(Emuch - Net) Carbon Quantum Dots and Their Applications

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Carbon quantum dots and their applications

Cite this: Chem. Soc. Rev., 2015,
44, 362
Shi Ying Lim, Wei Shen and Zhiqiang Gao*

Fluorescent carbon nanoparticles or carbon quantum dots (CQDs) are a new class of carbon
nanomaterials that have emerged recently and have garnered much interest as potential competitors to
Published on 15 October 2014. Downloaded on 10/12/2014 00:32:21.
conventional semiconductor quantum dots. In addition to their comparable optical properties, CQDs
have the desired advantages of low toxicity, environmental friendliness low cost and simple synthetic
routes. Moreover, surface passivation and functionalization of CQDs allow for the control of their
physicochemical properties. Since their discovery, CQDs have found many applications in the fields of
Received 4th August 2014
DOI: 10.1039/c4cs00269e
chemical sensing, biosensing, bioimaging, nanomedicine, photocatalysis and electrocatalysis. This article
reviews the progress in the research and development of CQDs with an emphasis on their synthesis,
functionalization and technical applications along with some discussion on challenges and perspectives
www.rsc.org/csr
in this exciting and promising field.
1. Introduction
The unique properties of carbonic nanomaterials such as nanodiamonds, fullerenes, carbon nanotubes, graphene sheets and
fluorescent carbon nanoparticles or carbon quantum dots (CQDs)
have inspired extensive studies on them due to their great
potential for a wide variety of technical applications. Among the
electronic and physicochemical characteristics of CQDs, their
optical properties and their fluorescence emissions in particular have attracted increasing interest in recent years. For many
years, semiconductor quantum dots have been extensively investigated for their strong and tunable fluorescence emission
properties, which enable their applications in biosensing and
bioimaging. However, semiconductor quantum dots possess
Department of Chemistry, National University of Singapore, Singapore 117543.
E-mail: [email protected]; Fax: +65 6779-1691; Tel: +65 6516-3887
certain limitations such as high toxicity due to the use of heavy

metals in their production.13 It is known that heavy metals are
highly toxic even at relatively low levels, which may prove
prohibitive to any clinical studies.4,5 This prompted the creation
of CQDs to replace semiconductor quantum dots due to their
low toxicity, biocompatibility, low cost and chemical inertness in
addition to having similar fluorescence properties.
The accidental discovery of CQDs during the separation and
purification of single-walled carbon nanotubes (SWCNTs) by
Xu et al. in 2004 triggered subsequent studies to exploit the
fluorescence properties of CQDs and create a new class of viable
fluorescent nanomaterials.6 Fluorescent carbon nanoparticles
received their name carbon quantum dots in 2006 from
Sun et al.7 who proposed a synthetic route to produce CQDs with
much enhanced fluorescence emissions via surface passivation.
CQDs are synthesised by two routes, namely the top-down route79
and the bottom-up route.3,1012 CQDs are typically quasi-spherical
Ms Shi Ying Lim was born in

Singapore. She received her BSc
in Chemistry from the National
University of Singapore in 2014
and is currently a graduate student
in the Department of Chemistry at
the same institution. Her research
focuses on camera-based fluorescence correlation spectroscopy.
Shi Ying Lim
362 | Chem. Soc. Rev., 2015, 44, 362--381
Ms Wei Shen received her BSc in

Chemistry from Zhejiang University in 2011. She is currently a
graduate student in the Department of Chemistry National
University of Singapore. Her
research interests include biosensors and optical assays for
nucleic acids and proteins.
Wei Shen
This journal is The Royal Society of Chemistry 2015
View Article Online
Review Article
Fig. 1 Chemical structure of CQDs. (Reproduced with permission from

ref. 13.)
nanoparticles comprising amorphous to nanocrystalline cores

with predominantly graphitic or turbostratic carbon (sp2 carbon)
or graphene and graphene oxide sheets fused by diamond-like
sp3 hybridised carbon insertions (Fig. 1).1316 Oxidised CQDs
contain considerable amounts of carboxyl moieties at their
surface. Depending on the synthetic route, the oxygen content
in the oxidised CQDs ranges from 5 to 50% (weight).14 As shown
in Fig. 1, there are many carboxyl moieties on the CQD surface,
which impart excellent water solubility and suitable chemically
reactive groups for further functionalization and surface passivation with various organic, polymeric, inorganic or biological
materials to CQDs. Upon surface passivation, the fluorescence
properties of CQDs are enhanced. Surface functionalization
also modifies their physical properties, like their solubility in
aqueous and non-aqueous solvents.
As a group of newly emerged fluorescent nanomaterials, CQDs
have shown tremendous potential as versatile nanomaterials
for a wide range of applications, including chemical sensing,
biosensing, bioimaging, drug delivery, photodynamic therapy,
photocatalysis and electrocatalysis. Compared to conventional
semiconductor quantum dots, the unique attributes of CQDs, for
example their benign chemical composition, tunable fluorescence emissions, facile functionalization and excellent physicochemical and photochemical stability (non-photobleaching or
non-photoblinking), render them very attractive for technical
applications. Together with other advantages such as low cost
Dr Zhiqiang Gao is an associate

professor at the Department of
Chemistry National University of
Singapore. He received his BSc
and PhD in Chemistry from
Wuhan University. The following
years he worked as a postdoctoral
fellow at bo Akademi University
and The Weizmann Institute of
Science. After spending three years
in the United States and eight years
at the Institute of Bioengineering
and Nanotechnology, he joined
Zhiqiang Gao
NUS in April 2011. Research in his
laboratory currently includes electrochemistry, analytical chemistry
and materials science.
Chem Soc Rev
and ease of synthesis,17 CQDs are in a favourable position for

achieving unprecedented performance. On the other hand,
complex procedures for their separation, purification and
functionalization, their generally low quantum yields, and
ambiguity in their geometry, composition and structure are
some of the issues that need to be tackled before they can truly
outperform their semiconductor quantum dot counterparts in
areas like bioimaging, biosensing and nanomedicine. This
article reviews the progress in the research and development
of CQDs and their technical applications. We first examine the
fluorescence properties of CQDs and their tunable emissions.
Then, we discuss the various synthetic approaches for their
production and possible surface passivation and functionalization routes to impart desired properties to CQDs. Finally, we
discuss in great detail the applications of CQDs in chemical
sensing, biosensing, bioimaging, nanomedicine, photocatalysis
and electrocatalysis, especially the advantages they could bring to
these fields. In view of several excellent review articles focusing on
dierent aspects of CQDs, such as their synthesis and physicochemical properties,14,18 surface functionalization,19 bioimaging
and biosensing19,20 and photocatalysis and optoelectronics,18 it
is hoped that this article will provide a comprehensive overview
of the current status of CQD research and open new perspectives
toward the research and development of CQDs with much
improved physicochemical properties.
2. Fluorescence properties of CQDs

CQDs are a new class of nanomaterials that have attracted
significant attention in the past decade. Two classes of fluorescence emission mechanisms have been proposed for CQDs
even though the exact origins of their fluorescence emissions
remain debatable and more research is needed in order to paint
a clearer picture of the mechanisms of their fluorescence emissions.
The first class of fluorescence emission mechanism is that of
bandgap transitions caused by conjugated p-domains, while
the second class involves more intricate origins associated with
surface defects in CQDs.
2.1 Fluorescence emissions from bandgap transitions of
conjugated p-domains
For the first class of fluorescence mechanism, bandgap transitions arise from conjugated p-domains. These p-domains are
isolated by creating sp2 hybridised islands rich in p-electrons
through the reduction of graphene oxides obtained by using
Hummers method of oxidising and exfoliating graphite flakes.21
They are created in a way that there are no p-connections
between the sp2 islands, because any p-connections between
the sp2 islands would lead to interisland quenching of desired
fluorescence emissions.22,23
In this type of bandgap transitions, single-layer graphene
sheets have to be used to prevent interlayer quenching.24
The single-layer graphene sheets are used as precursors for
electronically slicing into isolated p-conjugated domains, which
resemble large aromatic molecules with extended p-conjugation
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Fig. 2 (A) CQDs with strong absorption in the UV region and weak
emissions and (B) CQDs with weak absorption in the near UV-vis region
but strong multicolour emissions in the visible region. (Reproduced with
permission from ref. 13.)
of specific electronic energy bandgap for optical absorption and

fluorescence emissions.25 Such electronic transitions display
strong absorption in the ultraviolet (UV) region, but weak or no
fluorescence emissions (Fig. 2A). The strong absorption is likely
due to light absorption by a large amount of high density pelectrons in the sp2 hybridised islands, which form excitonic
states while the weak emissions are possibly a result of quenching via radiationless relaxations to the ground state during
exciton migration to energy traps.13
2.2
Fluorescence emissions of surface defect-derived origins
The second class of the fluorescence mechanism arises from

surface-related defective sites generally any sites that have nonperfect sp2 domains will result in surface energy traps. Both sp2
and sp3 hybridised carbons and other functionalised surface
defects,26,27 such as carbonyl-related localised electronic states,24,28
present in CQDs contribute to their multicolour emissions that are
concentrated in the blue and green regions of the visible light
spectrum. These surface defects behave like aromatic molecules
that are individually incorporated into solid hosts, exhibiting multicolour emissions due to the existence of multiple surface defects
with different excitation and emission properties.13,25
Robertson and OReilly suggested that the optical properties
of carbon nanomaterials which contain both sp2 and sp3 bonds
Review Article
are determined by the p-states of the sp2 sites.29 Thus, the

bright surface defect-derived fluorescence of CQDs is due to the
recombination of electronhole pairs in the strongly localised p
and p* electronic levels of the sp2 sites. These sites lie between
the bandgap of the s and s* states of the sp3 matrix,30,31
leading to strong visible emissions. Such electronic transitions
exhibit weak absorption in the near ultraviolet-visible (UV-vis)
region but strong emissions in the visible region as shown in
Fig. 2B. In addition, upon surface passivation or functionalization, the surface defects become more stable to facilitate more
effective radiative recombination of surface-confined electrons
and holes, thus achieving brighter fluorescence emissions.25
2.3
Tunable fluorescence emissions of CQDs
One unique property of CQDs is their tunable fluorescence

emissions. Generally, CQDs possess tunable emissions even
without any surface passivation, but they usually have very low
quantum yields due to unstable surface defects leading to
reduced radiative recombination.
Upon surface passivation with organic or polymeric materials,
such as poly(propionyl ethyleneimine-co-ethyleneimine) (PPEI-EI)
attached to the CQD surface, surface defects are stabilised and
strong fluorescence emissions both in solution-like suspension
and in solid state were detected. The emissions of such passivated
CQDs covered a broad range of the visible region and extended
into the near-infrared (NIR) region as shown in Fig. 3.7
It should be noted that the surface passivation agents used were
not emissive in the visible and NIR regions, thus any fluorescence
emissions observed must have originated from the surfacepassivated CQDs. The tunable emission property of CQDs is
clearly demonstrated in Fig. 3. From the fluorescence spectra of
PPEI-EI-passivated CQDs, it is evident that the emissions are
broad and excitation wavelength-dependent.7,26 The tunable
emissions of the surface-passivated CQDs could be a result of
varied fluorescence characteristics of particles of dierent sizes
of the CQDs and the distribution of dierent emissive sites
on the surface of the CQDs. However, the exact mechanism
accounting for the excitation wavelength-dependent emission
Fig. 3 (A) Aqueous solutions of PEG1500N-passivated CQDs (a) excited at 400 nm and (b) excited at the indicated wavelengths; (B) absorption and
emission spectra of PPEI-EI passivated CQDs in water with increasing lex from 400 nm on the left with 20 nm increments. Inset: emission intensities
normalized to quantum yields. (Reproduced with permission from ref. 7.)
364 | Chem. Soc. Rev., 2015, 44, 362--381
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Review Article
remains to be established and the requirement for surface

passivation in order to produce fluorescence emissions is
poorly understood. Experimental observations are not helpful
since controversial results are often observed. Moreover, the
optical properties of CQDs are closely associated with the
synthetic routes used in their preparation. For example, Sun
and co-workers attributed the fluorescence emissions to the
radiative recombination of excitons of surface energy traps of
CQDs. Upon surface passivation, these energy traps are stabilised
and therefore become emissive a phenomenon that has been
observed in semiconductor quantum dots.32 They postulated that
there must be a quantum confinement effect of emissive energy
traps on the surface of the CQDs. Nonetheless, such tunable
fluorescence emission property of CQDs provides an added
advantage in the selection of different emission wavelengths with
different excitation wavelengths that can be applied to optical
labelling and fluorescence imaging.
In addition to the excitation wavelength-dependent emission,
several reports have indicated that the fluorescence emissions of
CQDs are pH-dependent.10,33,34 Liu and colleagues noticed that
the fluorescence intensity of their CQDs decreases when the pH
of the solution is shifted from the optimal value of 7.0 regardless
of whether pH is increased or decreased.10 In another report, it
was observed that the fluorescence intensity of CQDs only shows
a slight decrease of B3% when the pH of the solution is changed
from 5 to 9.33 Jia et al. reported that CQDs prepared from direct
heating of ascorbic acid solution show a practically linear
dependence on the pH of the solution in the range of 4.0 to
8.0. The fluorescence intensity decreased by as much as 90%
from pH 4.0 to 8.0. Varying the pH of the solution from 4.0 to 8.0,
corresponding to the deprotonation of the carboxyl groups on
the surface of the CQDs, might cause electrostatic doping/
charging to the CQDs and shift the Fermi level.35 As seen above,
the significantly large variation of fluorescence intensity with the
pH of the solution and the synthetic routes used in the preparation of the CQDs adds additional complexity in finding out a
widely accepted fluorescence emission mechanism.
2.4
Up-conversion fluorescence
In addition to conventional down-conversion fluorescence

emissions, reports have also shown that certain CQDs have
up-conversion fluorescence emission properties.1,26,34,3639
Up-conversion fluorescence emission is an optical phenomenon
wherein the fluorescence emission wavelength is shorter than
the used excitation wavelength, which is particularly attractive
for in vivo bioimaging since bioimaging at longer wavelengths
especially in the NIR region is usually preferred owing to the
improved photon tissue penetration and reduced background
auto-fluorescence. Caos team first observed that their CQDs
emit visible light when excited by a 800 nm femtosecond pulsed
laser,1 thereby suggesting that such CQDs possess up-conversion
properties. Later, several other groups also observed up-conversion
fluorescence emissions from CQDs prepared by drastically different
synthetic routes.26,34,3639 For instance, Jia et al. demonstrated that
CQDs prepared by directly heating ascorbic acid solution at 90 1C
exhibit excellent up-conversion fluorescence emission properties
Chem Soc Rev
in addition to their normal down-conversion fluorescence emission.34 Upon excitation in the NIR region of 8001000 nm, green
light with a peak wavelength of 540 nm was emitted from their
CQDs. The up-conversion florescence emissions likely originated
from a multi-photon excitation process an essential feature of
up-conversion fluorescence emission.
This is, however, not without dispute. In view of the practically constant energy dierence of B1.1 eV between the excitation light and emission light, Shen and colleagues argued that
the multi-photon excitation is inadequate to account for the
up-conversion fluorescence emission properties of CQDs.26
They postulated that the up-conversion fluorescence emission
originates from the relaxation of electrons from a higher energy
state of the p orbital (LUMO) to the s orbital since some electrons
would inevitably transit to the LUMO when a large number of lowenergy photons excite the electrons in the p orbital. Of course, the
electrons in the s orbital can also be excited, but they only emit
conventional down-conversion light.
On the other hand, Wen et al. believed that some of the apparent
up-conversion fluorescence emissions are artefacts originating from
the conventional down-conversion emissions which have been
excited by the leaking component from the second diraction in
the monochromator of the spectrofluorometer.40 By simply inserting
a long pass filter into the excitation pathway the leaking component
can be removed. Thus, great care must be taken when interpreting
the fluorescence emissions of CQDs and further clarification is
necessary to explain up-conversion CQDs.
3. Synthesis of CQDs
3.1
Top-down synthetic route
Synthetic approaches for CQDs are generally classified into two

categories top-down and bottom-up. The former involves
breaking down larger carbon structures, such as nanodiamonds,41
graphite,7 carbon nanotubes,42 carbon soot,10 activated carbon43
and graphite oxide44 by methods like arc discharge, laser ablation
and electrochemical oxidation. Xu et al. discovered the first
example of fluorescent CQDs when they were purifying SWCNTs
from arc-discharged soot.6 The arc-discharged soot was oxidised
with nitric acid, extracted using sodium hydroxide solution
and the black suspension from the extract was then subjected
to gel electrophoresis to obtain CQDs. Subsequently, Sun and
colleagues pioneered the synthesis of CQDs by laser ablation of
a carbon material using argon as a carrier gas in the presence
of water vapour.7 Nanosized carbon particles in aggregates of
different sizes were formed but these CQDs gave no obvious
fluorescence emissions. Therefore, the sample was given an acid
oxidative treatment followed by surface passivation in order to
observe bright fluorescence. Zhous group first described an
electrochemical method to prepare CQDs.42 It involved growing
multi-walled carbon nanotubes on a carbon paper, which was
then inserted into an electrochemical cell that contained degassed
acetonitrile with 0.1 M tetrabutyl ammonium perchlorate as the
supporting electrolyte. To significantly cut down the cost of the
starting materials and increase the scale of CQD production,
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a one-step electrochemical approach utilising low-cost and readily available graphite as a carbon source was recently proposed
by Ming et al.45 The prepared CQDs were predominantly multilayer graphene oxide exhibiting both down- and up-conversion
fluorescence emissions.
3.2
Bottom-up synthetic route
On the other hand, the bottom-up approaches synthesise CQDs

from molecular precursors such as citrate,46 carbohydrates47,48
and polymersilica nanocomposites3 through combustion/
thermal treatments, and supported synthetic and microwave
synthetic routes. For instance, Lius team reported a synthetic
method based on the use of modified silica spheres as carriers
and resols as carbon precursors (Fig. 4).3 Bourlinos et al.
described an easy, one-step thermal decomposition method
of obtaining fluorescent CQDs from ammonium citrate.46 Zhu
and co-workers showed that CQDs are readily formed by heating
a solution of poly(ethylene glycol) (PEG) and saccharide in a
500 W microwave oven for 2 to 10 min.49
Cost is one of the important determinants of CQDs becoming
viable competitors to semiconductor quantum dots. However, the
above-described approaches require either costly precursors,
complex instrumental set-ups or post-treatments to synthesise
fluorescent CQDs. Recently, green synthetic approaches were
introduced. With these green routes, CQDs were produced in
one step without the need for expensive materials and elaborate
experimental set-ups. Lis team was one of the first groups to
introduce the concept of preparing fluorescent CQDs using a
simple and green route.50 Their approach only involved a single
electrochemical treatment step of ethanol with sodium hydroxide.
This approach is less costly and easier to manage, and the CQDs
produced were found to possess desirable fluorescence properties
along with high water solubility, stability and sensitivity to pH.
Thereafter, the use of other inexpensive and biocompatible starting
materials, like ethanol,50 citrate,51 glucosamine,52 ascorbic acid,53,54
Review Article
saccharides,49,55,56 candle soot,57 watermelon peels,58 pomelo

peels,59 orange juice,60 strawberry juice,61 sugar cane juice,62
chicken eggs,63 chitosan,64,65 organogel66 and gelatine,67 were
developed. Many of these green CQDs displayed excellent
performance in cell imaging and chemical sensing applications.
Table 1 summarises the representative examples of the green
synthetic routes developed for the preparation of CQDs.
In addition to acid-oxidative treatment and surface passivation, other methods have been explored in a bid to increase
quantum yield and obtain CQDs with better fluorescence
properties. One approach is to dope newly-produced and
surface-passivated CQDs with inorganic compounds such as
ZnS and ZnO.74 An aqueous suspension of CQDs and Zn(CH3COO)2
was hydrolysed with NaOH or precipitated with Na2S to obtain
ZnO- and ZnS-doped CQDs, respectively. In the case of doping
with ZnO, an additional thermal annealing step was required to
transform Zn(OH)2 to ZnO. The respective quantum yields of
the ZnS- and ZnO-doped CQDs in aqueous solutions were above
50% and around 45% with the former being very close to
the quantum yield of commercially available semiconductor
CdSe/ZnS quantum dots.55 It was speculated by the authors that
doping might have reinforced the surface passivation eect or
even served as an additional form of surface passivation mode
together with the existing organic passivating agents. These
doped CQDs were shown to have strong multi-photon fluorescence properties,55 giving them great potential in the field of
one- and two-photon excitation imaging applications.
3.3
Surface passivation and functionalization
Surfaces of CQDs possess high sensitivity to contaminants in

their environment, such that their properties are easily aected
by tiny levels of contaminants. In order to alleviate this problem,
surface passivation of CQDs is performed to reduce the detrimental
eect of surface contamination to their optical properties.75
Surface passivation is usually attained by the formation of a
Fig. 4 Supported-synthesis of CQDs using modified silica spheres as carriers and resols as carbon precursors. (Reproduced with permission from ref. 3.)
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Table 1
Chem Soc Rev
Summary of representative green synthetic routes for CQDs
Precursor
Synthetic method
Phenol/formaldehyde resin, silica particle

Ascorbic acid
Citrate
Carbonisation at 900 1C, NaOH etching

Heat treatment at 90 1C
Carbonisation in air at 300 1C or hydrothermal
treatment at 300 1C
H2SO4, HNO3 treatment, amine passivation
Alkali- or acid-assisted ultrasonic synthesis
Microwave treatment (500 W)
Electrochemical treatment (2540 V)
Hydrothermal treatment at 180 1C
Microwave oven at 100 W
HNO3 oxidation
Carbonisation at 220 1C
Plasma irradiation (50 V, 2.4 A)
Microwave oven
Topochemical polymerisation
H2SO4 treatment
Microwave oven (700 W)
Carbonisation at 300 1C
Carbonisation with P2O5
Carbohydrate
Carbohydrate (glucose)
poly(ethylene glycol) and saccharide
Ethanol in NaOH solution
Citrate
GlucosamineHCl
Ascorbic acid
Ascorbic acid
Glucose
Sucrose
Candle soot
Watermelon peels
Pomelo peels
Orange juice
Strawberry juice
Sugar cane juice
Chicken egg
Chitosan
Chitosan
Organogel
Gelatine
Hair fibre
Ionic liquids
3-(3,4-Dihydroxyphenyl)-L-alanine, L-histidine,
and L-arginine
Citric acid and ethylenediamine
Acetic acid
Grass
thin insulating layer, usually by the attachment of polymeric

materials, such as oligomeric PEG, PEG1500N, on an acid-treated
CQD surface.7 It was shown that eective surface passivation is
an essential step in order to produce CQDs with high fluorescence intensities. Furthermore, Dong and co-workers reported
that electrochemiluminescence activities are partly responsive
to surface passivation, where the surface-passivated CQDs
exhibited weak electrochemiluminescence activities but strong
fluorescence.43 In contrast, CQDs whose surfaces are unpassivated or naked might emit colourful fluorescence, but their
quantum yields are generally low,9,10,42,57,76 except for a recent
report by Shens group.77 After reductive treatment with NaBH4,
they demonstrated that hydrothermally treated CQDs have
quantum yields as high as 40.5%.58 These bare CQDs might
serve as good alternatives to acid-treated CQDs since their
surfaces are prone to oxidative erosion during chemical oxidation using strong acids. However, this method of synthesising
bare CQDs with high quantum yields does not seem to be
highly ecient and reproducible. Therefore, many still relied
on the acid treatment and surface passivation to enhance the
quantum yield of CQDs. Wang et al. prepared CQDs with
quantum yields as high as 60%,78 which puts them on par with
the best commercial CdSe/ZnS semiconductor quantum dots in
aqueous solutions. Precursor CQDs were first synthesised using
the method described by Sun et al. and surface passivated with
PEG1500N.7 To form acyl chlorides on their surface, these
Quantum
yield (%)
Application
Ref.
14.7
3.22
3
Bioimaging
pH sensing
3
34
46
13
7
3.16.3
4
68
5.7
6
1.12.4
3
7.1
6.9
26
6.3
5.76
6.8
43
31.6
11.1
1.655.14
Hg2+ sensing
Bioimaging, pH sensing
Bioimaging
Bioimaging
Bioimaging
Bioimaging
Hg2+ sensing
Bioimaging
Hg2+ sensing
Bioimaging
Printing
Bioimaging
Bioimaging
Bioimaging
Quercetin sensing
Bioimaging
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
80
2.56.2
Fe3+ sensing, printing

Bioimaging
Cu2+ sensing
71
72
73
precursor CQDs were then treated with thionyl chloride. Following

that, the acyl chlorides reacted with PEG1500N when the CQDs were
kept at 110 1C. The sample of the treated CQDs was subsequently
loaded onto an aqueous Sephadex G-100 gel column and eluted
with water. At the end of the column, individual fractions were
collected. While all fractions produced similar fluorescence spectra,
the quantum yield was found to be higher for the later eluted
fractions. A quantum yield between 55 and 60% was reached in
the last fraction,59 which probably consisted of smaller and
better-passivated CQDs.
Anilkumars group introduced the concept of crosslinking
surface passivated CQDs for better optical performance.79 They
showed that crosslinking of the passivating PEG1500N on the
surface of CQDs results in the formation of fluorescent particles
that contain multiple CQDs in covalently-bound clusters (Fig. 5).
Interestingly, it was observed that the fluorescence properties of
the CQDs in each particle are additive and up to seven CQDs exist
in a single particle for maximum brightness when one particle is
subjected to fluorescence imaging. It was suggested that crosslinking most likely results in the stabilisation of surface functionalization by reinforcing the structure of the soft shell of PEG1500N
molecules that surround the hard fluorescent CQD cores, thus
achieving improved fluorescence emissions.
Functionalization of CQDs is important because the introduction of functional groups, such as amines and carboxyls, can
impose dierent defects on the CQD surface. These defects
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the quantum yield of CQDs. As demonstrated by Zhu et al.,71

nitrogen-doped CQDs (N-CQDs) exhibit a quantum yield of 80%,
comparable to most organic dyes and semiconductor quantum
dots. Leveraging on the synergistic eect of N- and Mg-doping, a
quantum yield of 83% was recently reported.82 Nonetheless,
unlike organic dyes and semiconductor quantum dots of which
both composition and structure are well-defined, considerable
ambiguities in the composition and structure of CQDs are likely
the cause of their low and often varied quantum yields. Therefore, in addition to significantly enhancing the quantum yields
of CQDs, synthetic approaches with high reproducibility
and scalability that are capable of producing geometrically,
compositionally and structurally well-defined CQDs with high
reproducibility and scalability are urgently needed.
Fig. 5 Crosslinking of PEG1500N-functionalised CQDs by reaction with
dimethyl pimelimidate in a pH 8 phosphate buer. (Reproduced with
permission from ref. 79.)
4. Applications of CQDs
4.1
work as excitation energy traps and lead to large variations in

fluorescence emissions.63,64 In fact, oxidative treatment using
strong acids is a simple and very eective means to introduce
carbonyl and carboxyl groups on the surface of CQDs, imparting greater water solubility to the CQDs.14 It has been shown by
Lius group that an oxidant is a necessary component to
produce visible fluorescence emissions.10 His group proposed
that an additional function of this acid oxidative treatment is to
possibly break down carbon aggregates into smaller nanoparticles.
Therefore, an oxidative acid like nitric acid was often added to
the reaction mixture in the synthesis of CQDs.
Very often, surface passivating agents act as functionalising
agents as well, where the physical properties of the CQDs are
modified together with their fluorescence properties. Thus, there
is no need for additional modification steps in the later stage of
synthesis. For example, Dong and colleagues used branched
polyethylenimine (b-PEI) as both the surface passivating and
functionalising agent, where the polyamines passivate the CQD
surface and the free amine groups allow for the functionalization
of the passivated CQDs.80 In another report, surface passivation
was achieved using diamine-terminated oligomeric PEG, thereby
achieving bright luminescence and surface functionalization of
CQDs simultaneously.81
As a class of novel fluorescent nanoparticles with environmental and biological benign composition and high biocompatibility,
major technical applications of CQDs would naturally be in the
fields of bioimaging and biosensing. In order to rival their
organic dye and semiconductor quantum dot counterparts, a
high quantum yield of CQDs is vital for these applications.
Consequently, extensive research eorts have been devoted
to engineering CQDs to improve their quantum yields. A wide
variety of synthetic routes for the preparation of CQDs have
been developed. Although a quantum yield as high as B80%
has been obtained,71 the majority of the CQDs synthesised so
far have quantum yields below 10% (Table 1). In addition to
surface-passivation, doping with heteroatoms and nitrogen in
particular has shown great potential to significantly enhance
368 | Chem. Soc. Rev., 2015, 44, 362--381
Chemical sensing
An interesting application of CQDs is in the field of chemical

sensing. The detection of heavy metals such as Hg2+ is of utmost
importance because of their hazardous eect on the environment and human health. CQDs were used for chemical sensing
due to their low toxicity, water solubility, high photostability and
superior chemical stability.
One of the first attempts of utilising CQDs in chemical sensing
is the selective detection of Hg2+ in aqueous solutions51,61,6887
and live cells.87 Goncalves and colleagues demonstrated that
the fluorescence emissions of both CQD solution and CQDs
immobilized in solgel are sensitive to the presence of Hg2+,84,85
In their study, laser-ablated and NH2-PEG200 and N-acetyl-Lcysteine-passivated CQDs were used as fluorescent probes. It
was observed that the fluorescence intensity of the CQDs is
efficiently quenched by micromolars of Hg2+ with a Stern
Volmer constant of 1.3 105 M1. Therefore, judging from
the relatively large magnitude of the SternVolmer constant,88 the
quenching provoked by Hg2+ is probably due to static quenching
arising from the formation of a stable non-fluorescent complex
between CQD and Hg2+. A substantial improvement in the sensitivity down to nanomolars was later realised by replacing the laserablated CQDs with N-CQDs. Again, static quenching is thought to
be responsible for the quenching of fluorescence but with a much
larger SternVolmer constant of 1.4 107 M1, two orders of
magnitude higher than that of the previous system.85 It was
suggested that the presence of nitrogen element in the N-CQDs,
most probably CN groups on the N-CQD surface, is responsible
for the much improved performance of Hg2+ sensing.
More recently, Yan and co-workers adopted the Hg2+CQD
system for selective detection of Hg2+ in aqueous solution as
well as in live cells.87 The authors reported the synthesis of two
types of CQDs using citric acid with 1,2-ethyldiamine (CQD-1)
and N-(b-aminoethyl)-g-aminopropyl (CQD-2) that possess high
quantum yields of 65.5 and 55.4%, respectively. They studied
the effective and selective quenching of fluorescence emissions
of CQD-1 and CQD-2 by Hg2+. Both CQDs acted as selective and
sensitive fluorescent probes for the detection of traces of Hg2+
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Chem Soc Rev
Fig. 6 UV-vis (black lines) and fluorescence spectra of (a) CQD-1 and (b) CQD-2 aqueous solutions in the absence (blue lines) and presence (red lines) of
Hg2+; fluorescence responses of (c) CQD-1 and (d) CQD-2 aqueous solutions in the presence of 20 mM of dierent metal ions. (lex = 360 nm).
(Reproduced with permission from ref. 87.)
in both aqueous solutions and live cells. Upon the addition of

20 mM of Hg2+, the fluorescence intensity of CQD-1 was rapidly
quenched by 80%, while that of CQD-2 was quenched by 55%,
and both remained stable after 1 h of observation (Fig. 6). This
substantiates the viability of using CQD-1 and CQD-2 as
chemical sensing probes for Hg2+. The selectivity of CQD-1
and CQD-2 toward Hg2+ was then assessed by comparing the
extent of fluorescence quenching of CQD-1 and CQD-2 by the
addition of 20 mM of different metal ions. As shown in Fig. 6,
among all metal ions tested, Hg2+ quenched both the fluorescence of CQD-1 and CQD-2 to the largest extent. Such quenched
fluorescence was reversible and could be recovered by adding a
strong chelating agent such as EDTA, making these CQDs
reversible fluorescent probes. Furthermore, successful attempts
were made in detecting Hg2+ in cultured cells.87
Other applications of CQDs in chemical sensing included
the detections of Cu2+,8996 Fe3+,97,98 Pb2+,99 Cr(VI)100 and Ag+.93
Similar to the Hg2+ sensing, most of the procedures proposed
are based on the above-mentioned fluorescence quenching by
the metal ions. For example, Liu et al. reported a procedure for
selective detection of Cu2+ in aqueous samples such as tap
water by CQDs modified with lysine and bovine serum albumin
(CQDs-BSA-Lys).89 Highly sensitive detection of Cu2+ was achieved
by making use of the coordination reaction of Cu2+ with both
the COOH and NH2 groups of the CQDs-BSA-Lys. To improve
the sensitivity of the assays, apart from coating CQDs with
various polymeric materials, metalorganic frameworks (ZIF-8

zinc imidazolate frameworks)94 and silica nanoparticles95 were
employed in the configuration of more sensitive CQD-based
fluorescent probes. For instance, Lin and co-workers showed
that highly sensitive nanocomposite fluorescent probes can
be readily prepared by encapsulating b-PEI-coated CQDs into
ZIF-8. Leveraging on the synergistic effect of the strong fluorescence of the encapsulated CQDs and the selective accumulation
effect of the ZIF-8 host, as low as 80 pM Cu2+ was detected by
the CQD-ZIF-8 nanocomposite probes.74 It is envisioned that
the same strategy can be extended to the preparation of other
CQDmetalorganic framework probes for highly sensitive and
selective detections of many other analytes.
Along with the development of sensitive metal ion assays,
CQDs have also found niche applications in the detections
of pH,93,101 C2O42,96 PO43,102 CN,103 F,104 S2,105 ClO,106
I 85,107 and NO2 gas.108 Contrary to the metal ion assays which
leverage on the fluorescence quenching mechanism, many of
the anion assays are based on the fluorescence enhancement
(fluorescence recovery) of the already quenched CQDmetal
complexes. For example, in the I assay, the fluorescence of
the CQDs was recovered due to the formation of more stable
complexes between I and the metal ions, displacing the CQDs in
the CQDmetal complexes.107 Furthermore, assays for small organic
compounds including ascorbic acid100 via fluorescence enhancement; and 4-nitrophenol,109 quercetin,69 2,4-dinitrophenol and
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2-amino-3,4,8-trimethyl-3H-imidazo[4,5-f]quinoxalin110 through
fluorescence quenching have been reported.
Apart from utilising the fluorescence of CQDs as an analytical
signal, recent studies have revealed that CQDs exhibit good
chemiluminescence111 and electrochemiluminescence.112 Therefore, several groups have developed chemiluminescent assays for
NO2 113 and Co2+;114 and electrochemiluminescent assays for
traces of pentachlorophenol115 and Cu2+.116
So far, a wide variety of procedures and a large number of
starting materials have been used in the preparation of CQDs
for the assays, thus leading to substantial batch-to-batch and
lab-to-lab variations. Such variations in the synthesis of CQDs
have serious consequences since studies have suggested that
the fluorescence characteristics are strongly dependent on
the composition of CQDs and residue chemical groups on
their surface; and dierent starting materials and procedures
inevitably produce CQDs with rather dierent physicochemical
properties and optical properties in particular. Standardisation
is therefore urgently needed in the preparation of CQDs and the
assessment of the performance of CQDs.
4.2
Biosensing
CQDs were also used in biosensing based on the use of antibodies and their gene-recombinant fragments. In this scheme,
CQDs are mainly applied in immunoassays as fluorescent labels.
This was shown in an example by Posthuma-Trumpie et al.117
with an emphasis of the use of CQDs in lateral flow and
microarray immunoassays. CQDs are less costly, more stable
and more sensitive, hence they were chosen over other commonly used fluorescent labels for this study. CQDs were shown
to have higher sensitivity as labels in lateral flow assays (LFAs)
in comparison to gold or latex nanoparticles.118 It was claimed
that CQDs exhibit sensitivity in the picomolar range.13 In a
general example of nucleic acid LFA (NALFA) (Fig. 7), the
discriminating tags on the amplicons are recognised by their
Fig. 7 Schematic illustration of NALFIA. (Reproduced with permission

from ref. 117.)
370 | Chem. Soc. Rev., 2015, 44, 362--381
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respective antibodies and fluorescence signals are provided by

the attached CQDs.
rster resonance energy transfer
Employing the principles of Fo
(FRET) and homogenous immunoassay, Bu and co-workers119
proposed an immunosensor for quick and specific detection of
4,4 0 -dibrominated biphenyl (PBB15) a persistent organic
pollutant that disturbs the endocrine system.120 This immunosensor comprised of gold nanoparticle (AuNP)-functionalised
anti-PBB15 antibodies and CQD-labelled PBB15 antigens that
function as the fluorescence acceptors and donors, respectively.
As a result of FRET, the fluorescence of the CQDs was effectively
quenched by the AuNPs. Upon the addition of PBB15 to the
solution, the CQD-labelled antigens were released from the
AuNP surface due to competitive immunoreaction and fluorescence recovery occurred. This immunosensor serves as a good
example for future development of immunoassays to detect
other analytes with suitable antibodies and antigens.
The concept of fluorescence quenching was also applied
to the detection of nucleic acids, where the level of selectivity
was so high that even a single-base mismatch could be identified.121 First, a single-stranded DNA (ss-DNA) labelled with a
fluorescent dye adsorbed onto a CQD, eectively quenching the
fluorescent dye. When the ss-DNA hybridised with its complementary target to form a double-stranded DNA (ds-DNA), the
newly-formed ds-DNA desorbed from the CQD surface and the
fluorescence recovered. This application showed great prospects
in the detection of single-nucleotide polymorphisms based on
the fluorescence intensity changes.
Another application of CQDs was based on the exploitation
of aptamers, which are target binders selected from a large
nucleic acid library.13 The aptamers are usually coupled with a
conformational change induced by the target and could possibly
result in a detectable change in radiometric response.122 Such an
application was realised by Xus group,123 who demonstrated
that thrombin induces aptamer-functionalised CQDs to form a
sandwich-structure with aptamer-functionalised silica nanoparticles through specific thrombinaptamer interaction. This
assay was highly specific to thrombin with a detection limit of
1.0 nM, making it one of the more sensitive fluorescent assays
for thrombin. Stable fluorescent CQDs prepared using a singlestep microwave pyrolysis method were used for the detection of
proteins after they were separated by gel electrophoresis.124
Staining of proteins using these CQDs turned out to give
comparable or even better sensitivity as compared to conventional staining agents such as Coomassie Brilliant Blue and
Ag+. Water-soluble CQDs, prepared from thermal combustion
of rice straws in a furnace under insufficient air flow, were used
for rapid detection and counting of bacteria cells in sewage
water.125 These CQDs selectively interacted with the receptors
on the bacterial cell membrane only.
In addition to macrobiomolecules, CQDs have also shown
promise as fluorescent probes in the detection of small bioanalytes like anti-bacterial drugs. One such example was
shown by the experiments performed by Niu and Gao.126 First,
fluorescent N-CQDs were produced from glutamic acid through
a one-step pyrolysis method. These N-CQDs were subsequently
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used for the detection of amoxicillin. Amoxicillin is a common

drug used to treat bacterial infections. The authors found that
amoxicillin molecules eectively separate the N-CQDs from
each other, thus lowering the frequency of non-radiative transitions that ultimately leads to a rise in fluorescence intensity.
CQDs were also applied to the detections of other small
bioanalytes such as dopamine,98,127,128 ascorbic acid100 and
glucose.129 For instance, Qus group synthesised highly fluorescent CQDs using dopamine as carbon source and applied them
to label-free detection of dopamine. Similar to the anion
sensing mentioned earlier, dopamine eectively recovered the
fluorescence of the already quenched Fe3+CQD complex. It was
observed that the enhancement of the fluorescence is proportional to the dopamine concentration in the range of 0.110 mM
with a detection limit of 68 nM.98 However, dopamine was
believed to be an efficient quencher in another report.128 This
controversy likely originates from the different carbon sources
and synthetic routes used in the preparation of the CQDs.
Therefore, caution must be taken when interpreting the data
and standardisation in CQD synthesis is urgently needed.
4.3
Bioimaging
As previously discussed, CQDs have multiple advantages over

semiconductor quantum dots, including comparable optical
properties and good chemical and photochemical stability.
Most importantly, carbon is largely non-toxic and environmentally friendly. These traits make CQDs very desirable as alternatives to semiconductor quantum dots to visualise biological
systems both in vitro and in vivo.62 In general, the carbon cores
of CQDs themselves are not toxic and any cytotoxicity of CQDs
is primarily due to surface passivating agents on the CQD
surface.130 It has been demonstrated that surface passivating
agents of low cytotoxicity can be used safely at high concentrations for in vivo imaging. For example, PEGylated CQDs showed
no noticeable toxic eects in vivo up to 28 days when intravenously injected 840 mg kg1 (CQD/bodyweight) of the
PEGylated CQDs into mice for toxicity evaluation. Physiological
indicators were all at similar levels for mice exposed to different
dosages of CQDs and the NaCl control, thereby suggesting the
non-toxicity of CQDs at exposure levels and times beyond those
typically used in in vivo imaging studies. No abnormalities were
observed in harvested organs although the amounts of CQDs
found in liver and spleen were higher than those found in other
organs.16 Moreover, cell viability was measured after cells had
been treated with different amounts of CQDs. It was found that
the average cell viability is greater than 95% at CQD concentrations up to 1.8 mg ml1. These results clearly demonstrated
that CQDs are much more biocompatible than semiconductor
quantum dots.14,131 Even if agents with high cytotoxicity profiles are used to coat CQDs, CQDs modified with these agents
can still be used for in vivo applications if these agents are
maintained at low concentrations and/or the incubation time is
kept relatively short.
It was revealed that organic dye-conjugated CQDs are eective fluorescent probes for H2S. A FRET process took place in
the presence of trace amounts of H2S, turning the blue emission
Chem Soc Rev
Fig. 8 Fluorescence images of the organic dye-conjugated CQDs loaded

live cells before (A, D) and after incubating with 30 (B, E) and 100 mM H2S
(C, F). (Reproduced with permission from ref. 132.)
of the organic dye-conjugated CQDs to green.132 Previous work

has proved that H2S can penetrate cell membrane by simple
diusion.133 Using a fluorescence microscope, the ability of the
organic dye-conjugated CQDs to visualise changes in physiologically relevant levels of H2S in live cells was evaluated. Fig. 8
displays the fluorescence images of HeLa and L929 cells incubated with the organic dye-conjugated CQDs before and after
being treated with H2S. As seen in Fig. 8, the intracellular
fluorescence of the organic dye-conjugated CQD-stained cells
exposed to H2S for 30 min at 37 1C turned green, clearly indicating
that the organic dye-conjugated CQDs are promising fluorescent
probes to track H2S level change in live cells.132 In another
example, CQDs synthesised using N-(b-aminoethyl)-g-aminopropyl methyl-dimethoxysilane as a carbon source selectively
interacted with Cu2+ because of the residue ethylenediamine
groups on their surface.95 Additionally, dual-emission probes for
Cu2+ were prepared by coating such CQDs on the surface of
Rhodamine B (RhB)-doped silica nanoparticles. The fluorescence
of the CQDs was eciently quenched by Cu2+, while that of RhB
was negligibly aected. Utilising these probes, successful attempts
were made in in vivo imaging of Cu2+ in live cells.95
Cell images obtained by Hsu et al. showed that CQDs are
mostly localised in the cytoplasm and cell membrane.134 It was
also shown that water-soluble CQDs passivated with PPEI-EI
could label the cell membrane and cytoplasm of MCF-7 cells
and they do not reach the nucleus.1 Furthermore, CQDs
synthesised from activated carbon selectively labelled the cell
membrane and cytoplasm of COS-7 cells.135 On the other hand,
cells incubated with silica-encapsulated CQDs were found to
only exhibit bright fluorescence in the cytoplasmic area.136
Fowley and colleagues prepared CQDs that were enclosed in an
amphiphilic biocompatible polymer, which were subsequently
found to travel across Chinese hamster ovary cell membrane
and settle in the cytosol.137 Hus team prepared b-PEI-coated
CQDs with a quantum yield of 54.3% and these CQDs were
observed to distribute uniformly throughout the cytoplasm.138
These examples clearly show that the localisation of CQD varies,
depending on the choice of the surface passivating agents and
the mode of surface passivation.
Before imaging, cells are usually incubated with CQDs so
that the CQDs can be internalised by the cells. This ability of
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Fig. 9 (a) Emission spectra of CQDs at dierent excitation wavelengths; fluorescence images of MCF-10A cells treated with CQDs upon excitation with
(b) UV, (c) blue and (d) green light. (Reproduced with permission from ref. 134.)
cells to take in CQDs was revealed to be dependent on temperature, where no CQDs were found to internalise into the cells at
48 1C.1 It was proposed that CQDs likely translocate into cells by
endocytosis. Also, it was suggested that the uptake of CQDs may
be enhanced by coupling CQDs with membrane translocation
peptides, so as to facilitate this translocation procedure by
overcoming the cell membrane barrier.139,140
As mentioned above, CQDs are able to exhibit multicolour
emissions, which is a huge advantage that sets them apart from
the majority of labelling agents. This allows researchers to
control and choose the excitation and emission wavelengths.141
As illustrated in Fig. 9, the property of tunable emissions of
CQDs was clearly visible,134 where light at dierent wavelengths
was emitted upon excitation at dierent wavelengths. This property
was also seen in HepG2 cells incubated with 4,7,10-trioxa-1,13tridecanediamine-passivated CQDs, which portrayed multicolour
emissions when excited at dierent wavelengths.142 Green CQDs
prepared from sugar cane juice also exhibited multicolour emissions upon dierent excitation modes in bacteria and yeast cells.62
Notably, Ray et al. revealed that surface passivation might not be
necessary to achieve a high level of fluorescence intensity required
for cell imaging.57 CQDs prepared from the thermal combustion of
soot and treated with acid were able to translocate into Ehrlich
ascites carcinoma cells successfully even though they were not
coated with any surface passivating agents.57
If the excitation wavelength is red-shifted enough, CQDs
could emit in the NIR region. Although the emission in the NIR
region is relatively weak, CQDs have great potential for in vivo
fluorescence tracking studies141 because the animal body is
practically transparent in the NIR region.143 Yangs group was
the first to explore the viability of CQDs as contrast agents in
live mice.15 In their experiments, PEG1500N-passivated CQDs
were injected subcutaneously into mice and bright fluorescence
emissions were observed, only fading away 24 h after the
injection. If the CQDs were injected intravenously, emissions
were only observed in the bladder region, thereby suggesting
that urine extraction is the main exiting route for intravenously
introduced CQDs. The same group also successfully tracked the
migration in lymph vessels using ZnS-doped CQDs (Fig. 10).15
In another report, Cao et al. employed the ZnS-doped CQDs
for in vivo imaging in mice, which showed comparable brightness with the well-established CdSe/ZnS quantum dots.144
However, after intradermal injections of the CQDs and CdSe/
ZnS quantum dots into mice, it was observed that though both
372 | Chem. Soc. Rev., 2015, 44, 362--381
Fig. 10 Tracking of migration through lymph vessels using ZnS-doped

CQDs. (Reproduced with permission from ref. 15.)
types of quantum dots moved to the axillary lymph nodes, the

former moved at a much slower rate than the latter.36 This was
ascribed to the PEG molecules on the CQD surface, which
reduce the interaction between the CQDs and the lymph cells.
Of particular interest was the observed competitive performance of the CQDs in vivo to that of the CdSe/ZnS quantum
dots. The above results suggest that CQDs may be further
developed into a new class of high-performance yet non-toxic
agents for bioimaging.144
The exact mechanism of CQD uptake by cells remains to be
elucidated, but increasing experimental evidence suggested
that CQDs are likely internalised by the cell through endocytosis without significant infiltration to the cell nucleus.1,14,18,19
In addition, the interaction between protective/functional coatings
on CQDs is believed to play an important role in selective cell
targeting. In future, better targeting ability of CQDs to cells and
perhaps even the nuclei may be achieved by conjugating CQDs
with facilitating proteins or peptides, enabling the CQDs cross
the cell membrane barrier more readily.
4.4
Nanomedicine
CQDs, being small fluorescent nanoparticles which can be

synthesised quickly via many inexpensive and simple synthetic
routes, serve as good alternatives to other fluorescent nanomaterials. CQDs are also very attractive in nanomedicine
because they do not show any visible signs of toxicity in animals
and thus can be used for in vivo studies.145 This is exemplified by
in vivo toxicity studies in mice, where mice were intravenously
injected with CQDs and tested after four weeks. It was concluded
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that their organs and internal functions are hardly aected. The
high biocompatibility of CQDs was also supported by prothrombin time assays in plasma samples. The results indicated
that CQDs do not limit the activity of thrombin and do not lead
to any blood coagulation.134
The work by Bechet and co-workers showed that CQDs can
be used for photodynamic therapy. Photodynamic therapy is a
clinical treatment mainly for superficial tumours.146 It involves
the localisation and accumulation of photosensitizers in the
tumour tissue, following which they are irradiated with a
specific wavelength, triggering the formation of singlet oxygen
species that result in cell death. It has been validated that CQDs
have high inhibition eect on MCF-7 and MDA-MB-231 cancer
cells.134 This phenomenon was attributed to CQDs being able to
generate more reactive oxygen species, making them promising
photosensitizers. It was also noted that the circulation and
uptake of CQDs in the body is dependent on their surface coating
and the route of administration.147 Huang et al. investigated the
eect of the injection route on the distribution, clearance and
tumour uptake of CQDs.81 It was learnt that CQDs are quickly
and eectively excreted from the body when intravenous, intramuscular and subcutaneous injection routes are used. Additionally, the high tumour-to-background fluorescence contrast and
low fluorescence levels in other tissues and organs demonstrated
the suitability of CQDs to act as photosensitizers as they are able
to localise selectively into tumours (Fig. 11).
Juzenas and colleagues also explored the use of CQDs as
photosensitizers in photodynamic therapy to destroy cancer
cells.148 Small CQDs functionalised with PPEI-EI (PPEI-EI-CQDs)
were prepared. Upon irradiation with UV light, these CQDs
displayed substantial photodynamic eect in Du145 and PC3
cells. It was proposed that photo-induced generation of singlet
oxygen (Type II mechanism) and other reactive oxygen species
and radicals (Type I mechanism) is responsible for the observed
photodynamic eect. TiO2 is one of the most popular semiconductor photocatalysts, but it can only be excited with UV
light due to the size of its bandgap.149 Unfortunately, UV
radiation has a low penetration power and can only penetrate
slightly into the skin tissue, thus resulting in poor photodynamic eciency in deep tissues.150 Compared to TiO2, PPEI-EICQDs have the additional advantage of tunable bandgap, where
their bandgap can be made smaller to allow excitation at longer
wavelengths. This would allow for the destruction of buried
tumours because light at longer wavelengths can penetrate deeper
into tissues. By attaching a photosensitizer (chlorin e6) to CQDs, a
synergistic photodynamic therapy platform was developed.151 It
was shown that the CQDs can indirectly excite the photosensitizer
Chem Soc Rev
by FRET mechanism. Moreover, the capability of up-conversion

fluorescence emissions of CQDs is more attractive in photodynamic therapy. As demonstrated by Fowley et al.,152 the
up-conversion property of CQDs is potentially useful in the
treatment of deep-seated tumours in photodynamic therapy. In
their study, a conventional photosensitizer (protoporphyrin IX)
was first conjugated to CQDs. The photosensitizer was indirectly
excited via FRET by the up-conversion fluorescence emission of
the CQDs upon excitation at 800 nm. The excitation light of
800 nm is in the phototherapeutic window and can penetrate
human tissue four times deeper than the 630 nm light used in
clinical photodynamic therapy.
In addition to phototherapy, CQDs can be used for radiotherapy. As described in a report by Andrius et al.,153 PEG-CQDs
coated with a silver shell (C-Ag-PEG CQDs) could be used as
radiosensitizers in Du145 cells. When irradiated with low
energy X-rays, electrons were ejected from the C-Ag-PEG CQDs,
which in turn generates free radicals and damages the cancer
cells surrounding the CQDs, reducing the damage of normal
cells and increasing therapeutic selectivity.
In the field of nanomedicine, a fusion of nanotechnology
and medicine, CQDs could function as nano-carriers for tracking and delivery of drugs or genes. In particular, CQDs with
fluorescence in the red or NIR region would be the most
desirable because background illumination from endogeneous
fluorophores can be avoided during imaging.154 Demonstrated
by Hus team, bPEI-coated CQDs (bPEI-CQDs) displayed great
potential in the application of gene delivery.138 These CQDs
have a large number of amino groups on their surface, which
could condense DNA to aid in their function as gene carriers. In
order to check for the viability of these CQDs as gene carriers,
the authors carried out additional transfection experiments
using enhanced green fluorescent protein (EGFP) gene, which
served as the reporter gene. As presented in Fig. 12, the overlay
of the three images revealed that the pPEI-CQDs exhibit high
fluorescence intensity and transfection eciency comparable
to EGFR. Evidently, the gene carried by the bPEI-CQDs was
successfully brought into the cells. Because of its significant
positive charge density and proton-sponge eect, bPEI spontaneously attracts and condenses gene (polyanionic DNA strands)
to form toroidal complexes that are readily taken up by cells
through endocytosis. The un-protonated amine moieties in the
complexes are thought to buer endolysosomal pH, thereby
allowing cytoplasmic release of gene.155
Drug delivery systems (DDSs) based on nanotechnology are
increasingly developed in recent years. The most widely investigated DDSs are based on AuNPs, but the issue of toxicity limits
Fig. 11 Fluorescence images of tumour-bearing mice. (Reproduced with permission from ref. 81.)
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Besides serving as drug carriers and fluorescent tracers,

CQDs were found to be able to control drug release. An example
was given by Lai and colleagues where CQDs loaded with DOX
could control the release of DOX in HeLa cells.164 Any prerelease of DOX before its uptake by the target cells was reduced,
thus drastically increasing the anti-cancer ecacy of this drug.
Moreover, CQDs functionalised with PEG oligomers allowed for
a longer circulation time in the physiological systems before they
targeted the selected tissues to achieve localised therapy.165
However, thus far, there have not been any reports of CQDs that
can specifically target a disease state,81 thus severely limiting
their uses in therapeutics.
Fig. 12 Fluorescence images of 293T cells transfected with (A) EGFR and
(B) DNAbPEI-CQD complexes; (C) the bright field image (D) the overlay
of the three images. (Reproduced with permission from ref. 138.)
their applications in clinical therapy.156 AuNPs also require thiol

groups for drug loading through Authiol interaction, which
imposes a further limitation of drug choice.154 In addition,
AuNPs are difficult to track in in vivo systems because they cause
the quenching of fluorophores.157 Therefore, CQDs serve as good
alternatives to AuNPs since different functionalizations could
result in many possibilities for conjugation with drug molecules
in combination with targeting agents, expanding the drug
choices for delivery.154
Zheng and co-workers conjugated a platinum(VI)-based anticancer pro-drug oxidised oxaliplatin (Oxa(VI)COOH) on the
surface of CQDs through chemical coupling.158 The pro-drugconjugated CQDs were taken up by cancer cells through endocytosis and the drug was released upon the reduction of Oxa(IV)
COOH to oxaliplatin(II) because of the highly reducing environment in cancer cells. It was also demonstrated that the distribution
of the pro-drug-conjugated CQDs can be closely tracked by
monitoring the fluorescence signal of the CQDs, thereby offering
great help in the customisation of the injection time and dosage
of the medicine. To engineer a controlled-release mechanism,
Karthik et al. introduced a photosensitive molecule (quinolone)
to the CQD-based drug delivery system.159 The strong fluorescent
properties of the CQDs serve as a conventional means to precisely
track the distribution of the drugCQD conjugates and the quinoline molecules on the surface of the CQDs serve as triggers for
photo-regulated drug release. Other drug-releasing mechanism
like pH-triggered drug release has also been tested.160,161 In an
attempt to enhance the loading capacity of CQDs, Mewada and
co-workers tested the drug carrying and folic acid-mediated delivering capacities of highly fluorescent swarming CQDs.162 Folic
acid on the CQD surface was used as a navigational molecule
thanks to its widespread association with most types of cancer
cells.163 The drug loading capacity for an anti-cancer drug
doxorubicin (DOX) was estimated to be B86% and the release
of DOX from the DOX-loaded CQDs followed first order release
kinetics at physiological pH an ideal drug release profile. More
interestingly, due to the better targeting ability of the folic acid
molecule, the DOX-loaded CQDs showed a higher killing rate of
cancer cells than free DOX and were less toxic to normal cells.162
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4.5
Photocatalysis
In recent years, photocatalytic processes have gained tremendous

momentum as greener alternatives in organic synthesis.166169
Interest in photocatalysis has been motivated in part by the
realisation that sunlight is effectively an inexhaustible energy
source. However, the high energy of UV and short wavelength
visible light may adversely damage organic compounds.166 The
demonstrated capability of harnessing long wavelength light and
energy exchange with solution species of CQDs offers an excellent
opportunity for their use as photocatalysts in organic synthesis.
Indeed, a recent study has indicated that smaller CQDs (14 nm)
are effective NIR light-driven photocatalysts for selective oxidation of alcohols to benzaldehydes with good conversion efficiency
(92%) and selectivity (100%), due to their excellent catalytic
activity for H2O2 decomposition and NIR light driven electron
transfer property.170 Further studies suggested that the photocatalytic activity of CQDs can be effectively modulated by doping
the CQDs171 and by tailoring the surface groups.172,173 On the
other hand, larger CQDs (510 nm) synthesised by electrochemical ablation of graphite showed light-induced proton
properties in solution, which can be used as acid catalysts to
catalyse a series of organic transformations in aqueous media
under visible light.174 More recently, Liu et al. reported the
utilisation of the photochemical properties of AuNPCQD
nanocomposites for high-efficiency and high-selectivity photocatalytic systems for green oxidation of cyclohexane.175 The
AuNPCQD nanocomposites yielded 63.8% conversion efficiency
and 99.9% selectivity for the oxidation of cyclohexane to cyclohexanone using H2O2 as the oxidant under visible light at room
temperature.175 Given its versatility in the design of the nanocomposite photocatalysts, this approach deserves more attention
since it may provide an exciting solution for the development of
high-performance photocatalysts and green synthetic routes for
the chemical industry.
As one of the most popular photocatalysts, TiO2 has been
used in the removal of organic pollutants and in the generation
of H2 through water splitting.176 However, a major drawback in
its photocatalytic eciency resides in its ineective utilisation
of visible light as the irradiation source. Because the bandgap
of bulk TiO2 lies in the UV region (3.03.2 eV), only less than 5% of
sunlight is utilised by TiO2. Therefore, bandgap engineering by
possible modification of TiO2-based materials is one of the plausible
approaches to enhance the performance of TiO2 photocatalysts.
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Fig. 13 Possible catalytic mechanism of theTiO2CQD nanocomposites

under visible light. (Reproduced with permission from ref. 36.)
In view of their attractive optical properties and up-conversion

in particular, a nanocomposite of CQDs and TiO2 is expected to
realise the efficient usage of the full spectrum of sunlight.
Using methylene blue (MB) as a model compound, Li et al.
showed that TiO2CQD nanocomposites are able to completely
degrade MB (50 mg mL1) within 25 min under visible light
irradiation, where only o5% of MB is degraded when pure TiO2
is used as the photocatalyst.36
Apart from harvesting visible light and converting it to
shorter wavelength light through up-conversion (Fig. 13), which
in turn excites TiO2 to form electronhole pairs,36,177179 it is
believed that the CQDs in the nanocomposites facilitate the
transfer of electrons from TiO2 and the electrons can be shuttled
freely along the conducting paths of the CQDs, allowing charge
separation, stabilisation and hindering recombination, thereby
generating long-lived holes on the TiO2 surface.180 The longerlived holes then account for the much enhanced photocatalytic
activity of the TiO2CQD nanocomposites. Likewise, similar
behaviour was observed with CQDTiO2 nanotube composites
in the photocatalytic degradation of MB181 and CQDTiO2
nanosheet nanocomposites in the photocatalytic degradation
of RhB.182 Further to the above TiO2CQD-based photocatalysts, other metal oxide nanoparticleCQD nanocomposites like
Fe2O3CQD,183,184 ZnQCQD185 and Cu2OCQD;186 and metal
phosphateCQD composite (Ag3PO4CQD),187 were also used to
harness the full spectrum of sunlight in their respective photocatalytic systems. Moreover, Kang and colleagues reported
SiO2CQD nanocomposites in the photocatalytic degradation
of MB36 and selective hydrocarbon oxidation.188 Nonetheless,
more work is needed to improve the lifespan of the abovementioned photocatalysts before they can be employed in
practical scenarios. Such work will be worthwhile because the
photocatalytic activities of the nanocomposites are much
greater than that of the well-known TiO2.
In recent years, researchers have succeeded in utilising TiO2
CQD nanocomposites as photocatalysts to generate H2 through
water splitting. One of the first reports was authored by Zhang
and co-workers.189 They noted that TiO2 nanotube arrays loaded
with CQDs are capable of producing H2 from water through
photocatalysis under visible light. As schematically depicted
in Fig. 14, the TiO2 nanotubes function as active sites for the
photochemical reduction of water into H2 and the CQDs as
photosensitizers. The presence of the CQDs effectively extends
Chem Soc Rev
Fig. 14 Illustration of the sensitization mechanism of CQDs. (Reproduced

with permission from ref. 189.)
the light harvesting range of the TiO2 nanotube arrays to the

visible and NIR regions. As a result, a four-fold enhancement
in photocurrent density and a hydrogen evolution rate of
14.1 mmol h1 at 0 V (vs. Ag/AgCl) were obtained.189 To further
improve the photocatalytic efficiency, the TiO2CQD nanocomposites were modified by adding narrow bandgap semiconductor
quantum dots (CdSe) to them to leverage on the up-conversion
property of the CQDs and the synergistic effect between the CdSe
quantum dots and the CQDs.190 Similar to the TiO2 nanotube
arrayCQD nanocomposites, photochemical production of H2
from water under irradiation from visible light was observed.
The nanocomposites were stable in the catalytic reaction and
the photocurrent density was dependent on the size of the
CQDs. The highest current density of 0.9 mA cm2 was
obtained with 3.8 nm CQDs, which is four times higher than
that of pristine TiO2.191
In addition to being used as photocatalysts, CQDs have been
capturing the attention of researchers as potential photosensitizers in solar cells. For example, a CQDRhBTiO2 system
showed that the CQDs effectively bridge the RhB molecules to
the TiO2 substrate by acting as a one-way electron transfer
intermediary. Comparing to the RhBTiO2 system, the presence
of CQDs significantly enhanced the photoelectric conversion
efficiency by as much as seven times.192 In another report, a
CQD/TiO2 electrode was employed in a solar cell. The photocurrent density was 2.7 times larger than that of pristine TiO2
electrode under visible light illumination.181 Enhanced performance
of a solar cell was also obtained when N-CQDs were used as
photosensitizers.193 Although the photo-to-electricity conversion efficiency of the above-mentioned solar cells is far from
satisfactory, these findings definitely encourage more research
in the application of CQDs in photovoltaic devices.
4.6
Electrocatalysis
For technological relevance in clear energy production like

fuel cells and clear fuel production, oxygen reduction reaction
(ORR) and its reverse reaction oxygen evolution reaction
(OER) are at the centre of intensive research. Because of the
sluggish kinetics of ORR,194 electrocatalysts are usually used to
improve the kinetics of ORR and of which platinum is the
state-of-the-art. Unfortunately, the formidably high cost of
platinum-based electrocatalysts has prompted researchers to
look for non-platinum-based electrocatalysts for ORR, aiming
Chem. Soc. Rev., 2015, 44, 362--381 | 375
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Fig. 15 Cyclic voltammograms of (a) N-CQD/graphene and (b) commercial Pt/C on a GC electrode in N2-saturated 0.1 M KOH, O2-saturated 0.1 M KOH
and O2-saturated 3 M CH3OH solutions. (Reproduced with permission from ref. 196.)
at achieving comparable or even better electrocatalytic efficiency

than that of platinum-based electrocatalysts.
The ultra-small size of CQDs along with their high stability
and good electrical conductivity makes them interesting contenders as electrocatalytic materials for ORR. Previous investigations on graphene have indicated that doped nitrogen atoms
in carbon materials, especially in the form of pyridinium
moieties, play a critical role in enhancing their electrocatalytic
activities toward ORR.195 One of the pioneering reports on the use
of CQDs as electrocatalysts for ORR was by Li and co-workers.196
They demonstrated that N-CQDs with oxygen-rich functional
groups prepared via an electrochemical procedure are electrocatalytically active toward electrochemical reduction of oxygen.
The onset potential of ORR was found to be 0.16 V (vs. Ag/AgCl),
which is close to that of commercial platinum-based electrocatalysts (Fig. 15). Similar results were later obtained by Yan
and co-workers197 and Liu et al.198 with N-CQDs synthesised by
totally dierent procedures. A comparison between nitrogenfree CQDs and the N-CQDs suggested that the electrocatalytic
activity of the N-CQDs is indeed closely associated with the
N-doping eect. In addition, the N-CQDs exhibited excellent
tolerance to a possible crossover eect from methanol. Firstprinciples investigations of the N-CQDs suggested that pyridinic
and graphitic nitrogen are responsible for the observed electrocatalytic activity.199 In another report, Zhu and colleagues investigated the electrocatalytic activity of CQDs prepared from natural
biomass soy milk.200 Similar to the N-CQDs, a much enhanced
electrochemical reduction profile of oxygen was obtained.
Likewise, OER also suers from sluggish kinetics and a high
over-potential is required in order to drive OER at a reasonably
high rate. Currently, the best electrocatalysts for OER are
ruthenium- and iridium-based materials. Again, the formidably
high cost of these materials has urged researchers to search for
alternative electrocatalysts that can oer high eciency in OER
and yet readily available at low cost. Unfortunately, reasonably
high electrocatalytic activity of CQDs toward OER has yet to be
reported. On the other hand, CQD-based hybrid materials such
as CQDNiFe-layered double-hydroxide composites have shown
some promise in OER.201 It was reported that the composites
exhibit high electrocatalytic activity toward the oxidation of
water at a relatively low over-potential of B235 mV in 1 M KOH
376 | Chem. Soc. Rev., 2015, 44, 362--381
at a current density of 10 mA cm2, which is comparable to

those of the most active perovskite-type electrocatalysts. It was
suggested that the synergistic effect arising from strong association of the CQDs with the NiFe hydroxide greatly facilitates
charge transport, thereby improving the catalytic activity of the
NiFe hydroxide. It is likely that this kind of CQD composites
will offer new opportunities for OER as well as many other
electrocatalytic applications.
5. Conclusion and outlook

Since the discovery of CQDs in 2004, a number of simple, lowcost and ecient routes for the synthesis of CQDs have been
developed. This is in drastic contrast to the much more
laborious and expensive chemistry that is required to synthesise other fluorescent nanoparticles, for example noble metal
nanoparticles and semiconductor quantum dots. Growing evidence
has suggested that the defects in CQDs play a critical role in their
observed fluorescence emissions. Consequently, approaches and
techniques that are capable of facially manipulating the population
and location of the defects in CQDs are both fundamentally
and technically critical in the synthesis of CQDs. The physicochemical properties of CQDs, including their fluorescence
properties without photobleaching and photoblinking, their
facile emission tuning and their chemical stability, enable the
development of highly sensitive sensing platforms. It is believed
that CQDs will play an increasing role in analytical and bioanalytical science in the near future. Unfortunately, CQDs with
high quantum yields still remain rare. Future research eorts
should be directed to significantly enhancing the quantum
yield of CQDs in addition to the preparation of geometrically,
compositionally and structurally well-defined CQDs. Meanwhile,
research in the applications of CQDs in sensing and bioimaging
should focus on enhancing the sensitivity, selectivity and robustness of the sensing and bioimaging platforms and on the use of
delayed fluorescence techniques to minimise the background
and to ooad the interference of auto-fluorescence of biological
samples.
The advent of CQD research has heralded a new chapter
in biomedicine. The proof-of-concept experiments mentioned
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above have confirmed that CQDs are able to contribute to the

advances of biomedicine via applications in bioimaging and
nanomedicine. The excellent chemical and photochemical stability
of CQDs together with their chemically non-toxic composition give
a clear advantage in the context of in vivo biomedical applications.
With these attractive features, CQDs have clearly become a legitimate competitor to the conventional semiconductor quantum dots
as bioimaging agents with comparable or even better performance
due to their excellent biocompatibility, high optical performance
without photoblinking and the ability to be functionalised with
various moieties. More importantly, by conjugating targeting moieties and therapeutic components, CQDs will enable theranostics
which holds the potential to address the challenges of cancer
heterogeneity and adaptation. Therefore, CQDs have the technical
capability that will enable the development of new diagnostics,
therapeutics and preventives, which can cause a paradigm shift in
the way we diagnose, treat and prevent cancer. Nonetheless, in drug
delivery and controlled release, a more fundamental question that
should be probed is why CQDs would be ecacious at all. What are
the advantages of CQDs for drug delivery compared with monoclonal antibodies in conjugation with anticancer drugs,202 and
nanospheres made of biodegradable polymers?203 The applications
of CQDs in nanomedicine should then be to first determine the
tasks for which CQDs are particularly valuable although preliminary results are encouraging. Further research is required in the
development of CQDs with better targeting ability to target specific
cell types and specific cell compartments. It is also essential that
CQDs to be used in bioimaging use relatively low-energy excitation
sources, preferably red or NIR sources, thus making them more
eective in tissue penetration and reducing the interference from
background fluorescence. Consequently, a major challenge in CQD
research is the synthesis of CQDs with brighter fluorescence
emissions excitable by red or NIR sources. Also, more research is
desired on the synthesis of CQDs with controlled shape, size and
functionalities. Although significant findings have been reported
with regard to the applications of CQDs, their exact mechanism
of cellular uptake and precise toxicological eect remain to be
elucidated due to the fact that the pharmacokinetics and biodistribution of CQDs are dependent upon multiple factors such
as size, shape, surface chemistry and so on. Through rational
design and optimisation of these factors, non-specific uptake of
CQDs can be significantly reduced and blood circulation can be
extended, thereby conferring CQDs enhanced abilities in targeting
specific tissues in the human body. First, surface functionalization
is the most important factor to alter and fine-tune the pharmacological properties of CQDs. For example, CQDs with oligomeric
PEG coatings exhibited much lower toxicity, longer blood circulation half-life and better tumour targeting eciency in vivo than
CQDs without appropriate surface coatings.81 Moreover, the right
shape and size of CQDs can result in reduced non-specific capture
by macrophages, which can also aect their excretion route,
circulation half-life, as well as how they will interact with dierent
tissues in vivo. Therefore, there is a need for reliable techniques to
produce CQDs with controlled and consistent properties. Considerably more research must be carried out before the viability of
CQDs can be fully realised and the development of CQDs for
Chem Soc Rev
potential biomedical uses should proceed in parallel with a thorough evaluation of the cytotoxic eect of CQDs.
The general strategy for the adoption of environmentally benign
CQDs as photocatalysts in synthetic chemistry represents an attractive approach in the development of green chemistry, which may
eventually lessen the burden of energy consumption, product
clean-up and waste disposal. The immediate goal in this emerging
area should be geared toward the discovery of photochemical
solutions for increasingly ambitious synthetic goals. The longterm goals should be to improve eciency and synthetic utility
and to eventually perform chemical synthesis under sunlight.
Compared to other applications of CQDs, there have been
fewer studies in the usability of CQDs as electrocatalysts for
ORR and OER. In-depth theoretical and experimental studies
are needed to delicately design CQD-based electrocatalysts with
desirable electrocatalytic activity and long-term operation stability. The combination of CQD doping and CQD-based nanocomposites with other nanomaterials may open up new
avenues to systematically study the eect of structural parameters and chemical compositions on the catalytic performance of the electrocatalysts, thus leading to fundamental
insights and practical applications.
Although still in the midst of development, CQDs have already
shown immense potential to play a big role in nanotechnology
for the development of assays, sensors, bioimaging agents,
drug carriers, phototherapy, photocatalysis and electrocatalysis.
Despite the fact that many optical and electronic properties of
CQDs are not well understood yet, there is no doubt that CQDs
will play a huge role in bioimaging and biomedical research in the
near future upon further development. Being highly versatile,
CQDs have the propensity to be rationally modified according to
dierent needs. Applications of CQDs in niche areas such as
photocatalysis exemplify the versatility of CQDs in the most
unexpected areas. It is heartening to witness the diversion of
research interest in CQDs away from traditional fields such as
bioimaging, and into more urgent and pressing needs such as
green chemistry and clean energy production. The fact that
the advantages of CQDs are being recognised by researchers
with interest in areas as diverse as materials science, synthetic
chemistry, drug delivery, nanomedicine and clean energy suggests
that research on CQDs will continue to grow in synergistic
relationship with intellectually adjacent fields. It seems clear that
the future of CQDs remains promising.
Acknowledgements
This work is supported by Ministry of Education and the
A*STAR-ANR Program.
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Chem Soc Rev

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Carbon quantum dots and their applications

Shi Ying Lim, Wei Shen and Zhiqiang Gao*

Published on 15 October 2014. Downloaded on 10/12/2014 00:32:21.

in this exciting and promising field.

certain limitations such as high toxicity due to the use of heavy

Ms Shi Ying Lim was born in

Shi Ying Lim

362 | Chem. Soc. Rev., 2015, 44, 362--381

Ms Wei Shen received her BSc in

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Fig. 1 Chemical structure of CQDs. (Reproduced with permission from

nanoparticles comprising amorphous to nanocrystalline cores

Dr Zhiqiang Gao is an associate

This journal is The Royal Society of Chemistry 2015

Chem Soc Rev

and ease of synthesis,17 CQDs are in a favourable position for

2. Fluorescence properties of CQDs

Chem. Soc. Rev., 2015, 44, 362--381 | 363

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of specific electronic energy bandgap for optical absorption and

Fluorescence emissions of surface defect-derived origins

The second class of the fluorescence mechanism arises from

are determined by the p-states of the sp2 sites.29 Thus, the

Tunable fluorescence emissions of CQDs

One unique property of CQDs is their tunable fluorescence

364 | Chem. Soc. Rev., 2015, 44, 362--381

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remains to be established and the requirement for surface

In addition to conventional down-conversion fluorescence

This journal is The Royal Society of Chemistry 2015

Chem Soc Rev

Top-down synthetic route

Synthetic approaches for CQDs are generally classified into two

Chem. Soc. Rev., 2015, 44, 362--381 | 365

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Bottom-up synthetic route

On the other hand, the bottom-up approaches synthesise CQDs

saccharides,49,55,56 candle soot,57 watermelon peels,58 pomelo

Surface passivation and functionalization

Surfaces of CQDs possess high sensitivity to contaminants in

366 | Chem. Soc. Rev., 2015, 44, 362--381

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Chem Soc Rev

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