydrotalcites-enhanced peroxynitrous acid chemiluminescence
for high selectivity sensing of ascorbic acid. Analyst 137(8):
1876–1881. https://doi.org/10.1039/C2AN00030J
30. Barberis A, Bazzu G, Calia G, Puggioni GM, Rocchitta GG,
Migheli R, Schirra M, Desole MS, Serra PA (2010) New
ultralow-cost telemetric system for a rapid electrochemical detec-
tion of vitamin C in fresh orange juice. Anal Chem 82(12):5134–
5140. https://doi.org/10.1021/ac100303p
31. Gong J, Lu X, An XQ (2015) Carbon dots as fluorescent off-on
nanosensors for ascorbic acid detection. RSC Adv 5(11):8533–
8536. https://doi.org/10.1039/c4ra13576h
32. Fong JFY, Chin SF, Ng SM (2016) A unique “turn-on” fluorescence
signalling strategy for highly specific detection of ascorbic acid
using carbon dots as sensing probe. Biosens Bioelectron 85:844–
852. https://doi.org/10.1016/j.bios.2016.05.087
33. Li LB, Wang C, Luo JX, Guo QW, Liu KY, Liu K, Zhao WJ, Lin
YQ (2015) Fe3+-functionalized carbon quantum dots: A facile prep-
aration strategy and detection for ascorbic acid in rat brain
microdialysates. Talanta 144(1):1301–1307. https://doi.org/10.
1016/j.talanta.2015.08.003
34. Schubert EF, Kim JK (2005) Solid-state light sources getting smart.
Science 308(5726):1274–1278. https://doi.org/10.1126/science.
1108712
35. Steele RV (2007) The story of a new light source. Nat Photonics
1(1):25–26. https://doi.org/10.1038/nphoton.2006.44
36. Dai S, Siao CB, Chung SR, Wang KW, Pan XQ (2018) Developed
One-pot Synthesis of Dual-color CdSe Quantum Dots for White
Light-emitting Diode Application. J Mater Chem C 6(12):3089–
3096
37. Suhail AM, Kadim AM, Ibrahim OA, Murad HI (2012) CdSe/ZnS
Core-Shell System Enhance the Efficiency of the White Light
Generation. Appl Phys Res 4(1):57–63. https://doi.org/10.1039/
C8TC00348C
38. Ziegler J, Xu S, Kucur E, Meister F, Batentschuk M, Gindele F,
Nann T (2010) Silica-Coated InP/ZnS Nanocrystals as Converter
Material in White LEDs. Adv Mater 20(21):4068–4073. https://doi.
org/10.1002/adma.200800724
39. Chuang PH, Lin CC, Liu RS (2014) Emission-tunable CuInS2/ZnS
quantum dots: structure, optical properties, and application in white
light-emitting diodes with high color rendering index. ACS Appl
Mater Interfaces 6(17):15379–15387. https://doi.org/10.1021/
am503889z
40. Tian Z, Zhang XT, Li D, Zhou D, Jing PT, Shen DZ, Qu SN, Zboril
R, Rogach AL (2017) Full-Color Inorganic Carbon Dot Phosphors
for White-Light-Emitting Diodes. Adv Optical Mater 5(19):
1700416–1700424. https://doi.org/10.1002/adom.201700416
41. Feng XT, Zhang F, Wang YL, Zhang Y, Yang YZ, Liu XG (2015)
Luminescent carbon quantum dots with high quantum yield as a
single white converter for white light emitting diodes. Appl Phys
Lett 107(21):3076–3081. https://doi.org/10.1063/1.4936234
42. Wang F, Chen YH, Liu CY, Ma DG (2011) White light-emitting
devices based on carbon dots' electroluminescence. Chem Commun
47(12):3502–3504. https://doi.org/10.1039/c0cc05391k
43. Tang L, Ji R, Cao X, Lin J, Jiang H, Li X, Teng KS, Luk CM, Zeng
S, Hao J (2012) Deep ultraviolet photoluminescence of water-sol-
uble self-passivated graphene quantum dots. ACS Nano 6(6):5102–
5110. https://doi.org/10.1021/nn300760g
44. Wu P, Li W, Wu Q, Liu YS, Liu SX (2017) Hydrothermal synthesis
of nitrogen-doped carbon quantum dots from microcrystalline cel-
lulose for the detection of Fe3+ ions in an acidic environment. RSC
Adv 7(70):44144–44153. https://doi.org/10.1039/C7RA08400E
45. Zhuo Y, Miao H, Zhong D, Zhu SS, Yang XM (2015) One-step
synthesis of high quantum-yield and excitation-independent emis-
sion carbon dots for cell imaging. Mater Lett 139:197–200. https://
doi.org/10.1016/j.matlet.2014.10.048
Microchim Acta (2019) 186: 516
46. Wang Y, Kalytchuk S, Zhang Y, Shi HC, Kershaw SV, Rogach AL
(2015) Thickness-Dependent Full-Color Emission Tunability in a
Flexible Carbon Dot Ionogel. J Phys Chem Lett 5(8):1412–1420.
https://doi.org/10.1021/jz5005335
47. Mao LH, Tang WQ, Deng ZY, Liu SS, Wang CF, Chen S (2014)
Facile Access to White Fluorescent Carbon Dots toward Light-
Emitting Devices. Ind Eng Chem Res 53(15):6417–6425. https://
doi.org/10.1021/ie500602n
48. Sun D, Ban R, Zhang PH, Wu GH, Zhang JR, Zhu JJ (2013) Hair
fiber as a precursor for synthesizing of sulfur- and nitrogen-co-
doped carbon dots with tunable luminescence properties. Carbon
64(11):424–434. https://doi.org/10.1016/j.carbon.2013.07.095
49. Chen PC, Chen YN, Hsu PC, Shih CC, Chang HT (2013)
Photoluminescent organosilane-functionalized carbon dots as tem-
perature probes. Chem Commun 49(16):1639–1641. https://doi.
org/10.1039/c3cc38486a
50. He JL, He YL, Chen YH, Lei BF, Zhuang JL, Xiao Y, Liang YR,
Zheng MT, Zhang HR, Liu YL (2017) Solid-State Carbon Dots
with Red Fluorescence and Efficient Construction of Dual-
Fluorescence Morphologies. Small 13(26):1700075–1700084.
https://doi.org/10.1002/smll.201700075
51. Zhang LJ, Xu CL, Li BX (2009) Simple and sensitive detection
method for chromium(VI) in water using glutathione-capped CdTe
quantum dots as fluorescent probes. Microchim Acta 166(1-2):61–
68. https://doi.org/10.1007/s00604-009-0164-0
52. Cui ML, Wang C, Yang DP, Song QJ (2017) Fluorescent iridium
nanoclusters for selective determination of chromium(VI).
Microchim Acta 185(1):8–16. https://doi.org/10.1007/s00604-
017-2553-0
53. Gao YF, Jiao Y, Lu WJ, Liu Y, Han H, Gong XJ, Xian M, Shuang
SM, Dong C (2018) Carbon dots with red emission as a fluorescent
and colorimeteric dual-readout probe for the detection of
chromium(VI) and cysteine and its logic gate operation. J Mater
Chem B 6:6099–6107. https://doi.org/10.1039/C8TB01580E
54. Ma YX, Chen YL, Liu JJ, Han YX, Ma SD, Chen XG (2018)
Ratiometric fluorescent detection of chromium(VI) in real samples
based on dual emissive carbon dots. Talanta 185:249–257. https://
doi.org/10.1016/j.talanta.2018.03.081
55. Zhang HQ, Huang YH, Hu ZB, Tong CQ, Zhang ZS, Hu SR (2017)
Carbon dots codoped with nitrogen and sulfur are viable fluorescent
probes for chromium(VI). Microchim Acta 184(5):1547–1553.
https://doi.org/10.1007/s00604-017-2132-4
56. Zhang HY, Wang Y, Xiao S, Wang H, Wang JH, Feng L (2017)
Rapid detection of Cr(VI) ions based on cobalt(II)-doped carbon
dots. Biosens Bioelectron 87:46–52
57. Carrasco PMA, García I, Yate L, Zaera RT, Cabañero G, Grande
HJ, Ruiz V (2016) Graphene quantum dot membranes as fluores-
cent sensing platforms for Cr (VI) detection. Carbon 109:658–665.
https://doi.org/10.1016/j.bios.2016.08.010
58. Xu N, Zhu Q, Kong XY, Meng L (2016) A sensitive detection of
Cr(VI) in wide pH range using polyethyleneimine protected silver
nanoclusters. Anal Methods 8(28):5684–5689. https://doi.org/10.
1039/c6ay01245k
59. Meng HM, Zhang XB, Yang C, Kuai HL, Mao G, Gong L, Zhang
W, Feng S, Chang J (2016) Efficient Two-Photon Fluorescence
Nanoprobe for Turn-On Detection and Imaging of Ascorbic Acid
in Living Cells and Tissues. Anal Chem 88(11):6057–6063. https://
doi.org/10.1021/acs.analchem.6b01352
60. Zhu J, Zhao ZJ, Li JJ, Zhao JW (2017) Fluorescent detection of
ascorbic acid based on the emission wavelength shift of CdTe quan-
tum dots. J Lumin 192:47–55. https://doi.org/10.1016/j.jlumin.
2017.06.015
61. Liu SY, Hu JJ, Su XG (2012) Detection of ascorbic acid and folic
acid based on water-soluble CuInS2 quantum dots. Analyst
137(19):4598–4604. https://doi.org/10.1039/c2an35908a
Microchim Acta (2019) 186: 516
62. Huang S, Zhu FW, Xiao Q, Su W, Sheng JR, Huang CS, Hu BQ
(2014) A CdTe/CdS/ZnS core/shell/shell QDs-based "OFF-ON"
fluorescent biosensor for sensitive and specific determination of
L-ascorbic acid. RSC Adv 4(87):46751–46761. https://doi.org/10.
1039/C4RA08169B
63. Mi CC, Wang TT, Zeng P, Zhao S, Wang NZ, Xu SK (2013)
Determination of ascorbic acid via luminescence quenching of
LaF3:Ce,Tb nanoparticles synthesized through a microwave-
assisted solvothermal method. Anal Methods 5(6):1463–1468.
https://doi.org/10.1039/C3AY26387H
64. Wang XX, Wu P, Hou XD, Lv Y (2012) An ascorbic acid sensor
based on protein-modified Au nanoclusters. Analyst 138(1):229–
233. https://doi.org/10.1039/C2AN36112D
65. Na L, Yu H, Ge Y, Song GWL (2016) “Turn-Off-On” Fluorescence
Switching of Ascorbic Acid-Reductive Silver Nanoclusters: a
Sensor for Ascorbic Acid and Arginine in Biological Fluids. J
Fluoresc 27(1):1–10. https://doi.org/10.1007/s10895-016-1957-2
Page 13 of 13 516
66. Huang H, Wang BD, Chen M, Liu MX, Leng Y, Liu XY, Li YX,
Liu ZN (2016) Fluorescence turn-on sensing of ascorbic acid and
alkaline phosphatase activity based on graphene quantum dots.
Sens Actuator B Chem 235:356–361. https://doi.org/10.1016/j.
snb.2016.05.080
67. Luo XL, Zhang WG, Han Y, Chen XM, Zhu L, Tang WZ, Wang JL,
Yue TL, Li ZH (2018) N,S co-doped carbon dots based fluorescent
“on-off-on” sensor for determination of ascorbic acid in common
fruits. Food Chem 258:214–221. https://doi.org/10.1016/j.
foodchem.2018.03.032
Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.