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Novel properties and applications of

carbon nanodots
Cite this: Nanoscale Horiz., 2018,
3, 565
Lian Xiaoa and Handong Sun *abc

In the most recent decade, carbon dots have drawn intensive attention and triggered substantial
investigation. Carbon dots manifest superior merits, including excellent biocompatibility both in vitro and
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in vivo, resistance to photobleaching, easy surface functionalization and bio-conjugation, outstanding

colloidal stability, eco-friendly synthesis, and low cost. All of these endow them with the great potential
to replace conventional unsatisfactory fluorescent heavy metal-containing semiconductor quantum
dots or organic dyes. Even though the understanding of their photoluminescence mechanism is
still controversial, carbon dots have already exhibited many versatile applications. In this article, we
summarize and review the recent progress achieved in the field of carbon dots, and provide a
comprehensive summary and discussion on their synthesis methods and emission mechanisms. We also
present the applications of carbon dots in bioimaging, drug delivery, microfluidics, light emitting diode
Received 15th May 2018, (LED), sensing, logic gates, and chiral photonics, etc. Some unaddressed issues, challenges, and future
Accepted 16th July 2018 prospects of carbon dots are also discussed. We envision that carbon dots will eventually have great
DOI: 10.1039/c8nh00106e commercial utilization and will become a strong competitor to some currently used fluorescent
materials. It is our hope that this review will provide insights into both the fundamental research and
rsc.li/nanoscale-horizons practical applications of carbon dots.

1 Introduction
a
Division of Physics and Applied Physics, School of Physical and Mathematical Carbon dots have become a hot topic of numerous scientific
Sciences, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore.
studies since their discovery1,2 due to their obvious advantages
E-mail: [email protected]
b
Centre for Disruptive Photonic Technologies (CDPT), School of Physical and
over conventional semiconductor quantum dots whose notable
Mathematical Sciences, Nanyang Technological University, 637371, Singapore toxicity and environmental hazards are well documented.3–6
c
MajuLab, CNRS-UCA-SU-NUS-NTU International Joint Research Unit, Singapore Both in vitro and in vivo toxicity evaluation have demonstrated

Lian Xiao received his Bachelor’s Handong Sun is currently an

degree in Physics from Sichuan associate professor in the School
University, China, in 2014. He is of Physical and Mathematical
currently a year 4 PhD student in Science, Nanyang Technological
the School of Physical and Mathe- University. He received his
matical Sciences, Nanyang Technol- Bachelor’s degree in Physics from
ogical University, Singapore. His Dalian University of Technology,
research interests include nano- and his Master’s and PhD degrees
materials, optical spectroscopy, from Huazhong University of
semiconductor physics, and micro- Science and Technology, and
fluidics. Hong Kong University of Science
and Technology, respectively. He
Lian Xiao Handong Sun was elected as a Fellow of the
American Physical Society in
2016. His research interests cover optoelectronic materials and
devices, semiconductor physics, optical spectroscopy, nanomaterials,
and applications in microfluidics.

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Review Nanoscale Horizons

which will be presented in detail in Section 2. What is exciting

for carbon dots is that researchers have successfully explored
highly luminescent carbon dots with a quantum yield up to
80%,22 which is comparable to conventional semiconductor
quantum dots, and further, the emission range can be tuned
from deep UV to near IR by careful selection of the synthesis
approach and precursors.13,17,23–28
To make better use of carbon dots and to tune their optical
properties, a full understanding of carbon dots emission is
essential. Ironically, the actual emission mechanisms of carbon
dots are still controversial even though some breakthroughs have
been obtained in recent years. In Section 3, we summarize and
display the emission models proposed by different authors and
Fig. 1 Number of publications about carbon dots since 2006. Dates are also provide the key evidences for each emission mechanism.
generated from the Web of Science up to April 16, 2018; search criteria: Some of the mechanisms are mutually complementary, while
topic ‘‘carbon dots’’ or ‘‘C-dots’’ or ‘‘carbon nanodots’’ or ‘‘graphene
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some are in sharp conflict. We speculate that different emission

quantum dots’’; database: Web of Science Core collection.
mechanisms may be applied to one or more kinds of carbon dots,
but these may not be valid to all kinds of carbon dots.
that carbon dots exhibit excellent biocompatibility, which, The applications of carbon dots are presented in Section 4.
along with their photostability, chemical inertness, ease of In this review, we focus on the optical and optoelectronic
surface functional group modification, and low cost, endow applications, including bioimaging, drug delivery, microfluidic
carbon dots with vast potential scope to be applied in various applications, light emitting diodes (LEDs), sensing, especially
fields.2,7,8 The exploration of a stable, fast, low-cost synthesis for high-resolution ratiometric sensing, chemical logic gates,
approach is a prerequisite to make use of carbon dots, and and chiral photonics. Carbon dots have demonstrated good
fortunately numerous breakthroughs have been achieved over performances in all of the above applications. In the last
the past decade. Consequently, carbon dots have become the section, we provide a brief summary and discuss the challenges
center of significant research efforts to develop an alternative and future prospects of carbon dots in further exploration.
to replace the unsatisfactory traditional fluorescent materials, This article is not intended to be a comprehensive review (or a
and the publications about carbon dots have continuously complete list of the published results) in the research field of
increased since 2006, as seen in Fig. 1 (the dates are generated carbon dots, but rather aims to provide some selective helpful
from the Web of Science up to April 16, 2018, with the search insights, as chosen from our direct experience as well as the
criteria: topic ‘‘carbon dots’’ or ‘‘C-dots’’ or ‘‘carbon nanodots’’ recent literature of the subject. We hope that this review article
or ‘‘graphene quantum dots’’, database: Web of Science Core can present a clear picture of carbon dots, from their synthesis,
collection). Carbon dots synthesized from different approaches to their characterization and applications, and give valuable
share some similar features, such as less than 10 nm size, insights into both their fundamental physics and practical
bright fluorescent emission, rich hydrophilic surface groups applications. In addition, we also hope to offer some perspectives
which endow carbon dots with excellent water solubility, and and clues to further improve the optical properties and to aid the
biocompatibility. However, some contradictory behaviors, like exploration of more far-reaching applications of carbon dots.
non-photoblinking2,9 and photoblinking,10–12 pH-stable13 and
pH-dependent PL,14,15 carbon dots size-dependent13,16–18 and
size-independent PL,19,20 excitation-dependent20 and indepen- 2 Synthesis approaches
dent PL,13,21 have been reported by different research groups.
All of these attributes indicate that carbon dots represent a Since they were first discovered fortuitously by Xu et al. in
much complex system than expected. It seems that the diverse 2004,1 and later named by Sun et al. in 2006,2 researchers have
behaviors of carbon dots result from the different synthesis paid intense attention to carbon dots because of their striking
approaches, that is, different synthesis methods will result in advantages. However, a stable, economic, easy, and fast synth-
different types of carbon dots.21 Therefore it is necessary to esis method is a prerequisite to further explore the properties
provide the synthesis method when talking about carbon dots. and applications of carbon dots. Overall, carbon dots synthesis
Thus prior to the discussion about the optical properties and methods can be divided into two categories, either top down or
applications, we first present the synthesis approaches of carbon bottom up, based on the starting carbon source. Top-down
dots adopted during the past decades in Section 2 of this review. methods are realized by directly exfoliating a bulk carbon source,
After more than 10 years of efforts, numerous synthesis methods, such as graphite, graphene, or carbon fiber, into nano-scale
including several intriguing one-step approaches, have been carbon dots, followed by surface treatment. Opposite to direct
discovered by researchers. Generally, the carbon dots synthesis exfoliation, bottom-up methods synthesize carbon dots from a
methods can be divided into two categories: top down and carbon element containing small molecules, such as glucose
bottom up, and each of these contains many sub-categories, or citric acid. In this part, we review the main progress in the

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synthesis of carbon dots achieved by researchers in both top-down 2.1.2 Laser ablation/irradiation approach. Later, In 2006,2
and bottom-up approaches. To improve and tune the optical proper- Sun et al. proposed a new approach to synthesize fluorescent
ties, such as the quantum yield, emission wavelength, and photo- carbon-based nanomaterials and termed them as carbon
stability, surface passivation and hetero-atom doping are employed dots. Briefly, A Q-switched Nd:YAG laser (1064 nm, 10 Hz) was
during the carbon dots synthesis process. It is worth emphasizing utilized to ablate a carbon target fabricated by hot-pressing
that it’s not reasonable to evaluate which method is the ‘‘best’’ graphite and cement. A following acidic treatment was accom-
synthesis approach. As we discussed in Section 1, different kinds plished using 2.6 M nitric acid solution with refluxing for
of carbon dots exhibit different and even opposite properties, another 12 h. There was no detectable PL emission from the
thus we suggest that the choice of the synthesis method depends acidic treatment sample. However, once a simple molecule was
on the intended application and its requirements. linked to the surface of the dots by surface treatment, bright
luminescence could be observed from the carbon dots. The
2.1 Top-down approaches for fabricating carbon dots authors demonstrated that both diamine-terminated oligo-
2.1.1 Arc-discharge method. In 2004,1 Xu et al. utilized the meric poly(ethylene glycol) H2NCH2(CH2CH2O)nCH2CH2CH2NH2
preparative electrophoresis method to purify arc-discharged (average n B 35, PEG1500N) and poly(propionylethyleneimine-co-
single-welled carbon nanotube soot. After purification, the crude ethyleneimine) (PPEI-EI) could be used to surface passivate the
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nanotube soot was segregated into three isolated parts: long acid-treated carbon nanoparticles. In a typical surface treatment
nanotubes, short tubular materials, and a new kind of nanodots, process, the mixture of the acid-treated carbon particles and small
which were located in a fast-moving band. Surprisingly, the molecules (PEG1500N or PPEI-EI) was heated to 120 1C for 72 h. The
nanodots could emit bright light under 365 nm light excitation. resultant carbon dots had an average diameter of 5 nm and showed
Further elution separated the mixed fluorescent band into bright photoluminescence (PL) with the quantum yield reaching up
green-blue, yellow, and orange sub-emission bands. The mole- to 10% when excited by a 400 nm laser, as illustrated in Fig. 2a–c.
cular weights of these three kinds of nanodots were determined The PL spectra changed with varying the excitation wavelength,
to be 3–10 K, 10–30 K, 30–50 K NMWL (nominal molecular termed as excitation-dependent PL, as depicted in Fig. 2b and c.
weight limit) by means of Centricon filtration devices. Element Besides, the carbon dots exhibited a much more stable emission
analysis indicated that these kinds of nanodots only contained under continuous photoexcitation for several hours.
C (55.93%), H (2.65%), N (1.2%), and O (40.33%), with no heavy Later, amended approaches involving combining the laser
metal components. ablation and surface modification processes into one procedure

Fig. 2 (a) STEM imagine of PEG1500N surface-passivated carbon dots. (b) Absorption and emission spectra for different excitation wavelengths from
400 nm to 600 nm with an increase step of 20 nm. (c) Photographs following excitation by different excitation wavelengths as indicated in the figures.
(a–c) Reproduced with permission from ref. 2. Copyright 2006, American Chemical Society.

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have also been reported.7,20,29,30 A Nd:YAG pulsed laser (wave- 1 nm, as revealed by AFM, while the emission spectra were
length of 1.064 mm and power density 6.0  106 W cm2) was different for different column bands carbon dots.
used to irradiate a mixture of graphite and organic solvent, In addition to candle soot, carbon dots synthesized from the
resulting in the carbon dots synthesis and surface modification chemical exfoliation of carbon fibers were reported by Ajayan’s
being accomplished simultaneously. Besides, researchers have group.18 A mixture of concentrated H2SO4 and HNO3 was
also proposed that the emission properties of carbon dots prepared to exfoliate the carbon fiber. The carbon fiber was
could be tuned by properly choosing the organic solvent, such added to the concentrated acid followed by 2 h sonic treatment.
as, PEG2000N, diamine hydrate, diethanolamine. After that, the mixture was heated to a certain temperature for
2.1.3 Electrochemical approach. The electrochemical 24 h with vigorous stirring. The synthesized carbon dots
approach to synthesizing blue carbon dots from multi-walled exhibited a relatively narrow size distribution (diameter between
carbon nanotubes (MWCNTs) was first suggested by Ding’s 1–4 nm) with a lattice parameter of 0.242 nm. The authors also
group.31 MWCNTs, fabricated by scrolling the layered graphene demonstrated that the optical properties (absorption and PL) of
on carbon paper by chemical vapor deposition (CVD), were used the carbon dots could be tuned by simply controlling the
for the working electrode in an electrochemical cell, comprising reaction temperature to yield different sizes of carbon dots.
a Pt wire counter electrode and a Ag/AgClO4 reference electrode. Later Ye and co-workers36 also employed concentrated H2SO4
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A degassed acetonitrile solution, which included 0.1 M tetra- and HNO3 to exfoliate coal to synthesize carbon dots.
butylammonium perchlorate (TBAP), was prepared as the
supporting electrolyte solution. After a certain number of cycles 2.2 Bottom-up approaches for fabricating carbon dots
with an applied potential from 2 to 2 V at a scan rate of 2.2.1 Thermal pyrolysis approach. The one-step thermal
0.5 V s1, the colorless electrolyte solution changed to dark pyrolysis method was first discovered by Emmanuel P. Giannelis’s
brown, which indicated the formation of carbon dots. The obtained group.37 Different ammonium citrate salts have been utilized to
carbon dots were purified by evaporating the acetonitrile, synthesize carbon dots, where the citrate part provides the carbon
re-dissolving in water, and dialyzing in a cellulose ester source, while the organic ammonium part serves as the surface
membrane bag. The purified carbon dots showed a narrow size modifier. Both organophilic and hydrophilic carbon dots could be
distribution of 2.8  0.5 nm with a lattice spacing of about 3.3 Å. achieved by choosing the right surface modifier, e.g., octadecyl
When excited by a 340 nm light source, the carbon dots emitted ammonium (C18H37NH3+) citrate salt for organophilic carbon dots
bright blue light with a quantum yield of 0.064. and 2-(2-aminoethoxy)-ethanol (OHCH2CH2OCH2CH2NH3+)
Li and co-workers32 also employed an electrochemical salt for hydrophilic carbon dots. Even for both kinds of carbon
approach to synthesize carbon dots, using the graphite as both dots, the linkages between the organic corona and cores were
the anode and cathode and a current intensity in the range accomplished through covalent amide linkages formed by the
of 10–200 mA cm2. They demonstrated that the electrolyte thermal dehydration of the ammonium carboxylate moieties,
environment played an important role in the carbon dots although the sample preparation pathways for organophilic and
formation. When the electrolyte was alkaline (for example, hydrophilic carbon dots were different. Specifically, organophilic
NaOH/EtOH), carbon dots could be synthesized successfully, carbon dots were synthesized by directly calcining the pretreat-
while an acid electrolyte (for example, H2SO4/EtOH) could not ment citric acid monohydrate in air at a temperature of 300 1C
form the carbon dots. (HR)TEM analysis showed that the synthe- for 2 h with a heating rate of 10 1C min1; however, in the case of
sized carbon dots had a diameter less than 4 nm with a lattice hydrophilic carbon dots synthesis, the mixture of citric acid
spacing of around 0.32 nm. monohydrate (2 g, 9.5 mmol) and HOCH2CH2OCH2CH2NH2
In addition to graphite and carbon nanotubes, other bulk (1.3 g, 12.4 mmol) was dissolved in 10 ml water, and dried at
carbon sources, such as graphene film, carbon fiber,33–35 have 65 1C, resulting in a thick syrup. A Teflon-equipped stainless steel
also been employed to synthesize carbon dots by means of autoclave was utilized to heat the thick syrup to a temperature of
electrochemical approaches. 300 1C for 2 h. For both kinds of carbon dots, the relatively low
2.1.4 Chemical exfoliation method. Liu and co-workers19 melting point of the ammonium citrate salt guaranteed the
were the first to employ an oxidative acid to synthesize carbon uniform growth of carbon dots from the liquid phase. TEM
dots from bulk candle soot, which was first prepared from analysis showed that the organophilic carbon dots constituted
smoldering candles. They refluxed the candle soot with 5 M HNO3 mono-disperse dots of near spherical shape with an average
followed by centrifugation and neutralization. Polyacrylamide diameter of 7 nm, while the hydrophilic carbon dots had a lower
gel electrophoresis (PAGE) was also utilized to further purify mono-disperse distribution with an average diameter of 7 nm.
and separate the different components of the soot mixture. Later Emmanuel P. Giannelis’s group38 did a comprehensive
The electrophoresis results indicated that the soot mixture investigation of the carbon dots pyrolysis process. Citric acid
consisted of three kinds of species: a fast-moving fluorescent monohydrate (C6H8O7) and ethanolamine (C2H7ON) were employed
band, a slow-moving non-fluorescent band, and an agglomerated to synthesize carbon dots in different pyrolysis temperatures in
band. The fast emission band could further separate into 9 sub- the absence of solvent and under reflux in air. The authors
bands located at different positions of the column, all of them demonstrated that, under the condition of low temperature,
were eluted from gels and dialyzed against distilled water several such as pyrolysis at 180 1C for 30 min (termed as CNP180), the
times. The obtained carbon dots had similar heights of about pyrolysis resulted in carbon dots precursors, and a strong

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PL emission originating from the organic fluorophores. There 2.2.2 Hydrothermal method. Carbon dots synthesized
were several pieces of evidence that supported the molecular from a hydrothermal method were first reported in 2011.48
assumptions: (1) no carbon dot particles could be observed by Briefly, glucose and monopotassium phosphate (KH2PO4) were
either DLS or TEM, and (2) the sample showed excitation- mixed with a certain molar ratio and dissolved in DI water.
independent PL with a remarkable quantum yield of 50%. Nitrogen was employed to remove the oxygen dissolved in
More specifically, the authors suggested38 the amide-related water. Then, the sealed Teflon-lined autoclave chamber was
molecules contributed to the emission of carbon dots molecular transferred to an oven and the mixture allowed to react
precursors, which was verified by FTIR, XPS, and 1H & 13C NMR. at 200 1C for 12 h. After that, the mixture was centrifuged at
To further confirm the amide-related functional groups, the 9000 rpm to separate the precipitate, whereupon the upper
amide was also synthesized by an alternative approach using supernatant was gathered and freeze-dried, followed by
citric acid monohydrate (C6H8O7) and ethanolamine (C2H7ON) re-dissolving the carbon dots into ethanol to form a suspension.
as the raw materials, and the results showed that the amide and After 2 h standing, the salt precipitated from the solution and
the carbon dots precursors exhibited similar optical behaviors, was removed by a PTFE syringe filter with a pore size of 1 mm.
which validated the mechanism. Further purification was finished by using a Spectra/Por dialysis
Higher temperature (e.g., at 230 1C for 30 min, CNP230) membrane whose cut-off molecular weight was 100 g mol1.
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pyrolysis triggered the carbon dots formation, which was verified by The advantage of this approach is that the carbon dots formation
TEM analysis, whereupon the carbon dots showed a spherical and surface treatment are accomplished simultaneously. Further-
morphology with an average size of 19 nm. The authors more, the PL properties of carbon dots could be tuned by altering the
claimed38 that the carbon dots formation was the result of extensive concentration of KH2PO4.48 When the molar ratio of glucose/KH2PO4
cross-linking reactions and the appearance of interchain imide was 1/36, the synthesized carbon dots emitted blue light when
bonds, as substantiated by the FTIR spectrum. Element analysis excited by UV light, while a molar ratio of 1/26 of glucose/
showed that the hydrogen component of CNP230 (44.85% C, 5.75% KH2PO4 resulted in green emission. TEM analysis indicated
H, 10.85% N) decreased compared to CNP180 (41% C, 7.8% H, that the average diameter was 1.83 nm for the 1/36 molar ratio
11.7% N). The PL quantum yield of CNP230 decreased to 15%, blue and 3.38 nm for the 1/26 molar ratio green carbon dots.
while the excitation-dependent PL started to appear. The observation of CQC by FTIR spectroscopy in both carbon
Increasing the temperature to 300 1C resulted in a darkening dots implied the occurrence of carbonization48 during the hydro-
of the sample and synthesized carbon dots with an average size of thermal process. In addition, the surface passivation occurred
8 nm. TGA-MA analysis uncovered38 that some CO2 emanated by means of the oxidation of –OH groups.
from the mixture during the pyrolysis, which contributed to the In addition to glucose, natural bioresources,14 e.g., orange
decrease in size of the carbon dots. Element analysis exhibited an juice, have also been utilized to synthesize carbon dots by
increased C component (50.5% C, 3.7% H, and 13.1% N), which means of a hydrothermal treatment at a relatively low tempera-
indicated the further carbonization. Different from CNP180 and ture of about 150 1C. The authors14 proposed that the carbon
CNP230, CNP300 displayed distinct excitation-dependent PL with dots emission was the result of the hydrothermal carbonization
the quantum yield of about 4%. Further increasing the pyrolysis of the organic components in the orange juice, such as sucrose,
temperature to 400 1C resulted in clusters and nonuniform glucose, fructose, and citric acid. TEM images showed that the
particles with the size reaching to several hundred nanometers, carbon dots had a spherical morphology with a narrow diameter
caused by the aggregation. Even though the resultant carbon dots distribution between 1.5 and 4.5 nm with a lattice spacing of
could still emit light, the intensity was very low. 0.18 nm. XPS and FTIR analysis disclosed the existence of many
Later, Fu Wang et al.39 synthesized carbon dots by means hydrophilic functional groups, such as –OH, –COOH, which
of pyrolyzing the citric acid in molten LiNO3 with argon as the endowed the carbon dots with excellent solubility in water. The
protecting gas. Compared to solid LiNO3, the molted alkali metal intriguing features of this approach is that neither post-surface-
nitrates could endow the nitrate anion with the ability to form an passivation treatment nor expensive chemicals are needed; thus
anion O2 or an oxygen atom O, which could serve as the oxidizing this work triggered continuous exploration about bioresources-
condition. Also, the surface passivation could strongly improve based carbon dots synthesis in a one-step manner.49,50
the emission intensity. In a typical experiment, a mixture of Later on, Pin-Che Hsu and co-workers51 proposed that
carbon dots and PEG1500N were dissolved into a mixture of water organic molecules containing amino and carboxylic acid groups,
and toluene. The surface passivation was started by separating the such as 2-amino-2-hydroxymethyl-propane-1,3-diol (TRIS),
water from the mixture through a water segregator, and the ethylenediaminetetraacetic acid (EDTA), and glycine, could
reaction finished when the water was totally removed from benefit the carbon dots formation. They claimed that carbon
the mixture. The passivated carbon dots had an increased diameter dots formation underwent four steps: dehydration, polymeriza-
of about 5–8 nm with the PL quantum efficiency reaching 10%. tion, carbonization, and passivation. Hydrogen bonds played
Beside the citric acid salt, other small molecules, such as a key role during the molecular assembly, where heating leads
ethylenediamine-tetraacetic acid salts, synthetic polymer, e.g., to polymerization occurring, resulting in a single burst
epoxy-enriched polystyrene (PS), and natural materials, such as of nucleation. Finally, the solutes reached to the surface of
hair, green tea, konjac flour, paprika,40–47 have also been employed the nuclei through diffusion, resulting in the growth of
to synthesize carbon dots by means of a thermal pyrolysis approach. carbon dots.

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Until now, by choosing proper organic molecules and To further facilitate the polymerization and dehydrogena-
adjusting the reaction environment (such as alkaline or acidic) tion of the resols, calcination of these polymer/F127/silica
with controlled surface function groups by means of hydro- structure was performed at a temperature of 900 1C for 2 h
thermal method, it is possible to synthesize carbon dots with with Ar as the protection gas. In addition, the surfactant F127
emission wavelength covering the whole visible range.17,48,52–55 was also totally released during the calcination process. After
2.2.3 Microwave heating method. The intriguing microwave- that, the carbon dots were released from the silica sphere by
assisted carbon dots synthesis approach was discovered and etching with NaOH solution. The surface passivation was still
first demonstrated by Yang’s group.56 This method possesses crucial for achieving bright photoluminescence. The post sur-
numerous merits, such as less time consumption, homogeneous face treatment was carried out by heating the mixture of carbon
heating, low cost. Briefly, poly(ethylene glycol) (PEG-200) and dots solution and diamine-terminated oligomeric poly(ethylene
saccharide (glucose, fructose, etc.) were dissolved in DI water to glycol), H2NCH2(CH2CH2O)nCH2CH2CH2NH2 (PEG1500N) at 120 1C
form a transparent mixture. A microwave oven was utilized to for 72 h. Element analysis exposed that the carbon dots contained
heat the solution at a power of 500 W for 2–10 min. The carbon C 64.65 wt%, H 7.67 wt%, N 1.13 wt%, and O (calculated)
dots were formed once the transparent solution was changed to 26.55 wt%. The average size of carbon dots was in the range of
a dark brown mixture. The carbon dots exhibited different average 1.5–2.5 nm. The absence of a discernible lattice structure indicated
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diameter sizes as the reaction time varied, e.g. 2.57  0.45 nm that these kinds of carbon dots were amorphous. The carbon
for 5 min heating, 3.65  0.6 nm for 10 min heating. X-Ray dots could emit bright PL with a quantum yield 14.7% when
photoelectron spectroscopy (XPS) unveiled that the main com- excited by a 360 nm light source.
ponents of the carbon dots were carbon and oxygen, and the In addition to silica, NaY zeolite have also been employed as
existence of the rich hydrophilic function groups endowed the a support to synthesize carbon dots.63,64 It was demonstrated that
carbon dots with good water solubility, allowing the carbon the anchor-assisted carbon dots showed similar PL behaviors with
dots to be used for the bioapplications. The PL quantum yield the non-support-approach synthesized carbon dots.
of the sample displayed an excitation-dependent behavior 2.2.5 MOF template-based approach. To achieve uniform,
varying from 6.3% to 3.1%. ultrasmall carbon dots, Zhi-Gang Gu and co-workers65 made
This novel approach opened a new avenue to synthesize use of the well-defined pore size of metal–organic frameworks
carbon dots,57 e.g., Sourov et al.58 and Qu et al.59 separately (MOFs) as a template to synthesize carbon dots. One of the
fabricated green emission carbon dots with a relatively high motivations of this approach was that MOFs possess rich
quantum yield, while blue emission carbon dots with a high isoreticulars, whose pore size vary from 1 nm to 10 nm and
quantum yield of 44.9% (excited by 360 nm) were reported by which offer the opportunity to synthesize carbon dots with a
Jiang et al.60 Furthermore, Tang et al.26 and Sun et al.61 even controlled size and morphology. The MOF powder was synthe-
achieved deep UV and near IR emission from carbon dots by sized using a solvothermal method. Glucose (carbon source)
using a microwave approach. was loaded inside the MOF pore by easily immersing the MOF
2.2.4 Anchor/support-based approach. Silica spheres were power into a mixture of glucose and EtOH/H2O (9 : 1). The
employed by Liu’s group as the carrier to synthesize carbon different weight of HKUST-1 MOF samples before (1.00 g) and
dots.62 The silica spheres could supply anchors which accelerated after (1.13 g) loading confirmed the successful loading of
the polymerization of the carbon source. In addition, the glucose. Glucose started to decompose when the loaded MOF power
aggregation of carbon dots was also suppressed by the spheres was heated to 200 1C, while the MOF template was still stable even
during high-temperature pyrolysis, which further benefited when temperature was as high as 280 1C, which was confirmed by
carbon dots formation. Briefly, the silica surface was first the thermogravimetric (TG) analysis. PXRD analysis demonstrated
treated by an amphiphilic triblock copolymer F127 (EO106PO70EO106, that the structure of the MOF was not destroyed during calcination.
Mw = 12 600; EO = ethylene oxide, PO = propylene oxide). The The prominent color changed from blue to green, which signified
surface treatment of silica by F127 surfactant was the prerequi- the carbon dots formation, while the considerable decrease in N2
site to synthesize carbon dots. The surfactant F127 triggered the adsorption ability from 130 cm3 g1 for pristine MOF to 5 cm3 g1
micellization-like self-assembly to occur on the sphere surface. for the calcinated MOF indicated the successful filling of the
After interaction with water, the copolymer chains of F127 were MOF pore by carbon dots.
extended on the surface of the sphere, resulting in a core–shell To release the carbon dots from the MOF temperate,
silica-F127 surfactant structure. The opened F127 shell contrib- aqueous KOH solution was utilized by the authors65 to dissolve
uted to the carbon source entering into the shell layer, which the template’ the whole procedure is illustrated in Fig. 3. After
benefited the molecular loading and polymerization. More spe- purification, the carbon dots exhibited a rather narrow size
cifically, the hydrophilic part of F127 (also called PEO blocks) distribution with an average diameter of 1.5 nm. Actually, this
offered more anchors for resol molecules and for strong hydro- size was close to the large pore size inside the HKUST-1 MOF
gen bond interaction, which contributed to the polymerization (HKUST-1 contains 3 kinds of pores: 1.35 nm, 1.1 nm, 0.5 nm);
of resol molecules, resulting in the construction of the polymer/ this was a result of the preference to form carbon dots nuclei in
F127 surfactant/silica sphere composites. After the surface treat- the largest pores, as proposed by the authors.65 By choosing
ment of silica, prepared resols were added as the carbon source different MOFs as templates with different pore sizes, the
to the suspension for the polymerization. authors synthesized different sizes of carbon dots, such as

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carbon dots, where a different color emission originated

from the different size effect. All of the different emission
carbon dots were synthesized by a hydrothermal method. Here,
hydrothermal treatment of a mixture of CA (citric acid) and
2,3-diaminonaphthalene ethanol solution for 4 h and 9 h resulted
in blue and green emission carbon dots, while hydrothermal
treatment of CA and 1,5-diaminonaphthalene ethanol solution
for 4 h and 9 h formed yellow and orange carbon dots, and red
emission carbon dots could be achieved by hydrothermal treat-
ment of a mixture of CA, 1,5-diaminonaphthalene and concen-
trated sulfuric acid. The wavelength of the absorption peaks of
the blue (B), green (G), yellow (Y), orange (O), and red (R) carbon
dots were located at 350 nm, 390 nm, 415 nm, 480 nm, and
500 nm respectively as illustrated in Fig. 4a, which displays a
continuous increase. The corresponding PL peaks were located at
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430 nm, 513 nm, 535 nm, 565 nm, and 604 nm for B, G, Y, O, and R,
respectively, as seen in Fig. 4b. Different from the previous reported
carbon dots, all of the carbon dots here exhibited excitation-
independent PL, and the PLE peaks coinciding with the absorption
peaks, both of which indicated that these carbon dots emission
Fig. 3 Illustration of carbon dots prepared by using the MOF pores as originated from the band emission. TEM analysis showed that the
templates. Reproduced with permission from ref. 65. Copyright 2017, size of the carbons dots were 1.95 nm (B-), 2.41 nm (G-), 3.78 nm (Y-),
Wiley-VCH.
4.90 nm (O-), and 6.68 nm (R-), respectively, and in addition, the
high degree of the crystallinity features for all the carbon dots were
HKUST-1 MOF for 1.5 nm carbon dots with the largest pore size exposed by HRTEM. Thus, the authors claimed13 that the carbon
of 1.35 nm, ZIF-8 MOF for 2.0 nm carbon dots with the largest dots emission originated from the band edge emission, and that the
pore size of 1.9 nm, and MIL-101 MOF for 3.2 nm carbon dots different color emission was the result of different effective band
with the largest pore size 3.4 nm. However, carbon dots gaps: 3.02 eV (B-), 2.61 eV (G-), 2.49 eV (Y-), 2.30 eV (O-) and 2.12 eV
synthesized from the same method without the MOF template (R-), where the band gaps were obtained from the absorption peaks
showed a nonregular size distribution with an average diameter (see Fig. 4d). These band gap emission results were also confirmed
of 4.5 nm. All of these results suggested the size and morphol- by UPS spectroscopy, which measured the HOMO and HOMO
ogy controllability offered by the MOF template. The PL of the values of the carbon dots, as presented in Fig. 4c. Combined with
carbon dots showed a red-shift as the size increased from the TEM analysis, the authors claimed13 that the different band gaps
1.5 nm to 4.5 nm when excited by UV light. resulted from the different quantum confinement/size effects. All of
Due to the intriguing controllability of the size and the carbon dots exhibited pH-stable (pH value varying from 2 to 13)
morphology,66,67 other templates, such as a mixed soft template emission peaks, which, combined with the monoexponential decay
(copolymer Pluronic P123) and hard template (ordered meso- of PL lifetimes, further confirmed that the carbon dots’ emission
porous silica (OMS) SBA-15), were also employed by Yang et al.68 originated from the band emission, instead of surface states emis-
to develop carbon dots with a uniform morphology. sion. In addition, all the excitation-independent emission carbon
The above-mentioned approaches are the most general dots possessed relatively high quantum yield: 75% (B), 73% (G),
bottom-up methods widely utilized by researchers to synthesize 58% (Y), 53% (O), and 12% (R).
carbon dots. The discovery of versatile bottom-up approaches, A quantum-confinement-induced PL spectral shift of carbon
especially fast and simple one-step synthesis methods, ensure the dots was also claimed by several other groups. Jiang et al.17
prerequisite of pushing carbon dots into practical applications. synthesized 6.0 nm, 8.2 nm, and 10.0 nm sized carbon dots by a
Furthermore, in addition to the general bottom-up methods, hydrothermal treatment method, which showed blue, green,
researchers also proposed some unusual approaches;69,70 for and red emissions, respectively (Fig. 4e–g). In addition to the
example, Liu et al.70 demonstrated a pathway using a catalase hydrothermal method, carbon dots synthesized by other
enzyme to decompose graphitic carbon nitride to synthesize approaches16,17 can also exhibit size-dependent PL. Li et al.32
carbon dots at room temperature. and Peng et al.18 separately synthesized carbon dots by utilizing
the alkali-assisted electrochemical and chemical exfoliation,
and both of them observed a size-dependent PL spectral shift
3 Emission mechanism from their carbon dots, as can be seen in Fig. 4h and i.

3.1 Band gap emission and quantum confinement effect 3.2 Surface states emission
By properly controlling the reaction precursor and time, Yuan To explore the emission mechanism of carbon dots, the purifica-
et al.13 claimed to be able to synthesize band gap edge emission tion of carbon dots is a prerequisite. Ding et al.25 employed the

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Fig. 4 (a and b) The absorption and PL spectra of B-, G-, Y-, O-, R- emission carbon dots. (c) HOMO and LUMO energy for different sizes of carbon dots,
obtained from UPS spectroscopy. (d) The corresponding absorption and emission peaks for different sizes of carbon dots. (e–g) 6 nm, 8.2 nm, and 10 nm
sized carbon dots (synthesized by Jiang et al.) emitted blue, green, and red light respectively, excitation wavelength 365 nm. (h and i) Relationship
between carbon dots size and band gap value for Li et al.’s sample and Peng et al.’s samples, respectively. (a–d) Reproduced with permission from ref. 13.
Copyright 2016, Wiley-VCH. (e–g) Reproduced with permission from ref. 17. Copyright 2015, Wiley-VCH. (h) Reproduced with permission from ref. 32.
Copyright 2010, Wiley-VCH. (i) Reproduced with permission from ref. 18. Copyright 2012, American Chemical Society.

silica column chromatography technique to purify carbon The increased degree of oxidation was also verified by XPS,
dots synthesized by the hydrothermal treatment of urea and where both the component of the carboxyl groups (represented
p-phenylenediamine at 160 1C for 10 h. The purified carbon by the intensity of the 289.0 eV signal) and the O element
dots emitted blue, green, yellow, and red light, respectively, continuously increased from blue to red emission carbon dots.
with these labeled as A, B, C, and D in Fig. 5. The UV-visible Based on the theory proposed by Chen et al.71 that the
absorption spectra of the purified carbon dots displayed dis- COOH groups on the sp2-hybridized carbons will generate
tinct absorption peaks in the longer wavelength region located local distortions, leading to a decrease of the energy gap, the
at 383, 410, 488, and 528 nm respectively, and the PLE spectra authors25 recommended the following emission mechanism:
of each carbon dot samples also exhibited only one peak close the emissive center is located at the surface of the carbon dots,
to the corresponding absorption bands. Different from the mainly constituted by the conjugated carbon atoms and the
ensemble carbon dots, which presented excitation-dependent bonded oxygen atoms; thus the energy difference between the
PL, the purified carbon dots disclosed an excitation-independent HOMO and LUMO of the carbon dots is intensely related to
PL behavior, as can be seen in Fig. 5a–d. Furthermore, time- the degree of oxidation. More specifically, the increased oxida-
resolved spectroscopy showed that all the carbon dots samples tion or O component leads to the decreased band gap, so the
underwent an analogous monoexponential decay process with red-shift of the PL of carbon dots originates from the increased
a lifetime of about 9 ns. All of these suggested that the purified surface oxidation, as represented in Fig. 5e. The PL spectra
different carbon dots samples manifested a uniformity in their of red emission carbon dots exhibiting a red-shift in acidic
optical properties, while (HR) TEM analysis unveiled that all the conditions also support the surface states emission. The
carbon dots samples also showed a similar size distribution authors attributed25 the pH-triggered PL intensity decrease
with an average diameter of 2.6 nm. In addition to the size, and peak shift to the protonation–deprotonation-induced surface-
the lattice constant of all the carbon dots also showed the charge modification.
same values of about 0.21 nm, as can be seen in Fig. 5a–d in the The mechanism of surface states emission was also adapted
lower parts; thus it became clear that the different color by Wang et al.72 to interpret the carbon dots emission in their
emission of carbon dots did not originate from the size effect samples. They even assigned the surface states emission to the
or quantum confinement. common origin of green light emission. They employed three
FTIR spectroscopy analysis signified that, as the carbon dots kinds of carbon dots to explore the green emission of carbon
emission changed from blue to red (sample A to sample D), the dots, namely carbon dots synthesized by: the electrochemical
degree of the oxidation continued to increase, which was treatment of a graphite rod, the microwave heating of citric acid
substantiated by the enhanced COOH bond signal located at and urea, and the hydrothermal treatment of graphene oxide
1759 cm1. Besides, compared to the blue and green carbon DMF solution. The three kinds of carbon dots displayed similar
dots, the yellow and red carbon dots appeared to hold a green emission spectra when excited by 400 nm, even though
more broad O–H band distribution, which suggested a higher the absorption spectra were different. By combining transient-
polarity, consistent with the column chromatography results. absorption and time-resolved spectroscopy, the authors suggested72

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Fig. 5 (a–d) Photographs under UV light, absorption and PL spectra, and the size distribution for blue, green, yellow, and red emission carbon dots,
respectively. All the purified carbon dots exhibited excitation-independent PL and showed a similar size distribution with an average diameter of 2.6 nm.
(e) Model for the tunable PL of carbon dots. The band gap decreased with the increasing degrees of surface oxidation, resulting in a red-shift of
carbon dots emission. (f) Wang et al.72 suggested that the green emission of carbon dots originated from hydroxyl and carboxyl surface functional groups.
(g) Pan et al. proposed that the blue emission of carbon dots originated from surface zigzag sites, which possess a carbene-like triplet ground state,
denoted as s1p1. (a–g) Reproduced with permission from ref. 25. Copyright 2016, American Chemical Society. (f) Reproduced with permission from
ref. 72. Copyright 2014, American Chemical Society. (g) Reproduced with permission from ref. 52. Copyright 2010, Wiley-VCH.

that the photoexcited hot carriers were first located at the hydroxyl group and carboxyl group, were the main functional
carbon core, followed by leaking fast to the emissive center groups for both the before and after surface-reduced carbon
and non-radiative traps. In other words, the graphitic carbon dots; thus they attributed72 the carbon dots green emission to
core did not contribute to the carbon dot emission but played a the hydroxyl and carboxyl surface functional groups, whereby
role as a temporary hot carrier reservoir. To identity the emis- the different quantity of carboxyl surface functional groups
sion center on the surface, NaBH4 was utilized to achieve before and after the surface reduction resulted in the different
the surface chemical reduction for all three kinds of carbon green PL spectra of the carbon dots. In addition, the authors
dots, which resulted in different emission spectra. FTIR spectra also claimed72 that the hybridization/interaction between the
analysis implied that the CQO functional groups, especially the carbon core structure and CQO functional groups was a

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prerequisite for the carbon dots emission as the pure CQO

could not contribute to the green emission.
The surface states emission origin of the carbon dots has
been accepted by many researchers,12,20,24,26,52,73–75 although
the actual emission fine structures on the surfaces of carbon
dots are still controversial; e.g., Pan et al.52 argued that the blue
carbon dots emission originated from the surface zigzag
sites possessing a carbene-like triplet ground state (Fig. 5g),
denoted as s1p1.

3.3 Molecular fluorophores and carbogenic core

Emmanuel P. Giannelis’s group38 proposed that, for the ther-
mal pyrolysis approach for obtaining synthesized carbon dots,
the emission mechanism was related to the pyrolysis tempera-
ture. Briefly speaking, a mixture of citric acid monohydrate
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(C6H8O7) and ethanolamine (C2H7ON) with a molar ratio of 1 : 3

was heated at a certain temperature for 30 min under reflux in
air. The authors propounded that when the pyrolysis tempera-
ture was low (e.g., 180 1C), it could not form carbon dots,
but instead formed carbon dots precursors. The precursor
contained some organic molecular fluorophores, which con-
tributed to the emission, with a PL quantum efficiency of 50%.
The claim of the molecular fluorophore emission was based on
the following experimental observations: (1) no carbon dots
Fig. 6 (a) During pyrolysis, the molecular fluorophores (blue groups) were
particles were observed by either DLS or TEM. (2) The sample
expended to generate a carbogenic core (black sphere), as seen in the
showed excitation-independent PL. To further identify the mole- upper illustration. So as the temperature increased, the PL intensity
cular structure, the authors employed38 FTIR, XPS, 1H and 13C corresponding to the carbon core (bold black line, lower part) increased
NMR spectroscopy to study the chemical bond of the carbon dots at the cost of the molecular fluorophores (blue line), along with
precursor. The results suggested that the amide-related fluoro- the decrease in the precursor emission (bold blue line, lower part).
Reproduced with permission from ref. 38. Copyright 2012, American
phore molecules were accountable for the precursor emission.
Chemical Society. (b) When the hydrothermal reaction time was short
Moreover, amide synthesized by an alternative approach using (e.g., less than 30 min), the emission center was mainly molecular fluoro-
citric acid monohydrate (C6H8O7) and ethanolamine (C2H7ON) as phores, e.g., 2-pyridone derivatives, while as the reaction time increased,
the raw materials demonstrated similar optical behaviors to the the carbon core, which contained an aromatic domain, appeared and
carbon dots precursor, which further validated the mechanism. played a more important role for carbon dots emission. Reproduced with
permission from ref. 76. Copyright 2017, American Chemical Society.
Increasing the pyrolysis temperature to 230 1C resulted in
the PL quantum yield decreasing to 15% and the appearance of
excitation-dependent PL. Further increasing the temperature to model to interpret the carbon dots emission (Fig. 6b). When the
300 1C or even 400 1C also resulted in a different PL quantum hydrothermal reaction time was short (e.g., less than 30 min),
yield. Element analysis showed that the carbon component the emission center was mainly molecular fluorophores, e.g.,
continued to increase with a concomitant decrease in the hydrogen 2-pyridone derivatives, while as the reaction time increased, the
component. Thus the authors claimed38 that the carbon dots carbon core, which contained an aromatic domain, appeared
underwent further carbonization as the temperature increased, and played a more important role for carbon dots emission.
which generated carbogenic cores at the cost of the carbon dots
precursor or molecular fluorophores. Both the carbon core and
amide-containing molecular fluorophores could contribute to 3.4 Polycyclic aromatic hydrocarbon molecular emission
the light emission. This model is illustrated in Fig. 6a.38 When Following the report on molecular emission,38 Alexander’s
the temperature was low, the emission was from molecular group9 proposed the polycyclic aromatic hydrocarbon fluorescent
fluorophores, while the carbogenic cores became the main molecular emission. The carbon dots utilized in the experiment
emission mechanism when the temperature was higher (e.g., were synthesized by the hydrothermal treatment of citric acid and
400 1C). Both molecular fluorophores and carbogenic cores ethylenediamine, and showed a diameter between 2 and 5 nm.
contributed to the carbon dots emission when the pyrolysis The authors claimed that the carbon dots were a kind of organic
temperature was moderate. molecular nano-crystal based on the following evidence: (1) XPS
Different from the high-temperature pyrolysis method, Ehrat spectroscopy indicated that there existed sp2 (e.g., CQO bond)
et al.76 synthesized carbon dots from citric acid and ethylene- and sp3 (e.g. C–C bond) hybrid bonds. (2) C 1s XPS spectra
diamine by means of a hydrothermal treatment. However, they showed a dramatic change after treatment by Ar-ion sputtering.
proposed a similar molecular fluorophores and carbogenic core Specifically, the authors declared that the carbon dots contained

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Fig. 7 (a and b) Absorption and normalized PL spectra of anthracene (light blue), pyrene (dark blue), and perylene (green) in a PMMA matrix
(concentration: 0.01 mol%) and CDs aqueous solution (black dashed line). (c) Absorption spectra of a PMMA film containing three PAHs (blue) (molecular
ratio: anthracene/pyrene/perylene/PMMA 10 : 10 : 1 : 20) and CDs aqueous solution (black dashed line), (d) PL spectra of the film stimulated by different
wavelengths, CD PL spectrum (black dashed line) also given for reference. (a–d) Reproduced with permission from ref. 9. Copyright 2015, American
Chemical Society.

many sp2 carbon domains embedded in a sp3 hybridized (e.g., perylene), resulting in the longer wavelength emission.
carbon matrix. Single particle measurements on the carbon Whereas, when the excitation wavelength was greater than
dots still exhibited excitation-dependent PL, indicating that 400 nm, both kinds of PAHs (large and small band gap PAHs)
there existed multi-chromophores in one carbon dot. As a could be exited directly, resulting in a red-shift of the carbon
result, the authors employed9 three basic polycyclic aromatic dots emission. Continuously increasing the excitation wave-
hydrocarbons (PAHs), namely anthracene (3 rings), pyrene length led to the small band gap PAHs absorption increasing
(4 rings), and perylene (5 rings), to mimic the emission nano- and the large PAHs band gap decreasing, contributing to the PL
domain, with poly(methyl methacrylate) (PMMA) chosen as the spectra of carbon dots showing a continual red-shift. Finally,
sp3 hybridized matrix. The authors stated that they chose these the authors also stated9 that there most likely existed other
PAHs because: (1) the absorption and PL spectra of these PAHs PAHs that were involved in the carbon dots optical process in
overlapped with those of the carbon dots, see Fig. 7a and b and addition to the above-mentioned three PAHs.
(2) their structures were relatively simple. After optimization,
the fixed molecular ratio of 10 : 10 : 1 : 20 for anthracene/pyrene/ 3.5 Slowed solvent relaxation or solvatochromic shift
perylene/PMMA was utilized to mimic the carbon dots. The Apart from the electronic structure of the carbon dots itself, the
results are reproduced in Fig. 7c and d, where it can be seen effect of the surrounding solvent molecular environment of the
that the absorption spectra of the PAH films and carbon dots carbon dots was also considered by Khan et al.,77 as illustrated
displayed a similar shape, A red-shift was observed for the in Fig. 8a. Different from the solid sample, the carbon dots
PL spectra when excited at 340 nm, while the PL line shape aqueous solution has two kinds of decay processes after photo-
and width were similar. Increasing the excitation wavelength excitation (time scale of about 1015 s) occurring simultaneously:
resulted in the PL spectra changing, but under the conditions (1) hot carriers (e.g., elections, holes) vibrational relaxation,
of 420 nm, 440 nm and 480 nm excitation, the PAH films PL which results in the well-known Stokes red-shift, and (2) solvent
spectra matched very well with the carbon dots emission. Based relaxation or dipolar reorganization, which takes place at the
on this model, the authors9 gave the following picture: when band edge, leading to a further red-shift of the emission spectra,
excited by short wavelengths (o400 nm), the PAHs that have commonly termed as the solvatochromic shift.77 According to
the largest bandgap (e.g., anthracene and pyrene) were mainly the Lippert–Mataga theory,78,79 a greater polarity of solvent will
excited (the authors claimed that the smaller band gap PAHs, lead to a larger red-shift of the emission spectra. The authors77
such as perylene, did not absorb strongly at shorter wave- assumed that the hot carrier variation time was much less than
lengths), and could emit light directly contributing to the main the fluorescent lifetimetf, thus only the solvent relaxation effect
peak emission, or transfer energy to the smaller bandgap PAHs (solvent relaxation lifetime: tr) was considered. When tf c tr,

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Fig. 8 (a) Illustrating solvent relaxation. (Fluorescent lifetime tf, solvent relaxation lifetime: tr). (b–e) Function of solvent dipole moment. (b and c) Time-
integrated PL spectra and time-resolved PL spectra as a function of time of the carbon dots in water. (d and e) Time-integrated PL spectra and time-
resolved PL spectra as a function of time of the carbon dots in dimethylformamide (DMF). The red arrow indicated that as the time increased, the
emission spectra red-shifted. The wavelength migration during the lifetime was 40 nm for water, while it reached to 100 nm for DMF. (f) Solvent-
dependent spectral shift. (g) Recombination of the electrons located at the surface with the valence band holes in the carbon dots crystalline core
contributing to the carbon dots emission. (a–e) Reproduced with permission from ref. 77. Copyright 2015, American Chemical Society. (f and g)
Reproduced with permission from ref. 82. Copyright 2016, American Chemical Society.

which means fast solvent relaxation, the solvent relaxation is spectra will red-shift as time increases, and (2) the time-
fully finished before the light emission, resulting in the solvato- integrated PL spectra will red-shift as the excitation wavelength
chromic shift being red-shifted, also called homogeneous increases. More specifically, the center of mass of the time-
broadening; when tf { tr, which is the case in a much slower integrated spectra caused by the solvent relaxation is determined
solvent relaxation, there is no solvent relaxation effect during by the following equation:81 u = ut=N  (ut=0  ut=N)tr/(tf + tr),
the PL; while when the fluorescent lifetime and solvent relaxa- where ut=N is the PL peak when the time is long enough,
tion time are the same order of magnitude e.g., tf D tr, a set of and ut=0 represents the instant that the PL occurs. It is obvious
sub-states will be formed, where all of the sub-states can that u = ut=N for tf c tr, u = ut=0 for tf { tr, and in both two
contribute to the emission maximum of the carbon dots. This cases, the emission spectra are independent on the detection
condition will lead to a broadened band emission, called time. Only when the two time constants are of the same order
inhomogeneous broadening. The temperature, solvent dipole do the time-dependent emission spectra appear.
moment, and fluorophore dipole moment all can affect The carbon dots employed by the authors77 were synthesized
by means of a microwave-assisted method. They synthesized
the inhomogeneous broadening, which is governed by the
3 different carbon dots from different starting materials (carbon
following equation:80 du ¼ dm a2 ðkTÞ1=2 , where a is the Onsagar dots 1 from chitosan and PEG, carbon dots 2 from adenine
sphere radius. Considering the dynamics of the relative slow sulfate, carbon dots 3 from sodium citrate and sodium
solvent relaxation, e.g., tf D tr, process, the initial energy sates thiosulfate, carbon dots 4 from potato-dextrose agar) but all
will be migrated to lower energy states during the PL lifetime, exhibited similar behaviors, thus the authors carried out the
which results in two effects: (1) the time-resolved emission analysis by using carbon dots 1 as a representative sample.

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Further purification of carbon dots 1 was achieved by column to the surface functional groups of carbon dots. Observation of
chromatography, which resulted in two kinds of carbon dots the solvent effect being more efficient for excited sates than
with different polarity: lower polarity carbon dots, which pre- ground states combined with the fact that the amide and
sented blue light emission, and the higher polarity carbon dots, carboxylic surface groups are assumed not to undergo any
which showed longer wavelength emission. Water and dimethyl- transitions at the 2–3 eV energy range have guided researchers
formamide (DMF), which have different dipole moments, were to propose that the carbon dots emission is a result of the
adopted by the authors77 to dissolve the carbon dots to explore the recombination of the electrons located at the surface with the
solvent polar effect. Both the water and DMF carbon dots solu- valence band holes in the carbon dots crystalline core,82 as
tions demonstrated time-integrated excitation-dependent PL and illustrated in Fig. 8f and g. The inhomogeneous broadening of
time-resolved PL spectra migration, as described in Fig. 8b–e. The the PL spectra is consider a the result of the size distribution,
results indicated that the solvent relaxation time was the same specifically, the size distribution affects the core band gap,
order as the PL lifetime, and the excitation-dependent PL was the resulting in the different efficient ‘‘energy band gap’’ between
result of solvent relaxation. Compared to water, DMF has a higher the valence band and the surface energy states.
dipole moment, which led to more populated sub-states, resulting
in the larger time-resolved emission spectra migration, reaching 3.6 Self-trapped exciton emission
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100 nm (see Fig. 8e) (but only 40 nm emission migration for the The PL spectra of carbon dots synthesized by the microwave
carbon dots aqueous solution). heating of glucose and urea manifested two distinct features:84
The two kinds of carbon dots purified from column (1) when exited by 442 nm, the emission wavelength started
chromatography also displayed different time-resolved emis- nearly from the excitation wavelength 450 nm with a broadened
sion spectra migration due to the different polarity properties, emission spectra over 1 eV, and (2) the emission intensities of
which was consistent with the author’s model.77 The less the whole spectra were the same as the magnitude, which was
oxidized and polar fraction carbon dots demonstrated a lower contrary to band edge emission, where the majority of the
or no time-resolved emission spectra red-shift, which could be emission intensity was located at the band edge. Based on these
interpreted by the faster photon emission before significant observations, it’s reasonable to speculate that the carbon dots
relaxation occurs. Whereas, the highly oxidized and high polarity emission originates from the localized emission. To verify this
carbon dots fractions were considered to hold a higher lifetime assumption, Xiao et al.84 employed polarization spectroscopy
value and showed clear time-resolved PL spectra migration, as for a comprehensive investigation and uncovered the emission
the high polarity carbon dots sustained significant solvent mechanism of carbon dots. Polarization spectroscopy can provide
relaxation during the PL lifetime, which resulted in a population information on the energy and momentum relaxation dynamics,
of the sub-states, contributing to the red-shift edge effect and which are closely related to the electronic structure and emission
time-resolved spectra migration. mechanism.85,86 Linear polarized light will align the momentum
Time-resolved anisotropic analysis estimated77 the rotational of photogenerated hot carriers (hot electrons and holes), with the
time of the dipole in the carbon dots to be in the range of 0.61 to corresponding principles ruled by the transition density matrix
1.51 ns (for pH = 7, although the values varied for different combined with the angular momentum distribution under dipole
emission wavelengths), i.e., the same order as the PL lifetime approximation.87 The radiative recombination of carriers with
(several ns) of carbon dots, consistent with the relatively slowed the aligned momentum will emit linear polarized light as the
solvent relaxation assumption. Combined with the pH-dependent selection rules are the same for photoexcitation and emission.
measurement, carbon-dots-concentration-dependent measure- However, the decay process of the hot carriers will randomize
ments, and single step photobleaching, the authors77 claimed the aligned momentum, resulting in an isotropic momentum
that carbon dots emission was neither from the quantum distribution of the ensemble carriers by means of collision
confinement nor particle heterogeneity, instead they proposed and/or phonon emission.85 As a result, the linearly polarized
that the carbon dots were a kind of single emitter, and fluorescence can only be obtained from hot carrier recombina-
the excitation-dependent PL was from the slowed solvent tion, where the momentum alignment/anisotropy excited by
relaxation or solvatochromic red-shift. Furthermore, based on the linear excitation light is totally or partially conserved, but
the observation of the blue-shift of carbon dots at high pH on the contrary, the thermalized carriers, which exhibit an
(410), the authors claimed77 that the emission center was isotropic momentum distribution, can only emit un-polarized
located at the surface of the carbon dots. light. Thus, the appearance of linearly polarized light unambiguously
Even though the polar solvent effect has been observed by indicates the momentum alignment, which is the result of the
some other groups,82,83 the slow relaxation of polar solvents hot carrier property. The linearly polarized emission of carbon
mechanism has been argued by some researchers.82 The appear- dots84 are depicted in Fig. 9. The carbon dots show distinct
ance of PL tunability even in apolar solvents combined with the emission anisotropy, as seen in Fig. 9a (The vertical axis is the
disappearance of the spectral migration during the PL lifetime of angle between the polarization of the excitation and emission
carbon dots (synthesized by the thermal pyrolysis of citric acid light with the excitation polarization fixed.) and linear polarized
monohydrate and urea) in all solvents contradicted the slow emission. To quantitatively analyze the emission anisotropy, the
relaxation hypothesis in the polar solvents mechanism. Instead, degree of linear polarization is defined as P = (I8  I>)/(I8 + I>),
some researchers82 have attributed the solvation-dependent PL where I8 and I> are the parallel (01) and perpendicular (901)

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Fig. 9 (a and b) Emission anisotropy and degree of linear polarization of carbon dots. (c) Electric-field modulation of carbon dots emission. (d) Time-
resolved spectroscopy for different emission wavelengths. (e) Electronic structure of self-trapped excitons, which contribute to carbon dots emission.
Excitation wavelength: 442 nm. (a–e) Reproduced with permission from ref. 84. Copyright 2017, Royal Society of Chemistry.

emission compared to the excitation light, respectively. The edge emission, where the fluorescence lifetime of the band
carbon dots exhibited extremely high linear polarization at the edge emission is much longer than the momentum and energy
instant of excitation, reaching to 0.5, and then continuously relaxation time (several orders of magnitude longer), and con-
decreased as the emission energy decreased, as seen in Fig. 9b. sequently the emission is from the isotropic momentum dis-
However, there was still a large polarization value for the trusted and thermalized carriers.
carbon dots (about 0.25 for 690 nm) even when the energy The localized emission was further confirmed by electric-
difference between the excitation and emission light was more field-modulation experiments,84 as can be seen in Fig. 9c. Both
than 1 eV, which unambiguously -implied the hot carrier properties. the line shape and the intensity of the carbon dots PL were
Based on these observations, the authors claimed84 that the stable even when the electric field was as high as 1500 V cm1,
carbon dots emission originated from the localized emission, which was consistent with the localized emission assumption,
where the momentum, energy, and vibrational relaxation were whereby the strong local potential field in carbon dots protects
strongly suppressed due to the existence of a strong local the hot carriers against the quenching/tuning effect by the high
potential field. As a result, the momentum relaxation time external electric field.88,89 Power-dependent PL experiments
became comparable or even longer that the fluorescent life- showed that the emission intensity of carbon dots exhibited
time, contributing to the highly polarized emission; therefore a linear relationship to the excitation power, even when the
the carbon dots emission was totally different from the band excitation power density was up to 1800 mW cm2, which

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implied that the carbon dots emission originated from self- range as the excitation energy increases. As reported by the
trapped excitons rather than defects.90,91 The self-trapped exciton authors,84 compared to 442 nm excitation, the linear polarization
property was further validated by time-resolved spectroscopy.84 decreased for the 325 nm excitation in the 460–690 nm range,
For self-trapped excitons, a smaller charge distance r possesses a which was a result of the further relaxation and momentum
larger wave function overlap with the transition matrix, and they randomization for the 325 nm excitation.
recombine first.92 As a consequence, the emission shifts to a
longer wavelength as the time increases, so the increased lifetime 3.7 Surface dipole emission center
for the longer emission wavelength can be predicted. The time- To reveal the single particle emission mechanism and its
resolved experiment results demonstrated that, as the emission structure information, a combined spectroscopic technique
wavelength increased from 478 to 615 nm, as seen in Fig. 9d, the was adapted by Ghosh et al.93 By combining high-resolution
PL lifetime also continuously increased, which corroborated transmission electron microscopy (HRTEM) with PL imaging
the self-trapped exciton emission. Combining photoexcitation, spectroscopy, they achieved the correlative measurement of PL,
relaxation, and polarization emission, an energy diagram con- the crystal structure, and the shape of a single carbon dot. The
tributing to the carbon dots emission was given by the authors,84 carbon dots were synthesized by a microwave-assisted method
as illustrated here in Fig. 9e, where the horizontal axis is the with sucrose as the carbon source and PEG as the passivation
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coordinate distance, which represent the relative distance r agent. The combined HRTEM disclosed that there existed two
between the hot carrier pairs. With time evolution after the kinds of carbon particles: one with an onion-like structure with
photoexcitation, the larger distance self-trapped exciton states an amorphous carbon shell, as seen in the left part of Fig. 10a.
become activated and emit longer wavelength because they EDX analysis indicated that the amorphous shell mainly con-
undergo a relaxation process. The excitation-dependent PL of tained oxygen and carbon elements. The diameter of the onion-
carbon dots could be also interpreted by the self-trapped exciton like carbon dots varied from 7 to 20 nm, but they had the same
model, whereby a monochromatic light source excites the self- lattice constant of about 0.35 to 0.36 nm. The other structure
trapped exciton states with energy equal to the excitation photon was a kind of fully crystalline carbon dots with diameters
energy. The subdued decay process results in the emission ranging from 2 to 5 nm and a lattice constant of 0.24 nm, as
starting from the excitation wavelength. When the excitation presented in the right part of Fig. 10a. All the individual single
wavelength changes, the photons excite different self-trapped carbon dots exhibited much narrower PL spectra compared to
exciton states as determined by the excitation photon energy, the ensemble carbon dots and displayed a longer wavelength
and the suppressed decay process is then performed in the tail, thus the author suggested that there existed two splitting
same way as shown before. As a result, the emission starts from bands in the carbon dots. By using two Gaussian functions to
the new excitation wavelength and the spectra also shift, as fit the emission spectra of single carbon dots, the authors
observed by the experiment.84 Another predicted phenomenon claimed93 that the splitting energy was in the range of 70 to
was the reduced linear polarization in the same fluorescence 150 meV and showed no relationship to the emission peak.

Fig. 10 (a) Two types of carbon dots. Left: The onion-like shaped structure, right: full crystalline structure. Scale bar 5 nm. (b) Consecutive imagines of
the excitation TDM for the same carbon dots particle, the third one presents a theoretically calculated excitation pattern, where the orientation of the
dipole is indicated by the white double arrow. Scale bar 1 mm. (c) Normalized PL spectra of different single CNDs (5 single carbon dots) on the surface of a
glass cover slide stimulated by 467 nm (red) and 488 nm (black) laser lines. The results show that the emission spectra varied for different single carbon
dots, while each single carbon dot presented the same PL spectra, even when the excitation wavelengths were different. (a–c) Reproduced with
permission from ref. 93. Copyright 2014, American Chemical Society.

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Based on the crystal structures of single carbon dots provided charged carriers with the lattice vibrational (phonon modes)
by HRTEM and the energy splitting information, the authors results in longer wavelength emission, while excitation-dependent
calculated the optical phonons contributing to the carbon dots PL in carbon dot ensembles originates from the different carbon
emission by using a density-functional tight-binding method. dots heterogeneity.
Three optical phonons were proposed93 to be involved in the
carbon dots emission: 98 meV phonon for onion-shaped struc- 3.8 Aggregate emission center
ture carbon dots, and 112 and 113 meV for fully crystallized Following the model of a single surface dipole emission center,93
carbon dots; thus the longer wavelength PL peak was the researchers have continued to explore the details of the structure
result of the coupling between the radiative carriers with the aspects that contribute to carbon dots emission.97 As the absorp-
optical phonons. The interaction between the electrons and tion of light occurs by the coupling between the photons and
lattice vibrations (phonons) led to coupled states that possessed aromatic species in carbon dots, two general energy coupling
lower energy. approaches have been considered: excitonic coupling between
Focused or defocused imaging with an azimuthally polarized the p electronic systems in carbon dots, which is efficient in
laser beam (APLB), which can measure and provide information the condition of a near contact, and dipole–dipole resonance
on the excitation or emission transition dipole moment (TDM), (also called Förster resonance energy transfer (FRET)), which
respectively,94–96 was employed in one study93 to uncover the
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possesses a longer interaction distance. The observed parallel

emission mechanism of carbon dots. The results are illustrated orientated excitation and emission transition dipole moment
in Fig. 10b. Both the excitation and emission TDM patterns (TDM) in single carbon dots93 demonstrate that it’s the
exhibited two nearby bright spots with an elliptical shape, excitonic coupling rather than the dipole–dipole interaction
indicating the fixed linear excitation and emission TDM. The that is responsible, as the dipole–dipole interaction will rotate
TDM projection to the surface of a glass cover slide is shown by the orientation of the emission TDM from the absorption TDM
the white arrows, which clearly show that the excitation and direction.97
emission TDM were orientated parallel to each other93 for the According to the theory proposed by Kasha,98 only two kinds
same carbon dots, while a projection perpendicular to the of aggregate conditions can contribute to the excitonic coupling
surface could not be detected. The fixed excitation and emis- effect for molecular complexes, namely J- and H-aggregates.
sion TDM suggested that the carbon dots behaved as a dipole Parallel-aligned molecular dipoles can constitute J-aggregates,
for both excitation/absorption and emission. Single step PL which have distinct absorption and PL spectra features.99
intermittency and bleaching between the on–off states and Compared to molecular monomers, both PL and the absorption
monoexponential decay of the lifetime were observed for a spectra of J-aggregates are narrow and shifted to longer wave-
single carbon dots, which indicated that the carbon dots were length. Furthermore, the Stokes shift between the excitation
a kind of a single quantum emitter. To further confirm the and emission is small, and all the properties of J-aggregates are
single emitter property of single carbon dots, the authors contradictory to the observations from single carbon dots. The
checked93 whether the PL spectra of the carbon dots changed other type of p–p stacked H-aggregates possess opposite proper-
when excited by different wavelengths. The results are dis- ties with large energy shifted absorption spectra compared to
played in Fig. 10c. There was no difference in PL spectral shape molecular monomers and a large Stokes shift between the
for all the five individual single carbon dots when excited by excitation and PL, consistent with experimental observation.
467 nm (red curve) and 488 nm (black curve) lasers. The results The energy diagram was given by Alexander P. Demchenko97
indicated that individual carbon dots were a kind of single and is illustrated in Fig. 11a, where it can be seen that the
emitter, and the excitation-dependent PL of carbon dots was p–p-stacked aggregates lead to the dimer excited state splitting
the result of heterogeneity. The authors also measured93 the PL into two energy states, consisting of a higher energy excitonic
quantum yield for different single carbon dots by means of a state and a lower energy excitonic state. According to the
nanocavity-based method, and the results demonstrated that classic theory proposed by Kasha,98 the relaxation to the lower
different single carbon dots possessed different quantum yields excitonic states is forbidden, which means that the pure
within the main range of 0–0.3, which was consistent with p–p-stacked H-aggregates are non-emissive centers, which
the single quantum emitter assumption. Considering that the also contradicts the observed bright emission from carbon
different crystal structures did not present distinct PL proper- dots. Considering the recently observed bright emission from
ties, the authors speculated93 that the defect emission center H-aggregates from other materials,100,101 the authors rationalized97
was located at the surface of the carbon dots rather than its the optical spectroscopic observations from the carbon dots
core. The surface emission center notion was also supported by within the concept of excitation theory. Different from J-aggregates,
the ion-quenching experiments. In addition, the homogeneous excitonic coupling in H-aggregates could occur by a cofacial
distributed PL peak and lifetime values indicated that the all stacking alignment determined by weak van der Waals inter-
the PL spectra originated from similar defect emission centers. actions. As a result, a slight rotation of the coupled monomer in
Based on the all the observations, the following emission H-aggregates could result in a non-zero transition probability
mechanism was suggested by the authors.93 A single carbon dot from the excited states to the lower excitonic states, which
is a single emitter with the defect emission center located at the represents the emission center; thus even a small structure
surface of the carbon dot, where strong coupling between the disorder could lead to transformation of non-emissive H-aggregates

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Fig. 11 (a) The H-type aggregates formed by p–p stacking or side-to-side stacking of the chromophores, then the resulting dimer excited states split
into higher energy and lower energy excitonic states. The disorder in the H-aggregates leads to the non-emissive lower excitonic states transferring to
the emissive excitonic states, which contributes to the carbon dots emission and large Stokes shift. Reproduced with permission from ref. 97. Copyright
2016, Royal Society of Chemistry. (b) The authors103 also proposed that both the H (rod-like, as indicated by red arrow) and J (flake-like, as indicated by
blue arrow) aggregates contribute to carbon dots emission. Reproduced with permission from ref. 103. Copyright 2016, American Chemical Society.

4 Applications
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to highly emissive H-aggregates. H-aggregates formed by

different mono-chromophores (e.g., number, size, shape, 4.1 Bioimaging
surface) exhibited different absorption and emission proper-
ties, which interpreted the heterogeneity of the lifetimes and PL Compared to fluorescent organic dyes and genetically engineered
spectra for different single carbon dots, while the energy decay fluorescent proteins, carbon dots have significant advantages,
process led to decay of the hot carriers to the lower excitonic like a high PL quantum yield, photostability, and resistance to
states, which contributed to the large Stokes shift. metabolic degradation, which endows them with huge potential
Different from the dyes’ molecular or supramolecular for use in bioapplications. While the toxicity evaluation of
H-aggregates, the authors suggested97 that the H-aggregates in carbon dots is necessary and a prerequisite for exploring the
carbon dots were assembled during the synthesis process by bioapplications of carbon dots, human breast cancer MCF-7 cells
means of a regular packing of graphene sheets. Accepting the and human colorectal adenocarcinoma HT-29 cells were employed
assumption proposed by Siddharth Ghosh et al.,93 the authors by Yang et al.7 to assess the in vitro toxicity of carbon dots
suggested97 that the cofacial positions of chromophores were synthesized by the laser ablation of graphite powder and cement
located at the surface of carbon dots, and that surface functional using PEG1500N as a surface passivation agent. All the observations
polar groups, such as CQO and CQN, could modify the optical of cell proliferation, mortality, and viability from both cell lines
properties of H-aggregates containing carbon dots. indicated that the carbon dots exhibited superior biocompatibility,
The aggregates-triggered emission was also adopted by several even when the concentration of carbon dots was up to 50 mg ml1,
research groups,102–106 but with some modifications. Arjun which is much higher than the practical application demand, for
Sharma et al.103 synthesized carbon dots by directly heating citric example in living cell imaging. Additionally, in vivo toxic evaluation
acid and urea. However, unlike the pure H-aggregates emission was also carried out by the authors using male CD-1 mice;7
center, they proposed that the carbon dots emission originated whereby, two groups of mice were intravenously injected with
from the discrete multiple electronic states, and they ascribed carbon dots at a concentration of 8 mg kg1 and 40 mg kg1
the PL excitation band of 350 nm, 450 nm, and 520 nm to the separately, while a third group of mice was injected with 0.9%
carbon dots monomers, H-aggregates (see Fig. 11b, red arrow), NaCl aqueous solution as the nontoxic control. During the four
and J-aggregates (see Fig. 11b, blue arrow), respectively. The weeks of the experiment, the behaviors of all the mice were
corresponding emission bands were 460 nm, 540 nm, and normal, whereby neither violent nor lethargic behavior was
600 nm, which suggested that both H and J-aggregates contributed observed. In addition, all the experimental mice exhibited no
to the carbon dots emission. Furthermore, H- and J-aggregates clinical anorexia or symptoms such as hair loss or scabs. Serum
manifested different PL responses with increased temperature, biochemistry assays uncovered that both the hepatic injury
whereby the PL intensity of H-aggregates increase with the indicators alanine amino transferase (ALT) and aspartate amino
temperature increase as the thermal activated higher excitonic transferase (AST) and kidney injury indicators uric acid (UA),
states are emissive, while the J-aggregates display decreased PL blood urea nitrogen (BUN), and creatinine (Cr) displayed similar
intensity as the thermal activated states return to the vibra- levels in the carbon dots-injected mice and in the control group
tional states, which are non-emissive. Therefore, the authors mice, which indicated that the carbon dots were nontoxic to the
also carried out temperature-dependent PL analysis,103 and the mice. Histopathological analyses showed that the carbon dots
results were as follows: the H aggregated band (450 nm/540 nm did not cause a structure change of the hepatic, splenic, and
excitation/emission band) presented an increased emission kidneys sections. All of the above observations unambiguously
intensity as the temperature increased, while the J aggregated demonstrated the nontoxicity of carbon dots both in vitro and
band (520 nm/600 nm excitation/emission band) exhibited a in vivo. Besides the mice evaluation, similar results were also
decreased PL intensity as the temperature increased, which was observed from an experiment with zebrafish,107 which also
consistent with the authors’ claims. exhibited the excellent biocompatibility of carbon dots.

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Moreover, the plane cell toxicity of the carbon dots (synthe- of time;116 thus the injected agents cannot accumulate in
sized by the microwave heating of citric acid and urea) was the body and their circulation time should be optimized.
also verified by Qu et al.59 A carbon dots aqueous solution with The bright emissive carbon dots could be used in in vivo
a concentration of 1.5 mg ml1 was adopted to grow bean bioimaging, thus they also enable the possibility to explore
sprouts, and the results indicated that the carbon dots could be the biodistribution and clearance in animals. A main challenge
ingested by the plant cells, thus resulting in bright emissive for carbon dots8 (synthesized by laser ablation of a carbon target,
bean sprouts, and also no obvious toxicity or plant growth followed by PEG1500N surface passivation) in vivo bioimaging is
inhibition were observed. the relative low quantum yield in the near-infrared (NIR)
Due to the excellent biocompatibility and bright fluorescence, wavelength range of 650–900 nm. In vivo imaging possesses
carbon dots are naturally considered for use in bio- and clinical high quality in the near-infrared (NIR) region as both the tissue
applications. Ya-Ping Sun et al. performed the pioneering work absorption and scattering are suppressed in this region. To
on carbon dots bioimaging.2 They first employed carbon dots overcome this issue, a near-infrared dye ZW800 (emission
(synthesized by laser ablation) to label the E. coli ATCC 25922 wavelength about 795 nm) was employed by Huang and
cells, as depicted in Fig. 12a–d, and the cells displayed different co-workers8 to link to the carbon dots by means of conjugating
colors when the excitation wavelength was changed. Later, the the dye NHS ester with amino groups on the C-dots. The
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same group also demonstrated the in vivo imaging of carbon resulted ZW800-carbon dots showed two absorption peaks at
dots,108 as can be seen in Fig. 12e–i. Female DBA/1 mice (B25 g) 420 nm and 770 nm and two emission peaks at 510 nm and
were injected with 30 mg carbon dots (dissolved in 30 ml aqueous 800 nm, respectively, corresponding to the carbon dots and dye
solution) via subcutaneous injection. As seen from Fig. 12f and ZW800. Various biological fluids (fetal bovine serum (FBS),
h, the subcutaneously injected mice showed bright green blood, urine, and tissue lysate) tests demonstrated that the
emission when stimulated by 470 nm, and red light emission ZW800-carbon dots exhibited photostability, chemical stability,
for 525 nm excitation. Following the author’s in vitro and in vivo and a low emission background.
imaging demonstrations, various cell lines7,14,17,30,62,109–113 The carbon dots in vivo dynamics was explored by means of
(such as HeLa cells, MG-63 cells) and animals8,107,114,115 (such three different injection routes: intravenous (iv), subcutaneous
as mice, zebra-fish) have been also imaged using diverse (sc), and intramuscular (im). The blood circulation behaviors of
fluorescent carbon dots. carbon dots were revealed by the relative PL intensity in the
For further preclinical and potential clinical applications, venous blood, which was analyzed using a Maestro all-optical
carbon dots must meet the requirements of the U.S. Food and imaging system. The results demonstrated that different injection
Drug Administration (FDA), where agents injected into the routes resulted in opposed carbon dots concentration dynamics.
human body must be removed entirely in a reasonable period For the iv injection approach, the carbon dots concentration in

Fig. 12 (a–d) Confocal microscopy images of E. coli ATCC 25922 cell lines using carbon dots as the fluorescent material. (a) 465 nm excitation,
(b) 477 nm excitation, (c) 488 nm excitation, (d) 514 nm excitation. (e–i) In vivo imaging. (e) Bright field image, (f and h) in vivo fluorescent imaging
for 470 nm excitation/525 nm emission and 545 nm excitation/620 nm emission, respectively. (g and i) Color-coded images for (b and d), respectively.
The carbon dots were subcutaneously injected into the mice. (a–d) Reproduced with permission from ref. 2. Copyright 2006, American Chemical
Society. (e–i) Reproduced with permission from ref. 108. Copyright 2009, American Chemical Society.

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blood continued to decrease post-injection. Quantitative analysis bladder imaging analysis. The bladder red emission imaging
disclosed that the PL intensity of the blood after 1 min of post- demonstrated that the intravenous (iv) injection exhibited the
injection was about 17.3 times higher than at 1 h. While for the fastest clearance and reached its maximum value after 10 min
subcutaneous (sc) and intramuscular (im) injection routes, the of injection, while the subcutaneous (sc) and intramuscular
carbon dots concentration gradually increased and reached (im) injections displayed a much lower urine clearance rate
the maximum value 30 and 20 min post-injection, respectively, within 10 min, as indicated by the relatively low emission
as indicated by the increased blood PL intensity. These blood intensity. More specifically, the urine clearance rate of the three
circulation behaviors were observed with both the carbon dots injection routes followed the sequence of iv 4 im 4 sc, which
part (420 nm excitation) and the ZW800 component (770 nm was in accordance with the carbon dots ZW800 clearance rate
excitation) emission. In addition to the blood circulation, the from the blood. The carbon dots ZW800 clearance mechanism
clearance or accumulation of carbon dots was evaluated by the was also confirmed by the carbon dots emission, while the
authors.8 Generally, nano-materials are cleared from the body strong background of urine in the visible range caused the
via two major approaches, namely the liver, which convert them contrast to be much lower. Besides, the positron emission
into bile, and the kidneys, which convert them into urine. tomography (PET) imaging results also suggested the same
Ex vivo imaging of the organs analysis demonstrated that for all urine clearance mechanism. We want to emphasize here that
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three types of injection, most of the carbon dots were gathered by different carbon dots samples may show different in vivo
the kidneys after 1 h post-injection. Also, the accumulation rate dynamics. Hong Bi’s group117 demonstrated that carbon
displayed the following sequence: im 4 sc 4 iv, whereas, on dots synthesized from the thermal pyrolysis of konjac flour
the contrary, only a small amount of carbon dots were collected accumulated in both the kidney and liver after 4 h of intravenous
by the liver. However, when the time increased to 24 h, no injection. While 24 h after the injection, all the carbon dots were
obvious PL signal could be detected regardless of the injection cleared from the mice; thus no PL signal can be detected from
approaches, as illustrated in Fig. 13a. All of these observations the organs.
ambiguously implied that the carbon dots were totally removed Another fascinating discovery by the authors8 was that the
from the body. Beside the ex vivo imaging, the authors8 also prominent and prolonged ZW800-carbon dots were uptaken by
employed the positron emission tomography (PET) imaging the tumor. Athymic nude mice bearing a subcutaneous SCC7
technique, which showed similar results, which thus further tumor were employed as the tumor model. All the ZW800-carbon
confirmed the low accumulation of carbon dots in the body. dots injected by the three routes manifested accumulation
Further urine clearance evaluation was analyzed by in vivo around the tumor, resulting in bright red light emission, thus

Fig. 13 (a) Ex vivo imaging of the biodistribution of C-dot particles. After the injection of ZW800-carbon dots, the major organs and tissues were
collected from Balb/C mice at 1 h (left) and 24 h (right), and subsequently, the bright field and NIR imaging were obtained using a Maestro imaging system.
Top, iv injection; middle, sc injection; bottom, im injection; bright field numbers: 1, liver; 2, spleen; 3, lung; 4, kidneys; 5, muscle; 6, intestine; 7, heart.
(b) Tumor accumulation of ZW800-carbon dots for different injection approaches. In vivo fluorescence images of SCC-7 tumor-bearing mice acquired
after 2, 4, 6, and 24 h injection: control (without injection); iv; sc; im (white arrow labels tumor; red arrow labels kidney). (c) Tumor fluorescence intensity
analysis. (a–c) Reproduced with permission from ref. 8. Copyright 2013, American Chemical Society.

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the tumor became distinguishable from the surrounding citric acid and polyene polyamine were employed by Zheng and
normal tissue. In addition to the tumor accumulation, the co-workers to carry oxaliplatin,123 a platinum-based drug, as
remaining carbon dots exhibited no accumulation for the other platinum-based drugs are the most efficient anticancer drugs
normal organs and were totally removed via the kidneys (red and are used in more than 50% of chemotherapeutic treat-
arrow), which was uncovered by the in vivo imaging analysis ments for clinical cancer patients. One of the oxaliplatin(IV)
using the Maestro all-optical imaging system. The carbon dots derivatives, Oxa(IV)-COOH, was employed to link with the
accumulation ability at the tumor site also displayed an injec- carbon dots, forming CD-Oxa, and the linkage was finished
tion route dependence. The subcutaneous (sc) injection route by the reaction between the amino groups on the carbon dots
gave the highest accumulation ability, and thus exhibited the surface and the activated COOH group of Oxa(IV)-COOH, where
brightest emission. The intravenous (iv) group displayed a the COOH group was activated by using EDC/sulfo-NHS, as
lower accumulation, but the light emission was still clear from shown in Fig. 14a. A newly appeared Pt 4f XPS signal confirmed
the tumor. The lowest accumulation ability was observed with the successful bonding of Oxa(IV) to the carbon dots. Induc-
the intramuscular (im) injection, which showed the minimum tively coupled plasma mass spectrometry (ICP-MS) analysis
PL intensity, as seen in Fig. 13b and c.8 unveiled that the platinum element of carbon dots-Oxa was
All the observations have great significance for clinical 1.5 wt%, corresponding to a 4.2 wt% oxaliplatin(IV). In addition,
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applications. Carbon dots displayed no accumulation over time the TEM data indicated that the size of carbon dots-Oxa was
for all the normal organs in body and could be entirely removed 2.71  0.43 nm, thus larger than the diameter of pure carbon
from the body via the kidneys,8 which meets the requirement of dots (2.28  0.42 nm).
the U.S. Food and Drug Administration (FDA). In addition, The synthesized carbon dots-Oxa was injected into the
the unique tumor accumulation ability implied that the carbon hepatocarcinoma 22 cell line (H22) liver cancer of Chinese
dots-carried drug may exhibit better therapeutic effect, as Kun Ming (KM) mice by means of intralesional injection,123
discussed in the next sub-section. Moreover, the in vivo perfor- and the dynamical distribution of the drug was observed with an
mance such as tumor targeting, blood circulation time, could in vivo optical imaging system using blue light as the excitation
be controlled by properly choosing the injection route. source. At the instant of exposure123 (Fig. 14b), a highlight
point was observed from the in vivo imaging due to the high
4.2 Drug delivery concentration of carbon dots, and the following delivery of
The excellent biocompatibility and clearance from the body of carbon dots-Oxa resulted in a fluorescent intensity decrease
carbon dots desirably meet the prerequisite for in vivo applica- from the initial position and a broadened intensity distribution.
tions. Rich and tunable function groups, such as amino, carboxyl, After 24 h post-injection (Fig. 14e), the PL signal became much
or hydroxyl, can endow carbon dots with the ability to carry weak, which implied a decrease of the oxaliplatin(IV) drug, thus a
therapeutic agents, generating theranostic nanomedicines.118–122 second injection was carried out by the authors123 and the PL
The bright emission of carbon dots provide the opportunity to intensity became strong again. Furthermore, the PL intensity
dynamically and in real-time monitor the drug distribution and declined over another 24 h (Fig. 14g), and then the PL signal
response. Carbon dots synthesized by the thermal pyrolysis of totally disappeared when the time reached 72 h (Fig. 14h), which

Fig. 14 (a) Linkage illustration between the Oxa(IV)-COOH and carbon dots. (b–h) In vivo imaging of H22 xenograft model mice for different periods of
time after intralesional injection. (b) Injection time; red circle means the tumor site (white light view). (c–e) Corresponding to the times of 2 min, 6 h and
24 h. (f) Second injection. (f–g) The in vivo imaging for 48 h and 72 h. (i) Tumor size of H22 xenograft model, where it can be clearly seen that the tumor
size continuously decreases. (j) Illustration of the charge-convertible carbon dots-based drug-delivery process: (1) negatively charged carbon dots
extend the circulation time in blood. (2) The drug accumulates at the tumor position via the enhanced permeability and retention effect. (3) Drug
response in the tumor microenvironment. (4) Drug uptake by the cancer cells. (5) Drug release from carbon dots carrier through a proton sponge effect.
(6) Cisplatin attaching with DNA to display cancer cell cytotoxicity. (a–i) Reproduced with permission from ref. 123. Copyright 2014, Wiley-VCH.
(j) Reproduced with permission from ref. 124. Copyright 2016, American Chemical Society.

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implied that the carbon dots were cleared from the body mono-dispersed droplets were also achieved by the authors130
entirely. The tumor size of the mice continued to decrease with using a flow focusing configuration, where the carbon dots
the time of therapy, from 6.5 cm3 at the initial exposure time to aqueous solution was the dispersed phase and the mineral oil
1.2 cm3 within 2 times injection, as observed by the authors123 acted as the continuous phase. The diameter of the droplets
(Fig. 14i). The dynamic drug distribution in the tumor and body followed an inverse relationship to the capillary numbers (Ca),
during the curing process were obtained by the fluorescence defined as Ca = mn/g, where m and n are the dynamic viscosity
of the carbon dots, suggesting it would be possible to achieve and characteristic velocity of the mineral phase, respectively,
‘‘personalized medicine’’, which means that the injection and g represents the interfacial tension between the dispersed
doses, time, etc. could be controlled for individual patients. (carbon dots aqueous solution) and mineral oil continuous
Later, charge-convertible carbon dots were also fabricated phases. A larger capillary number means a higher interfacial
for drug delivery by Feng et al.124 The carbon dots surface was shear force, thus the diameter of the droplets will decrease. The
negatively charged at pH = 7.4, thus corresponding to normal results are shown in Fig. 15b and c, where the generated droplets
physiological conditions, while the surface was reversed to changed from squeezing to dripping and finally reached jetting
positively charged when the pH decreased to 6.8, mimicking along with the increasing capillary number (Ca). Besides, the
the tumor microenvironment. The negatively charged carbon multiple component droplet, merged droplet and double emulsion,
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dots surface in the normal cell microenvironment suppressed which possess unique core–shell structures, were also demon-
the drug absorption of normal cells by means of electrostatic strated successfully by the authors130 by making use of superior
repulsion between the carbon dots surface and the negatively carbon dots. To further quantitatively measure the velocity of the
charged cell membrane, thus reducing the side effects. On the flow field, carbon dots fluorescent seeding particles were also
contrary, the positively charged carbon dots surface in the fabricated by stir-mixing 3 mm porous polystyrene microparticles
tumor cell microenvironment could promote the internaliza- with a carbon dots aqueous solution. The velocity field measured
tion and cancer drug absorption because of the electrostatic by the micro-particle image velocimetry (m-PIV) technique using
interaction with the negatively cell membrane (Fig. 14g). Both carbon dots seeding particles is exhibited in Fig. 15d and e, and
the in vitro and in vivo demonstration indicated124 that carbon matches very well with the simulation results (Fig. 15f).130 All of
dots could be used as an effective imaging-guided drug carrier the static and dynamic, qualitative and quantitative measure-
with increased therapeutic efficiency and deceased side effects. ments unambiguously exhibited the high potential of applying
carbon dots in microfluidics.
4.3 Microfluidics marker
Microfluidic systems have become a superior platform for 4.4 LEDs
investigating fluidic physics at the micro-scale.125,126 Their In 2010, Wang et al.39 achieved direct white light emission
dramatically increased surface-to-volume ratio results in surface from carbon dots, which offered the possibility to fabricate
tension and viscosity being dominant over the inertia effects, carbon dots-based white light emitting devices.132–135 Later,
thus making the fluid easier to manipulate. The typical micro- they carried out tests on white light emitting devices using
fluidic cases are static laminar flows and dynamic droplet white light carbon dots as the emissive layer.136 Briefly, the
formation, with both possessing various merits, such as less carbon dots were synthesized by a thermal pyrolysis method
reagents consumption, high sensitivity, high output, which using citric acid as the carbon source and 1-hexadecylamine as
makes them find numerous applications in bioassays, chemical the surface passivation agent, which showed a relative high
reactions, drug delivery, etc.127–129 Most of the applications are quantum yield of 60% with an average diameter of 5 nm.
based on fluid flow visualization in the microfluidic circuit. The device structure, energy alignment, and organic molecular
However, the currently employed fluorescent materials cannot structure adopted by the authors136 are illustrated in Fig. 16a–c.
balance the biocompatibility and low cost, which is an urgent The architecture of the device comprised three layers. The
issue for microfluidic applications, especially for bioapplica- buffer layer consisted of 40 nm poly(3,4-ethylenedioxythiophene):
tions. To address this issue, carbon dots (synthesized from the poly(styrenesulfonate) (PEDOT:PSS) in the anode, which had
microwave heating of glucose and urea) were, for the first time, two functions: (1) increase the work-function from 4.7 eV (ITO)
employed to visualize micro fluid flows by Sun’s group.130 The to 5.0 eV. (2) Increase the smoothness of the anode. The carbon
authors explored the mix dynamics of DI water and glycerol dots emissive layer was fabricated by a spin-casting method
with carbon dots dissolved DI water as the fluorescent marker. with an optimized thickness of 20 nm. A thicker film, e.g.,
At t = 0 s (Fig. 15a), the flat flow was determined by the 35 nm, would lead to bad charge transport in the carbon dot
hydrodynamic driving forces, where an applied electric field film, while a thinner film, e.g., 10 nm, would increase the
(136.36 kV m1) then ruptured the interface and resulted in the density of voids, grain boundaries, etc., both of which would
complete mixing at t = 3.76 s, as seen in Fig. 15a. The instability decrease the device EL efficiency. AFM measurements indicated
process was balanced by the pressure gradient, viscous dissipa- that the surface roughness of the carbon dot film was less than
tion, and electric-field induced body-force ruled by the ion 3 nm, which implied good compatibility between the carbon
species conversion law in each fluid. An electric field higher dots and the buffer layer. Finally, the electron transport layer
than a threshold ruptures the interface and leads to rapid was employed through 40 nm thick 1,3,5-tris(N-phenylbenz-
mixing at the micro-scale.131 In addition to the laminar flow, imidazol-2-yl) benzene (TPBI) due to its good electron transport

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Fig. 15 (a) Mixing evolution of carbon dots aqueous solution and glycerol at an applied electric field of 136.36 kV m1; scale bar 100 mm. (b) Droplet
formations in three typical regimes: squeezing, dripping, and jetting, which correspond to the different capillary number; scale bar 50 mm. (c) Relationship
between the capillary number and droplet diameter. (d–f) Flow velocity field measurement using a carbon dots-based seeding particle. (d) Fluorescent
imaging of a droplet generated with the carbon dots seeding particle distrusted in the dispersing phase. (e) The measured velocity field by using the
micro-PIV technique; scale bar 50 mm. (f) The simulation results of the velocity field of the droplet, which match very well with the measurements. For all
experiments and simulations, the flow rate of the dispersed phase and continues phase was 20 : 100 ml h1. Reproduced with permission from ref. 130.
Copyright 2017, Wiley-VCH.

ability. The electrode consisted of 1 nm LiF and 120 nm Al By modifying the device structure, color-switchable CD LEDs
fabricated by thermal evaporation. were demonstrated using the same carbon dots by Zhang’s
The pure carbon dots exhibited broad PL with an excitation- group.137 According to the excitation-dependent PL and time-
dependent emission feature, while the LED device displayed resolved measurement, the authors claimed that there existed
stable emission even when the voltage was increased to 10 V, as three emission channels, whose lifetimes were 2 ns, 5–6 ns and
shown in Fig. 16d.136 The Commission International d’Eclairage 14–15 ns, contributing to 420 nm, 460 nm, and 580 nm band
(CIE) coordinates of the emitted light were (0.40, 0.43) ((0.33, 0.33) emissions, respectively. In addition, the authors proposed137
for pure white light), with a color-rendering index CRI of 82. The that the relaxation process for high energy emission was faster.
WLED had a turn-on voltage of 6 V, with the maximum external Adopting this assumption to fabricate the carbon dot LED,
quantum efficiency (EQE) reaching 0.083% at a current density of different current injections would lead to the following conclu-
5 mA cm2, and a maximum brightness output of 35 cd m2 with sion: when the injection current density is low, the hot carries
a current density of 160 mA cm2 and voltage of 9 V. will relax by means of the fast decay channel, resulting in a high

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Fig. 16 (a–c) White light LED device structure illustration, energy alignment, and organic molecular structures. (d) Normalized electroluminescence
spectra of the carbon dots white light LED; inset is the photograph of the white light emission from the LED with a voltage of 9 V. (e–g) Schematic
diagrams of the device structure for tunable EL light, blue light, and white light emission LEDs respectively. (h–j) The corresponding EL spectra for the
tunable, blue and white carbon dots LEDs; insets are the photographs of the devices at different applied voltages. (a–d) Reproduced with permission form
ref. 136. Copyright 2011, Royal Society of Chemistry. (e–g) Reproduced with permission from ref. 137. Copyright 2013, American Chemical Society.

energy emission, e.g., 412 nm band or blue emission, while a as the ETL and 1 nm LiF and 150 nm aluminum as the cathode
high injected current density could stimulate all three emission double layer, the turn-on voltage was 5 V and the injection
bands. In addition, the highly populated excited states could current density could be tuned from relatively low to relatively
feed the lower emission band, e.g., the 480 nm and 580 nm high (reaching 600 mA cm2), while, as discussed above,
states, thus the lower band emission becomes dominant in the different injection current densities (or the corresponding applied
case of a high current injection. So by adjusting the injection voltage) resulted in different color emissions, as can be seen in
current, the authors achieved137 tunable color emission based Fig. 16h. Blue, cyan, magenta, and white light emissions occurred
on one kind of carbon dots. at voltages of 6 V, 7 V, 8 V, 9 V, respectively, while the Commission
The structure illustration of the CD LED device adopted by Internationale de l’Eclairage (CIE) coordinates for the four
the authors is shown in Fig. 16e–g.137 Briefly, the LED consisted of emission colors were (0.198, 0.151), (0.212,0.162), (0.260,
six layers: an ITO anode, 25 nm hole-injection layer, 40 nm hole- 0.221), and (0.318, 0.320).137
transport layer (HTL), 20 nm carbon dots layer, 5 nm electron To obtain pure blue emission CD LED, a low current injec-
transport layer (ETL), and top cathode layer. Poly(ethylene- tion density was necessary; thus the authors137 increased the
dioxythiophene):polystyrene sulfonate (PEDOT:PSS) was utilized thickness of the LiF layer of the cathode layer from 1 nm
as the hole-injection layer. Poly-(N,N 0 -bis(4-butylphenyl)-N,N 0 - to 5 nm, and as a result, the current density decreased to
bis(phenyl)benzidine) (poly-TPD) was employed as the HTL 150 mA cm2, resulting in a pure blue CD LED with a turn-on
because of its superior hole-transport capability, the matched voltage 5 V and a maximum luminance of 24 cd m2, as
energy alignment between poly-TPD and the PEDOT:PSS layer, illustrated in Fig. 16i. Similarly, a high current density injection
and as it was easy to synthesize a uniform thin film. The ETL and could result in white light emission. Thus, using ZnO nano-
the cathode layer were designed for a certain purpose. When particles as the ETL and with the cathode layer only containing
choosing 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) 150 nm Al, the high electron mobility of ZnO nanoparticles

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(2  103 cm2 V1 s1 for ZnO, one order of magnitude higher Carbon dots-based ratiometric pH sensing was first proposed
than TPBI 1  104 cm2 V1 s1) endowed a high injection by Wen and co-workers,152 using carbon dots synthesized by
current density to the emissive layer, resulting in white light the thermal pyrolysis of citric acid with 4,7,10-trioxa-1,13-
emission, as depicted in Fig. 16j. The white light CD LED tridecanediamine (TTDDA) as the surface passivation agent.
possessed the maximum luminance of 90 cd m2 with a Both pH-sensitive fluorescent fluoresceinisothiocyanate (FITC)
turn-on voltage of about 4.6 V. and pH-insensitive rhodamine B isothiocyanate (RBITC) were
Different from controlling the injection current density, utilized to post-treat the carbon dots, endowing the carbon dots
carbon dots with excitation-independent emission were also with two emission bands located at 515 nm and 575 nm (excited
proposed by Yang’s group to fabricate mono-color light emis- by 488 nm), respectively. The author’s demonstration152 indi-
sion LEDs.13 The carbon dots were synthesized by means of cated that, as the pH value changed from 5 to 9, which covered
hydrothermal methods. By controlling the carbon source (citric the full range of the physiological environment of the human
acid), nitrogen source (2,3-diaminonaphthalene or 1,5-diamino- body, the intensity of the 515 nm emission band increased
naphthalene), surface passivation/carbonization (concentrated substantially, while that for 575 nm only increased a little, thus
sulfuric acid), and reaction time, all blue, green, yellow, orange, it was clearly shown that the carbon dots exhibited a linear
and red emission carbon dots were achieved. All the carbon dots ratiometric response to the pH input (see Fig. 17a and b). In
addition, the authors also demonstrated152 that both the intra-
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exhibited relatively high quantum yields: 75% (B), 73% (G),

58% (Y), 53% (O), and 12% (R). The EL spectra of all the carbon cellular genres (such as ions, saccharides, and proteins) and
dots were consistent with the PL spectra with the peaks located redox substances (e.g., H2O2, ClO, reduced glutathione (GSH),
at 455 nm (blue), 536 nm (green), 555 nm (yellow), 585 nm GSH inhibitor (NEM), and GSH precursor (NAC)) have a neglectful
(orange), and 628 nm (red) and all displayed voltage-independent effect on the carbon dots ratiometric response, which verified the
EL colors. The authors13 attributed the tunable PL emission and selectivity of the carbon dots-based ratiometric sensing.
voltage stable EL emission to the band emission of carbon dots Small molecule linked carbon dot ratiometric sensors
with the quantum confinement effect. The CIE coordinates, possess high accuracy, although their ease of photobleaching,
maximum luminance, and current efficiency for the monochrome and the leaching of small molecules from the carbon dots
LEDs were13 ((0.19, 0.20), 136 cd m2, 0.084 cd A1), ((0.31, 0.47), limit their practical applications. To overcome these issues, a
93 cd m2, 0.045 cd A1), ((0.37, 0.52), 60 cd m2, 0.02 cd A1), label-free carbon dots ratiometric pH sensor was proposed by
((0.46, 0.48), 65 cd m2, 0.027 cd A1), ((0.55, 0.41), 12 cd m2, Huang’s group154 using carbon dots synthesized by the hydro-
0.0028 cd A1) for the blue, green, yellow, orange, and red thermal treatment of citric acid and basic fuchsin, where the
LEDs, respectively. fuchsin had a pH-sensitive property. The carbon dots displayed
two emission peaks located at 475 nm and 545 nm, respectively,
4.5 Sensing when excited by 380 nm. The pH-dependent experiments
The fluorescence intensity of carbon dots is closely related to uncovered that, as the pH values increased from 4.0 to 11.0,
the surrounding environment. The interaction between carbon the intensity of the 475 nm emission band continuously
dots and chemicals results in the quenching/enhancement of increased, while the intensity of the 545 nm emission band
carbon dots emission. Thus carbon dots can be used as a kind manifested a different performance which slightly increased
of fluorescent probe to detect the quantity of items. Various from acid to neutral condition, while further increasing the pH
sensors based on the fluorescence of carbon dots have been from 7 (neutral condition) to 14 (alkaline condition) resulted in
reported and can be generally categorized into the following the decrease of the 545 nm emission band, as shown in
groups: ion sensing,138–141 such as Eu3+, Fe3+, Fe2+, F, Tl+ Fig. 17c. The intensity ratio of 457 nm and 545 nm exhibited
(thallium); pH-value sensing;142–145 biomaterial sensing,145–148 such a linear relationship to the pH values in the range of 5.1 to 8.8,
as intracellular lysine, ascorbic acid, guanosine 30 -diphosphate-50 - as can be seen in Fig. 17d,154 which implied that the carbon
diphosphate (ppGpp); enzyme (e.g., thioredoxin reductase (TrxR)); dots could be used as a ratiometric pH sensor. The reproduci-
DNA; and temperature sensing.149–151 However, single fluores- bility experiments demonstrated that carbon dots emission
cent wavelength intensity change-related sensing requires strict could totally recover between the strong acidic environment
conditions. The fluctuation of the light source, concentration (pH = 4.0) and strong alkaline condition (pH = 11.0). In
of fluorescence probes, different optical paths, and even the addition, the authors also substantiated154 that both the metal
aggregation of the probes could devalue the reliability of the ions (such as Fe3+, Cu2+, Hg2+), biothiol (e.g., GSH, Cys), and
sensing results. Thus ratiometric sensing as an alternative has reactive oxygen species (ROS) (e.g., H2O2, HClO) had negligible
been proposed,143,145,152,153 as it can simultaneously collect influence on the ratiometric pH sensing, thus verifying the
information on the intensity change of two separated emission selectivity of the sensing. Living HeLa cells were employed by
bands. The intensity ratio of the two wavelengths is the the authors154 to inspect the function and applicability of the
indicator of the sensing item and is considered as the output. carbon dots sensor. The HeLa cells were treated by various
Compared to a single emission sensor, ratiometric sensing buffered solutions with different pH values (pH = 5.01, 5.64,
provides for self-calibration for both the light source and 6.46, 7.21, and 8.01). The results are displayed in Fig. 17e. As
sensing environment, and thus can vastly improve the sensing the pH values increased from 5.0 to 8.0, the blue emission
accuracy and reliability. corresponding to 475 nm band (465–495 nm, channel 1) increased,

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Fig. 17 (a) PL emission spectra of carbon dots in the pH range of 4.5–9. (b) The relationship between the intensity ratio (I515/I575) R and pH values. The
carbon dots were surface passivated by FITC and RBITC with different molar ratios from 1 : 1 to 1 : 30. (c) PL spectra of carbon dots in PBS buffer solution
with different pH values (stimulated by 380 nm); inset shows the corresponding color change under 365 nm UV. (d) Linear relationship between the
intensity ratio and pH value. (e) Confocal fluorescence images of HeLa cells. Channel 1: 465–495 nm band pass filter. Channel 2: 535–565 nm band pass
filter. The ratio of the two band emission was obtained by imaging processing. All the samples were stimulated by 380 nm. (f) PL emission spectra of
carbon dots for different concentrations of lysine: from 0.5–260 mM in 100 mM buffer solution with the pH value of 2. (g) Linearly relationship between
the intensity ratio (F440/F624) and the lysine concentration. (h) PL emission spectra of carbon dots for buffer solutions at different pH values (in the range
of 1.5–5.0); inset shows photographs of the buffer solutions under white light (upper) and UV light (lower) excitation, respectively, left to right: pH value
1.5 to 5.0. (i) The linearly relationship between the intensity ratio (F624/F440) and the pH values. (a and b) Reproduced with permission form ref. 152.
Copyright 2012, Wiley-VCH. (c–e) Reproduced with permission from ref. 154. Copyright 2016, American Chemical Society. (f–i) Reproduced with
permission from ref. 145. Copyright 2017, American Chemical Society.

but the 545 nm yellow light (535–565 nm, channel 2) showed a of 98 nM) and the pH value (linear performance in the range
slight decrease. The merged graphs of the blue emission and of 1.5–5) in a ratiometric manner, as seen in Fig. 17f–i.
yellow emission bands exhibited a pronounced color change154
as the pH value continued to increase, which could be clearly 4.6 Logic gates
seen by the naked eye. The fluorescence ratio imaging was The development of molecular devices can help to achieve
accomplished by using imaging processing, as illustrated in multifunctional ‘‘lab-on-a-molecule’’,155 and triggers the appli-
Fig. 17e. The calibrated ratio-pH function was also obtained154 cations of molecular information processing, communication,
by calculating the average PL intensity of the blue channel and molecular based biosensing, etc.156 All of these intriguing
yellow channel. Later, Song et al.145 also proposed another kind applications are based on basic logic operations, and the PL
of dual emissive carbon dots (synthesized by the hydrothermal signal is regarded as a desirable logic gate readout due to its
treatment of o-phenylenediamine and phosphoric acid). The fast response, increased signal-to-noise ratio, and high resolu-
carbon dots exhibited two emission bands at 400 nm and tion. All these good merits of fluorescent carbon dots make
624 nm, where the 400 nm blue emission could be enhanced them an effective competitor in logic gates.157–162
by lysine, while the 624 nm red emission band was inert to The prerequisite to achieve a carbon dots chemical logic gate
lysine. However, when the input was changed to different pH is to generate a variable PL output, which could be realized by
values, the results were different: as the pH value increased heavy metal ions causing PL quenching. A carbon dots aqueous
from 1.5–5.0, the 400 nm blue band became stable, while the solution synthesized by the thermal pyrolysis of lemon juice
624 red band emission decreased. In both cases, the intensity was adopted by Pal’s group,15 and displayed two absorption
ratio of the two emission bands manifested a linear relationship bands located at 268 and 320 nm, respectively. The authors15
to the input items (lysine or pH), thus the authors advised145 that also discovered that increasing the pH value to 10.2 resulted
the carbon dots could be used to sense both lysine (linear in an enhanced 268 nm absorption and the appearance of a
performance in the range of 0.5–260 mM with a detection limit new broad band at longer wavelength. The pH-dependent PL of

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carbon dots was also evaluated by the authors.15 Exited by PL spectra shift, the authors15 assumed that only one func-
360 nm, the PL intensity increased when the pH value increased tional group was involved in the emission of carbon dots. The
from 1 to 7, with the PL peak nearly remaining the same (the fact that both the pH-dependent absorption optical density
absorption difference of 360 nm was eliminated by the authors15 (@400 nm) and the PL peaks manifested a sigmoidal pattern
via normalizing the PL intensity to the relative absorption). On with a similar inflection point at pH = 7.9 led the authors to
the contrary, continuously increasing the pH value from 7 to 10 advocate that it was the phenolic functional groups that con-
led to a decrease of the PL intensity, along with an intriguing PL tributed to the carbon dots PL red-shift in high pH conditions.
spectral red-shift. The authors15 also discovered that different More specifically, the phenolic group was strongly coupled with
excitation wavelengths in the range of 320–380 nm resulted in the emissive center located at the surface of the carbon dots,
the same emission peak located at 445 nm for both acidic and which could modify the energy level of the emissive states.
basic conditions. However, when the excitation wavelength was Therefore, Pal et al.15 suggested the following pH-dependent PL
increased to 400 nm, the PL spectra of the carbon dots in mechanism: the high pH value condition leads to the deproto-
alkaline conditions showed a red-shift with the peak shifted to nation equilibrium of phenol 2 phenolate (where coupling
465 nm, while nearly no PL signal could be observed from acidic with phenol and phenolate will result in different energy
carbon dots. Both the pH-dependent absorption and emission states), namely the transformation between phenol and phe-
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spectra were completely reversible, which implied that neither nolate, which can tune the PL emission of carbon dots. The
the acidic or basic conditions degenerated the carbon dots. carboxylic functional groups cannot affect the PL properties of
Based on the opposite zeta potential values measured from carbon dots because there is no coupling between the emission
acidic (x = 0.13 mV for pH = 2.6) and basic (x = 7.8 mV for center and carboxylic groups, even though the carboxylic 2
pH = 9) carbon dots, the authors15 attributed the pH-dependent carboxylate deprotonation equilibrium also exists. Thus the
spectral shift and intensity variation to the pH-triggered proto- authors proposed15 that a tunable PL signal of carbon dots
nation and deprotonation. FTIR spectroscopy analysis implied could be achieved by properly controlling the surrounding
that two stretching bonds at the carbon dots surface gradually environment, e.g., the pH and surface chemical modification,
disappeared as the pH value was increased from 2.5 to 10. One e.g., the presence of Hg2+, which can offer the opportunity to
of the bonds was the CQO bond of the carboxylic acid with produce carbon dots-based chemical logic gates.
infrared absorption at 1725 cm1, along with the appearance of As observed by the authors,15 in an acidic environment,
two new carboxylate categories at 1575 and 1390 cm1. The e.g., pH = 2.7, both the carboxylic (even if the carboxylic group
other disappeared functional group was the C–OH stretching of was not directly coupled with emissive states, it could also affect
the phenolic category with absorption at 1220 cm1, which was the PL quenching process by means of electrostatic interaction)
converted to a phenolate bond at 1278 cm1. and hydroxyl categories were absolutely protonated, thus the
Generally, carboxylic functional groups possess a lower pKa Hg2+ could not quench the PL of carbon dots. As a result, the
value in the range of 4–5 due to their relative acidic properties, authors suggested15 that the YES logic gate could be realized by
while more basic phenolic functional groups hold a higher regarding the Hg2+ as the input and the PL intensity as the
pKa value of about 8–10. Considering that there was only one output, as can be seen in the left part of Fig. 18. Increasing the
inflection point for the pH-dependent absorption density and pH value to 8.9 (basic environment) results in the deprotonation

Fig. 18 PL spectra, corresponding logic gate, and Truth tables for ‘‘YES,’’ ‘‘NOT,’’ and ‘‘IMP’’ logic gates, respectively. Reproduced with permission from
ref. 15. Copyright 2017, American Chemical Society.

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of both the carboxylic and phenolic functional groups, and the acid chlorides and the (R) or (S)-2-phenyl-1-propanol
consequently, the surface of the carbon dots is negatively charged, (chiral molecular) resulted in enantiomerically pure esters
which could interact with the Hg2+, leading to PL quenching. and the formation of chiral carbon dots, as shown in Fig. 19a.
Therefore, the NOT gate was realized by Pal et al.15 in the The formation166 of the enantiomerically esters and chiral
condition of a basic environment when considering Hg2+ as the carbon dots was confirmed by 13C-NMR and FTIR spectroscopy,
input and the PL intensity as the output (middle part of Fig. 18). where the appearance of 120–150 ppm peak in the 13C-NMR
The authors also discovered that the quenched PL could be indicated the existence of the phenyl substituents and the 1731–
recovered by adding extra glutathione (GSH), as the thiol group 1727 cm1 (CQO stretch vibration), 1300 cm1 (asymmetric
in glutathione could combine with a Hg2+ ion and release the stretching vibrations of C–O–C), and 1200 cm1 (symmetric
carbon dots from the Hg2+ ion. But it should be noted that pure stretching vibrations of C–O–C) signals in the FTIR spectra
glutathione could not affect the PL properties of carbon dots. implied the occurrence of ester groups.
Therefore, the implication logic gate was fulfilled by Choudhury The chiral carbon dots N-methylpyrrolidone (NMP) solution
and co-workers15 by using the Hg2+ ion and glutathione as the was prepared for circular dichroism (CD) measurements.
chemical input and the PL intensity as the output, as seen in the However, the authors discovered that166 the chiral moieties at
right part of Fig. 18. If the pH, Hg2+, and GSH were all viewed as the carbon dots surface did not have any obvious chiral absorp-
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the chemical input and the PL intensity as the readout, a more tion with wavelengths longer than 300 nm, thus the pyrene
complex logic gate could also be demonstrated. molecule was introduced to the chiral carbon dots solution to
Carbon dots synthesized by an induction heater (500 W, aid forming a supermolecular species, which could trigger the
100 1C) of citric acid and ethylenediamine manifested chiral property transfer from the chiral carbon dots to the super-
pH-stable PL in the range of 4–11; however, they could be also molecular species by means of strong p–p stacking forces, as
used to realize a chemical logic gate.157 Chattopadhyay’s group observed from other carbon nano-forms.167–169 Consequently, the
uncovered that the PL intensity (excited by 365 nm, detected at pyrene/chiral carbon dots NMP solution displayed an obvious CD
433 nm) of the carbon dots could be quenched by picric acid via signal, as observed by the authors166 (Fig. 19b). More specifically,
static quenching. An additional mixture of acetonitrile, ethyl the S-chiral carbon dots exhibited a positive Cotton effect in the
acetate, and sodium chloride could transfer the picric acid to absorption range of 320–350 nm, while the R-chiral carbon dots
the organic phase, thus recovering the PL of the carbon dots. showed the opposite negative Cotton effect in the similar absorp-
Alternatively, the authors also discovered157 that carbon dots tion range. The authors attributed166 the small wavelength shift
could be quenched by Fe3+ through dynamic quenching, accom- of the CD signal for the R- and S-chiral carbon dots to the non-
plished by ultrafast carrier transfer between the carbon dots and identical surface functionalization and organization.
Fe3+ ions. A following treatment by ascorbic acid or cysteine In addition to the (R) and (S)-2-phenyl-1-propanol chiral
could reverse the PL quenching, whereby the ascorbic acid could molecules, the L/D-cysteine chiral molecule was also adopted
reduce the Fe3+ ion to Fe2+ ion and cysteine could yield a by Nozomu Suzuki et al.170 to synthesize chiral carbon dots.
complex with Fe3+, both of which could consume the Fe3+ ion Briefly, the carbon dots were synthesized by the chemical exfolia-
and release carbon dots emission. Diverse and multifunctional tion of carbon fiber in the presence of sulfuric acid and nitric acid,
logic gates were reported by the authors157 using the variable PL while a following carbodiimide/N-hydroxysuccinimide (EDC/NHS)
as the output: the NOT logic gate was realized by using the picric cross-linking method linked the L/D-cysteine to the surface of the
acid (or Fe3+ ion) as the input (input logic 1); for the Fe3+-ion- carbon dots by means of covalently bonding the amine group in
treated carbon dots system; whereby the input of ascorbic acid L/D-cysteine with the carboxylic group in the carbon dots, thus
(input logic 1) and cysteine (input logic 1) could result in the OR resulting in chiral carbon dots, labeled as L-/D-carbon dots. Both
logic, as only when both of the inputs were 0 (i.e., both the the pristine and chiral carbon dots exhibited a similar size
ascorbic acid and cysteine were absent), was the output 0 (namely distribution in the range of 2–7 nm and a broadened XRD peak
the PL intensity was low). By properly designing the system and at 2y = 251. In addition, both the position and the relative
chemical component input, even higher complex logical systems intensity of the A1g D band Raman signal at 1355 cm1 and
were demonstrated by Sk and co-workers.157 the E2g G band Raman signal at 1590 cm1 were the same for the
pristine and chiral carbon dots. All of these indicated that
4.7 Carbon dots chiral photonics the cysteine surface modification did not change the structure
Chirality plays an important role in various practical application of the center graphene carbon sheets, as suggested by the
fields, such as chiral drug recognition, chiral molecular biology, authors.170 The appearance of the S–H bond (2390 cm1) in
and chiral chemistry.163–165 Thus the combination of carbon the FTIR spectra implied that the cysteine ligands were linked to
dots with chirality can give rise to intriguing chiral optics based the carbon dots successfully, and the linkage was finished via
on carbon dots, as first proposed by M. Vázquez-Nakagawa covalent bonding, which was verified by the newly formed C–N
et al.166 In their pioneering work, the carbon dots were synthe- bond (830 cm1) in the chiral carbon dots.
sized by means of the chemical exfoliation (concentrated sulfuric CD spectral measurements demonstrated170 that both the
acid and nitric acid) of graphite, and thionyl chloride was L and D chiral carbon dots exhibited two chiral bands, as seen in
employed to convert the carbon dots surface carboxylic acid Fig. 19c: one located at the high energy band of 210–220 nm,
groups into acid chlorides. The simultaneous reaction between which was close to the chiral band of the pure cysteine at

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Fig. 19 (a and b) Chiral carbon dots synthesized by Martin’s group. (a) Structure illustration of chiral carbon dots obtained from the (R) or (S)-2-phenyl-1-
propanol. (b) Upper: Circular dichroism spectra of chiral carbon dots-(R)/pyrene (blue) and chiral carbon dots-(S)/pyrene (green) in NMP solution.
Bottom: UV-visible spectra of pyrene in NMP. (c) Circular dichroism spectra of carbon dots synthesized by Nicholas A. Kotov’s group.170 (d) Circular
dichroism spectra of chiral carbon dots synthesized by Guangjun Nie’s group.171 (e and f) The tunability of L- and D-carbon dots to ECAR (extracellular
acidification rate), where the basal glycolysis and the glycolytic capacity are the indicators of the ECAR. (a and b) Reproduced with permission from
ref. 166. Copyright 2016, Royal Society of Chemistry. (c) Reproduced with permission from ref. 170. Copyright 2016, American Chemical Society. (d–f)
Reproduced with permission from ref. 171. Copyright 2018, Royal Society of Chemistry.

209 nm, and another at a lower energy chiral band located at the conformation structure of the carbon dots themselves. The
250–265 nm, which had an opposite sign compared to the cysteine ligand was linked to the carbon dots by means of
chirality of cysteine used to modify the carbon dots. In addi- noncovalent intermolecular interaction. Intermolecular inter-
tion, the lower energy (located at 250–265 nm) chiral band action between the chiral molecule and the large carbon dots
manifested an overlap with the absorption peak at 260 nm and results in a buckling deformation, and as a result, the equili-
displayed a relatively high g factor of 1  104. By using the brium conformation of the carbon dots sustains a strong twist;
combined calculation methods of the semi-empirical ZINDO more specifically, L-cysteine and D-cysteine result in a right-
algorithm, MMFF algorithm, DFT+ZINDO algorithms, and by hand and left-hand twist, respectively, corresponding to
comparing with the XPS and CD spectral data, the authors the different twisted excitonic states. The twisted carbon dots
suggested170 that the high energy chiral band originated from could facilitate the electrons and holes to transfer to one of
the hybridization of the atomic orbit of the cysteine chiral the excitonic states, resulting in the longer wavelength
molecule and the molecular orbit of the small segment or edge chiral excitonic band. It’s clear that the chirality (i.e., rotatory
groups of the graphene sheet. The hybridization was caused by handedness) of the carbon dots was opposite to chirality of the
the symmetry-breaking triggered perturbation of the graphene modification chirality molecular, consistent with the authors’
surface edge states due to the existence of the chiral ligands on experiment observations.170
the surface. Such a mechanism was termed as170 ‘‘local chirality In addition to surface chiral molecular modification,172,173
induction.’’ However, the authors also pointed out that the local chiral carbon dots could also be directly prepared by the chiral
hybridization mechanism was not suitable for interpreting the precursor guanosine 5 0 -monophosphate, (5 0 -GMP).174 Briefly, the
longer wavelength chiral band (at 250–265 nm) because, based chiral molecular disodium salt of guanosine 5 0 -monophosphate,
on the theory, for the larger diameter 10–15 nm carbon dots, no Na2(50 -GMP) was heated by microwave at 160 1C for 5 min to
chiral band should be observed for wavelengths longer than synthesize chiral carbon dots. (HR)TEM analysis indicated that
220 nm even though local hybridization exists on the surface of the carbon dots had an average diameter of less than 5 nm, with
the large diameter carbon dots. On the contrary, the authors170 a highly disordered amorphous carbon core. The amorphous
attributed the longer wavelength chiral band to the change of carbon dots were also confirmed by Raman spectroscopy due to

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the absence of D band and G band signals for the carbon dots. Although carbon dots-based optoelectronic applications
The synthesized chiral carbon dots displayed several chiral have been demonstrated, e.g., in LEDs, their external quantum
peaks, including three positive peaks at 218, 270, and 300 nm, efficiency and maximum luminance are still low, so further
and two negative chiral peaks at 230 nm and 260 nm. The improvement of the efficiency is needed, which requires higher
similarity of the CD spectra of carbon dots and the 5 0 -GMP quantum yield carbon dots and proper device structure design.
indicated that the chiral structure was converted during the Both of these are related to a clear understanding of the optical-
carbon dots synthesis, as suggested by the authors.174 physical properties of carbon dots. As we discussed above,
The most exciting news for chiral carbon dots relates to the researchers have paid much attention to try to understand
recent achievements in the chiral control of bioreactions. the emission essence of carbon dots, and various break-
Xin et al.175 demonstrated that D-glutamic acid (D-Glu)-carbon throughs have been achieved in recent years, but there are still
dots could drastically destroy both the Gram-negative and Gram- some debates and challenges remaining. Even through differ-
positive bacteria cell wall, resulting in the death of bacteria, ent emission models proposed by researchers may contribute
while their counterpart L-glutamic acid (L-Glu)-carbon dots to different kinds of carbon dots emission, the fine structure
manifested negligible effect to bacteria, which suggested that chiral (e.g., for self-trapped exciton emission,84 the bond geometry
carbon dots could be used as chiral antimicrobial nanoagents. configuration, bond length, bond angle, and local potential
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L- and D-cysteine-based carbon dots have also been utilized to distribution) of the emission center is still a big issue. Thus
control the enzyme’s chiral activity,176 e.g., L-cysteine carbon dots more theoretical and experiment methods need to be employed
increased the laccase enzyme activity by 20.2%, while D-cysteine to uncover the mystery of carbon dots emission.
carbon dots exhibited the opposite behavior, suppressing the The carbon dots-based sensing platform may play a more
enzyme activity by 10.4%. Very recently, Li et al.171 even discovered important role in the future, especially for biosensing. The
that L/D-cysteine-based carbon dots could even affect the cellular discovery of ratiometric sensing and the demonstration of
energy metabolism. In the future, we believe that more chiral in vitro pH mapping imply a high potential for practical sensing
carbon dots-based applications will be explored,177 and chiral applications. However, to compete with commercial sensors,
carbon dots will become a new but fascinating field due to their carbon dots-based sensing should further improve the sensitiv-
huge potential practical applications. ity, selectivity, and robustness. Also, to achieve in vivo sensing
and mapping will also be a part of the future development of
carbon dots-based biosensing. Sun’s group130 demonstrated
5 Summary and prospects the potential to apply carbon dots in a microfluidic platform.
Considering the widespread applications, especially the bio-
Carbon dots as a new kind of carbon-based fluorescent material applications of such a microfluidic platform, we believe that
have triggered numerous investigations. Various breakthroughs bright fluorescent carbon dots will light up the micro-channels
have been obtained from their fundamental optical-physical and facilitate more applications based on microfluidic systems,
properties to potential applications. It’s believed that carbon dots such as bioassays, drug delivery, and biosystem mimics.
will play a more important role in various fields in the future. We want to highlight the discovery of chiral carbon dots.
Considering their excellent biocompatibility, it’s reasonable to One very exciting piece of recent news is that chiral carbon
predict that carbon dots will become an important platform for dots-based applications have started to appear; for example,
bioapplications. Thus, exploring high quantum yield NIR emis- chirality controlled enzyme activity and cellular energy
sion carbon dots is urgent for bioimaging, as near IR light metabolism.171,175,176 We predict that more and more chiral
manifests a high tissue penetration depth and deceased auto- carbon dots-based applications will appear in biology, catalysis,
fluorescent background. Carbon dots linked with proper moieties optic electronic, and sensing. However, at the current stage, the
and therapeutic drugs offer the potential to identify the challenge chiral carbon dots only hold UV range CD signals due to
of cancer heterogeneity and adaptation. However, as pointed out the chiral molecule; thus one of the future directions is to
by Gao et al.,178 before the practical clinical applications of carbon explore chiral carbon dots that possess visible and even near IR
dots, researchers should provide more evidence that carbon dots- range CD signals. Another big issue for chiral carbon dots is the
based drug delivery is better than monoclonal antibody-bonded circular polarized emission. Circular polarization emission has
anticancer drugs179 and biodegradable polymer-linked drugs.180 wide applications, such as in chiral sensing, chiral drug discovery,
Consequently, the next step for carbon-based nano-therapy is flat panel display, and quantum communications.163,181–183 While
to explore carbon dots that can hugely reduce the non-specific it’s still difficult to achieve circular polarized emission from
uptake by normal cells, while increasing the specific targeting carbon dots, which hugely hinders the applications of chiral
capability, especially enhancing the cancer cell specific targeting carbon dots, future research efforts should be paid to address
ability, and elongate blood circulation to increase the therapeutic this issue.
effect, i.e., to explore carbon dots targeted nano-medicine to In summary, researchers have achieved gratifying progress
achieve cancer-targeted therapy. Such carbon dots-based targeted with carbon dots in both understanding their fundamental
cancer therapy can vastly increase the therapeutic effect and aspects and in their practical applications in recent years, even
decrease the side effects, and thus may trigger a revolution in though there still exist some debates and challenges to over-
the diagnosis, treatment, and prevention of cancer.178 come. We believe that this kind of novel nanomaterial holds a

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bright future. Someday, carbon dots may replace some currently 16 B. Zhu, S. Sun, Y. Wang, S. Deng, G. Qian, M. Wang and
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There are no conflicts to declare. 20 S.-L. Hu, K.-Y. Niu, J. Sun, J. Yang, N.-Q. Zhao and X.-W. Du,
J. Mater. Chem., 2009, 19, 484–488.
21 V. Strauss, J. T. Margraf, C. Dolle, B. Butz, T. J. Nacken,
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This work was supported by Ministry of Education Singapore 22 S. Zhu, Q. Meng, L. Wang, J. Zhang, Y. Song, H. Jin,
through the Academic Research Fund under Projects RG105/16
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K. Zhang, H. Sun, H. Wang and B. Yang, Angew. Chem.,

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