Chemical Engineering Journal 454 (2023) 140069

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Review

Supra-(carbon dots) with versatile morphologies and promising

optical properties
Di Li a, *, Yanfei Qu a, Xiaoyu Zhang a, Weitao Zheng a, Andrey L. Rogach b, c, *, Songnan Qu d, e, *
a
Key Laboratory of Automobile Materials, MOE, School of Materials Science and Engineering, Jilin University, Changchun 130012 PR China
b
Department of Materials Science and Engineering, and Centre for Functional Photonics (CFP), City University of Hong Kong, Hong Kong SAR 999077 PR China
c
Shenzhen Research Institute, City University of Hong Kong, Shenzhen 518057 PR China
d
Joint Key Laboratory of the Ministry of Education, Institute of Applied Physics and Materials Engineering, University of Macau, Avenida da Universidade, Taipa, Macao
SAR 999078 PR China
e
Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macao SAR 999078, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Through non-covalent or covalent assembly of carbon dots (CDs), functional CD assemblies (supra-CDs) with
Carbon dots versatile architectures can be created. Among non-covalent forces, various supramolecular interactions can be
Assemblies used for this purpose, including amphiphilic interactions, H-bonding, electrostatic and π–π interactions, and van
Morphology
der Waals forces. Among covalent ones, chemical reactions including coordination interactions and interparticle/
Optical properties
Bio-applications
intermolecular covalent condensation of CDs result in the formation of supra-CDs. All these different kinds of
interactions of CD building blocks have an impact on energy band structures and photophysical and photo­
chemical processes and thus endow supra-CDs with intriguing optical properties. We review the recently
emerged research field of supra-CDs in terms of their synthesis, morphologies, assembly-induced optical prop­
erties such as emission quenching or enhancement, occurrence of polarized emission and optical chirality, and
underlying mechanisms. Their specific advantages for applications such as photothermal conversion and
photodynamic therapy are presented, in order to inspire further development of supra-CDs.

1. Introduction influenced by the core/surface physicochemical properties as well as

As a rather young member of the extended family of carbon-based
nanomaterials, carbon dots (CDs), which are carbon-based colloidal
nanoparticles with dimensions typically below 10 nm, have attracted
great attention and experienced rapid development in the past decade
by virtue of their well-documented biocompatibility, low cost, and
intriguing optical properties, in particular rather efficient color-tunable
photoluminescence (PL) [1–7]. CDs are generally considered to be
composed of the carbon-based core containing sp2/sp3 domains, and
functional groups at the surface which include organic moieties or
polymer side chains. As this kind of structures can be easily obtained by
conjugation/carbonization of widespread small molecules, polymers
and even natural sources of carbon, or decomposition of bulk carbon-
based materials, various kinds of precursors, synthesis routines and
post-preparative treatments have been developed to tailor the structure,
morphology and optical properties of CDs [8–17].
It is well established that the optical properties of CDs are strongly
interactions with environment [2,9,18–21]. For example, sp2 domains
and heteroatoms doping in the cores of CDs commonly influence the
intrinsic bandgap of CDs, and surface groups with electron donating/
withdrawing properties, different oxidation degrees, or molecular flu­
orophores play important roles in the alignment of energy levels and the
related optical transitions. Moreover, the PL of CDs is highly susceptible
to environment changes e.g. solvent, pH and temperature. Besides the
control of core/surface states, interparticle interactions provide yet
another pathway in regulating the optical properties of CDs, because
abundant surface groups of CDs offer active sites for supramolecular
interactions or chemical bonding. Consequently, exploring CDs as
building blocks, their assemblies denoted as “supra-CDs” can be con­
structed through either non-covalent or covalent assembly of CDs, which
exhibit extended dimensions, peculiar morphologies and optical prop­
erties absent in individual CDs, as illustrated in Fig. 1. The spatial
arrangement of CD building blocks and their interparticle interactions
not only determine the morphology of supra-CDs but also play important

* Corresponding authors.
E-mail addresses: dili@jlu.edu.cn (D. Li), andrey.rogach@cityu.edu.hk (A.L. Rogach), songnanqu@um.edu.mo (S. Qu).

https://doi.org/10.1016/j.cej.2022.140069
Received 12 July 2022; Received in revised form 7 October 2022; Accepted 24 October 2022
Available online 8 November 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
D. Li et al.
roles in their physicochemical properties. Accordingly, both energy
levels and electron transition pathways in supra-CDs are determined by
the synergistic effect of intrinsic electron structures and interparticle
interactions of CDs, which determine the related optical processes, such
as absorption, PL, photothermal conversion, and photosensitization
(Fig. 1). Due to such versatile morphologies and optical properties,
supra-CDs recently attracted increasing research efforts to deeply un­
derstand the underlying structures and photophysical mechanisms in
assembled state, to engineer their optical properties, and furthermore, to
explore their potential applications, e.g. imaging, sensing, photo­
catalysis, energy conversion, and phototherapy.
Moreover, the construction of supra-CDs has often been extended to
hybrid assemblies, where CDs are integrated via supramolecular in­
teractions or chemical reactions with other counterparts, such as organic
molecules, biomaterials, polymers, and inorganic nanostructures. For
example, CDs have been combined via ionic self-assembly with bio­
polymers such as DNAs, proteins, polypeptides, and enzymes, which
generated hierarchical assemblies featuring attractive optical charac­
teristics for biosensing and biocatalysis [22–26]. Energy and/or charge
transfer are important processes which strongly influence optical be­
haviors (e.g. activation or deactivation of emission) of hybrid CD as­
semblies. In particular, the photoinduced energy/charge transfer within
CD assemblies could be vital for their utilization in energy conversion,
including photosensitization, photocatalysis, and optoelectronics
[15,27–31]. Guldi’s group assembled CDs together with various mo­
lecular materials, including electron-donating porphyrins [32,33] and
tetrathiafulvalenes [34], as well as electron-accepting perylendiimides
[35], tetracyanoanthraquinodimethane [36], or polymer-wrapped sin­
gle-walled carbon nanotubes [37], to systematically investigate the
electron transfer in those hybrid assemblies. Charge transfer occurring
both in ground and excited states of these supra-structures was revealed,
influenced by supramolecular and covalent intermolecular interactions
[38]. Numerous hybrid CD assemblies have been constructed for en­
ergy/charge management as well as integration of multiple functions,
which could largely enrich the research of CDs and give rise to versatile
platforms for their specific applications. This review mainly focuses on
the interactions between CD building blocks in supra-CDs and the
resultant versatile optical properties, and thus only offers rather brief
introduction on the hybrid assemblies based on CDs.
Herein, we will consider the current research progress of supra-CDs,
in terms of their synthesis, morphologies and attractive optical proper­
ties. Driving forces of the formation processes of CD assemblies are
discussed, and the structure-related optical properties are revealed.
Finally, their specific advantages for applications such as photothermal
conversion and photodynamic therapy are presented, in order to inspire
further development of supra-CDs.
Fig. 1. Schematic illustration of formation of supra-CDs through non-covalent or covalent assembly, and some of their versatile optical properties. The green and
orange short wavy lines represent different kinds of surface groups on individual CDs, while the red short wavy lines represent the covalent bonds formed by the
corresponding surface groups of adjacent CDs.
2
Chemical Engineering Journal 454 (2023) 140069
2. Synthesis of supra-CDs
The synthesis of CDs, acting as building blocks of supra-CDs, can
involve either top-down or bottom-up routines; both of these approaches
have been extensively summarized in numerous reports [10,39,40]. The
abundant surface functional groups, such as O containing groups (e.g.
carboxyl, aldehyde, hydroxyl, epoxy), N containing groups (e.g. amine,
pyrrolyl, pyridyl), hydrophobic organic groups (e.g. alkyl chains) and
polymers (e.g. polyethylene glycol, polyethylenimine), as well as the
rigid carbon core dominated by sp2 domains can provide active sites on
CDs for further surface modification or interactions with other species.
As the construction of supra-CDs depends on the interactions of these
building blocks, their synthesis can be generally carried out in two ways,
namely through interparticle supramolecular assembly (non-covalent
assembly) and interparticle chemical condensation (covalent assembly).
In terms of non-covalent assembly, various supramolecular in­
teractions, including amphiphilic interactions, H-bonding, electrostatic
and π− π interactions and van der Waals forces, can occur between CDs
depending on their peculiar surface characteristics, and either one or
several of these interactions could trigger the formation of supra-CDs,
and stabilize them afterwards. For example, above the critical micelle
concentration, amphiphilic CDs (those possessing both hydrophilic and
lipophilic surface groups) could assembly into micelles or inverse mi­
celles in H2O or nonpolar organic solvents, respectively [41–43]. H-
bonding and/or electrostatic interactions could provide driving forces
for CD assembly in many cases, arising from the abundant surface
groups such as carboxyl and amino groups [44,45]. In some reports, the
layered structure of CDs’ core facilitated layer-by-layer stacking of CD
building blocks via π− π interactions and provided nucleation sites for
formation and structure evolution of supra-CDs [46,47]. In another
interesting case, the built-in chemical information of CDs, in term of
graphene core sizes, species and locations of surface groups, were found
to guide the assembly of CDs on water surface and control the CD ori­
entations [48]. CDs with large core size became aligned parallel to the
water surface, which was driven by van der Waals interactions, whereas
CDs with smaller core size and carboxylic acid groups changed the
orientation in assemblies with the rigid core aligning out of plane from
the water surface, because of the hydrophilic interactions induced by
carboxylic acid groups.
In terms of covalent assembly, chemical bonding of the building
blocks, e.g. coordination interactions and interparticle/intermolecular
covalent condensation, offer a way for production of supra-CDs. Some
surface groups on CDs, e.g. carboxyl groups can easily coordinate with
metal ions such as Fe3+, Al3+, Gd3+, Ca2+, Cd2+ and induce assembly of
CDs via coordination bond bridges [49–53]. In other cases, CDs can
fuse/interconnect via surface chemical bonds upon thermal/electro­
chemical treatment. For example, dehydration and carbonization
occurred between surface carboxyl and amino groups of neighboring
D. Li et al. Chemical Engineering Journal 454 (2023) 140069

CDs in solvothermal reactions and yielded supra-CDs composed of fused

particles [54,55]. Schiff base reaction of amine-passivated CDs and
carbonyl contained agents resulted in crosslinking of CDs into supra-CDs
[56,57].

3. Morphology control

Programmed assembly enables hierarchical organization of nano­

scale particles. The formation of CD assemblies depends on multiple
factors, including driving forces, particle interactions and environment,
and as a result, the morphology of the resulting assemblies may greatly
differ on basis of different dynamic processes [52,58]. Morphology
control from individual dots to spheres [59–63], capsules [64], vesicles
[65,66], rods [67], rolls [54], ribbons [43], fibers [65,68], tubes [69],
sheets [70], crystals [46,47], etc., which can appear at nano- to micro­
meter scales has been realized for CD assemblies through different
pathways, as will be considered in this section.
As an important kind of driving force for non-covalent assembly,
amphiphilic interactions can strongly impact the assembly processes of
CDs. Ding et al. prepared supra-CDs in the form of microspheres with
diameters in the range of 0.5–3 µm in a water-in-oil (W/O) emulsion
system [61]. CD building blocks were confined in the water droplets,
and interlocked through the van der Waals forces, electrostatic in­
teractions and hydrogen bonding of hydroxyl and ammonia groups on
their surfaces, which resulted in the formation of solid spheres. Hou
et al. produced analogous spherical supra-CDs of ca. 100 nm in size
through the assembly of amphiphilic CD building blocks in the oil-in-
water (O/W) inverse emulsion [62]. Jia et al. constructed supra-CDs
in the form of nanospheres (with diameters around 100 nm) via ionic
self-assembly of positively charged CDs using negatively charged
amphiphilic sodium dodecyl benzene sulfonate as the crosslinking re­
agent [63]. Different from the isotropic spheres, Xiong et al. synthesized
anisotropic carbon nanorods (length: 50 ± 5 nm, diameter: 20 ± 2 nm)
through solvothermal treatment of precursor-assembled inverse micelles
formed by quarternarized citric acid surrounded by amino­
propylisobutyl polyhedral oligomeric silsesquioxane (POSS), as illus­
trated in Fig. 2A [67]. These nanorods consisted of interlinked small
polyaromatic hydrocarbon domains (<5 nm) which formed during the
dehydration and carbonization of citric acid molecules inside the inverse
micelles; they could be visualized in transmission electron microscopy
(TEM) images by etching away the surface POSS-cage layer (Fig. 2B).
Amphiphilic CDs synthesized by Xi et al. could also form W/O inverse
emulsion in water-chloroform system, and freeze drying of aqueous
solution of these CDs produced a monolith consisting of aligned
microribbons made from nanofibers [43]. Nandi et al. reported uni­
lamellar spherical vesicles, hundreds of nanometers to micrometers in
size, assembled from amphiphilic CDs adopting a bilayer arrangement
[66]. Sarkar et al. found out that amphiphilic CDs with aliphatic/aro­
matic substitutions on the surface could form self-assemblies in
Fig. 2. (A) A scheme of the inverse micelle formation with a subsequent
dimethylsulfoxide-water solution. Once the surface passivation of these
carbonization occurring during the synthesis of carbon nanorods. Possible
CDs changed from cholesteryl to naphthyl to palmitoyl in sequence, the linkages of POSS-C3H6NH2 with polyaromatic hydrocarbon domains in the
morphology of the respective assemblies progressively transformed inner part of the rods are presented. (B) TEM image of a single carbon nanorod
from vesicles to fibers (Fig. 2C) [65]. Addressing other kinds of non- (denoted here as “CNR”) before and after etching, whose inner structure was
covalent interactions, Srivastava et al. observed that the mixture of visualized by etching away the surface POSS-cage layer. The resultant structure
CDs passivated with electron-accepting and electron-donating groups, (denoted as “aq-CNR”) consists of interlinked small quasi-spherical particles,
respectively, formed hierarchical structural assemblies with rod-like which can be attributed to polyaromatic hydrocarbon domains. Reproduced
(first stage) and hollow ring (second stage) morphologies [71]. Singh with permission [67]. Copyright 2019, American Chemical Society. (C) Sche­
et al. reported that CDs with hexabenzocoronene as a core and aliphatic matic representation of the formation of various assemblies from different
hydrocarbons at the surface assembled into ordered fibers with di­ surface functionalized CD-based amphiphilic structures. Reproduced with
permission [65]. Copyright 2019, Royal Society of Chemistry. (D) A scheme
ameters of 100 nm and lengths of tens of micrometers [68]. Chen et al.
illustrating the structural evolution of CDs towards carbon nanorolls (denoted
adjusted the mass ratios of m-trihydroxybenzene to water, which trig­
here as “CNRs”), and further towards carbon nanobelts (denoted here as
gered assembly of hydrothermally produced CDs into supra- “CNBs”) via the solvothermal fusion and photothermally induced unfolding
architectures with different morphologies including stringed micro­ steps, respectively. High resolution TEM image of a carbon nanoroll (E), and a
tubes, biforked microtubes, branch-like structures, and microtube arrays fragment of carbon nanobelt (F). Reproduced with permission [54]. Copyright
[72]. Maity et al. [73] investigated the influence of the chain length on 2021, American Chemical Society.
the self-assembly of CDs with poly(ε-caprolactone) of different

3
D. Li et al. Chemical Engineering Journal 454 (2023) 140069

polymerization degrees grafted on the surface. The CD assemblies
transformed from J-aggregates (polymerization degree of 3) to H-ag­
gregates (polymerization degrees of 7, 15, 21), along with variation in
morphology from toroid (polymerization degree of 3) to spheroid
(polymerization degree of 7) to rodlike (polymerization degrees of 15
and 21) structures, when the chain length of poly(ε-caprolactone)
increased. The authors ascribed this kind of behavior to the polymer
chain interactions including van der Waals forces and H-bonding, which
dictated the π stacking of CDs and resulted in different kinds of
assemblies.
Reports on assembly of CDs into superlattices realized by weak su­
pramolecular interactions are relatively scarce. Kim et al. reported that
CDs could assemble into superlattices with layer-by-layer internal
structures in a binary solution system comprising N,N-dimethylforma­
mide (DMF) and several other solvents, such as water, amyl alcohol, and
hexane [46]. Several shapes of the formed superlattices were visualized
using scanning electron microscopy (SEM), ranging from hexahedron,
truncated hexahedron to truncated octahedron in DMF-H2O (Fig. 3A-D),
rectangular rods in DMF-amyl alcohol, or slab-like particles in DMF-
hexane. Their different morphology was diversified due to intimate as­
sociation of CDs with those different solvents, resulting in the highly
faceted structures by forming efficient molecular packings and tuning
the cohesive energies of crystal facets. Xiong et al. obtained needle-like
microcrystals of CD assemblies (Fig. 3E) at the liquid–air interface using
templates of amphiphilic cellulose nanocrystals [47]. Microcrystals with
lengths of 53 ± 10 μm and diameters of 2.1 ± 0.5 μm exhibited multi-
lamellar morphology and were composed of nematic CD nanofibril
bundles (Fig. 3F). Moreover, microcrystals with several other shapes,
including long fibers (Fig. 3G), microflowers (Fig. 3H) and microplates
(Fig. 3I) could be obtained with an aid of different amphiphilic tem­
plates such as polyoxyethylene sorbitan monostearate (Tween 60),
polyvinylpyrrolidone, and hexadecyltrimethylammonium bromide,
respectively.
Various kinds of covalent interactions can also result in the formation
of supra-CDs with versatile morphologies. Liang et al. used a fusion
enabled by interface dehydration of CD building blocks as shown in
Fig. 2D to produce carbon nanorolls adapting the shape of multilayer
cylinders (diameter: 20–40 nm, height: 7–20 nm, as exemplified in TEM
image presented in Fig. 2E). Upon 655 nm laser irradiation, these carbon
nanorolls could be further uncoiled (Fig. 2D) into carbon nanobelts with
lengths reaching several hundreds of nanometers (Fig. 2F), which was
ascribed to the decrease of the interlayer H-bonding [54]. Hu et al. made
use of Schiff bases forming at the surface of CDs which triggered the
assembly of CDs into rod-like polycrystalline structures bundled
together [57]. Wang et al. observed that supra-CDs with hyperbranched
fractal structures could be formed via assembly and further carboniza­
tion of in situ generated CDs featuring low surface ζ-potential in hy­
drothermal process [74]. Upon electrochemical treatment, Gao et al.
fabricated crystalline graphite nanocapsules (10–20 nm in size) through
assembly and graphitization of CD building blocks using H2 gas bubbles
as soft templates [64]. Cheng et al. conducted electrophoretic deposition
of CDs with abundant carboxyl groups within a nanoporous anodic
aluminum oxide template, and obtained CD-based nanotubes with di­
ameters of ca. 200–300 nm and porous walls [69]. Hou et al. produced
ultrathin (2.15 nm in thickness) carbon nanosheets of several micro­
metres in lateral size through the CD assembly driven by thermal
treatment in the presence of Na catalyst [70]. Qu et al. used CDs with
carboxyl groups on the surface to assemble them into different structures
driven by coordination interactions with trivalent metal cations, such as
Al3+, Fe3+ [49]. These assemblies exhibited diverse morphologies
including chains, sheets, shells and stars, on a size scale of tens to
hundreds of nanometers, which was controlled by the energy of coor­
dination bonds between metal cations and carboxyl groups. A stepwise
assembly mechanism of CD aggregation in aqueous solution triggered by
Ca2+ cations was revealed by Li et al. [52], which involved protonation/
deprotonation of CDs and self-assembly into CD-water-CD for the first
step, edge-to-edge crosslinking of small CD pieces induced by Ca2+ and
then conversion into 3D structures via π− π stacking for the second step,
and subsequent aggregation into precipitates at the end.
Apart from the mentioned nano/micro-sized structures, CDs could
also assemble into macro-scale 3D architectures via different ap­
proaches. For example, 3D porous carbon-based frameworks were
formed by calcining CD building blocks [75,76]. Non-covalent in­
teractions drove CDs assembly into layered structures [77] or porous
solid networks [78]. Pal et al. found out that CDs could assemble into 3D
crystalline structures via complexation (growth of orthorhombic hopeite
structures) between the phosphate surface groups and Zn2+ cations [79].
4. Optical properties of supra-CDs
Different morphologies, and functional groups of supra-CDs can have
a significant impact on their photophysical properties, e.g. the align­
ment of energy levels in ground and excited state, and thus determine
their optical properties different from those of individual CD building

Fig. 3. (A)-(D) SEM images of assembled CDs, showing hexahedron, truncated hexahedron, octahedron, and truncated octahedron morphologies (scale bar: 200 nm).
Reproduced with permission [46]. Copyright 2017, John Wiley & Sons. (E) Confocal fluorescent microscopy image of needle-like microcrystals of CD under exci­
tation of 488 nm; frame (F) shows the atomic force microscopy (AFM) height image of these microcrystals. Optical microscopy image of (G) long CD crystal obtained
with an aid of Tween 60 (bottom left inset: the photo of a freestanding crystal handled by a regular tweezer), (H) CD microflower obtained with an aid of poly­
vinylpyrrolidone (bottom right inset: multiple CD discs formed after 1 day), and (I) CD microplates obtained with an aid of hexadecyltrimethylammonium bromide.
Top right insets in the frames (G), (H), and (I) provide photographs of the corresponding crystal dispersions. Reproduced with permission [47]. Copyright 2020, John
Wiley & Sons.

4
D. Li et al.
blocks. In this section, optical properties of supra-CDs including ab­
sorption and switchable/polarizable PL, the related photothermal con­
version and photodynamic processes, and their possible applications in
sensing, encryption, etc. will be considered.
4.1. Absorption
Energy levels of supra-CDs can be influenced by geometrical
arrangement of building blocks and their interactions, and conse­
quently, supra-CDs often exhibit absorption characteristics different
from those of the individual CDs. As an example, enhanced interlayer
π− π conjugation was realized in compact rolling geometry of supra-CDs,
which contributed to the narrow-band main absorption centered at 665
nm, while the main absorption bands of individual CD building blocks
and uncoiled supra-CDs in the form of nanobelts were located at shorter
wavelengths [54]. H-type and J-type aggregates refer to “side-by-side”
and “head-to-tail” packing arrangement of fluorophores in assemblies,
respectively. Dipolar coupling between monomers causes splitting of
excited energy levels, and only electronic transitions to higher (lower)
excited levels are allowed in H-(J-) aggregates. Consequently, a blue-
shifted (red-shifted) absorption and a suppressed (enhanced) radiative
decay rate are observed in H-(J-) aggregates as compared to their
respective monomers (Fig. 4) [80]. Various interparticle interactions,
and mostly interactions of the surface groups of CDs might dictate the
stacking geometry of CD cores (sp2 domains) and stabilize their as­
semblies, and result in the formation of H-/J-aggregates of CDs. Several
reports have revealed that assembly of CDs into H-type or J-type ag­
gregates could occur and induce blue or red shift of CD absorbance
respectively [63,81,82]. Devi et al. validated the existence of CD ag­
gregates in polar solvents via spectroscopic study [81]. Appearance of
the high-energy sharp absorption band (at ca. 260–300 nm) in aprotic
solvents and in highly viscous ethylene glycol revealed the formation of
H-aggregates through hydrogen bonding, whereas the low-energy ab­
sorption band (at ca. 300–350 nm) which was more intense in protic
solvents suggested that J-aggregates formed via dipole-dipole interac­
tion. Jia et al. reported the absorption redshift of ca. 50 nm for the CD
assembled nanospheres, which was ascribed to the formation of J-ag­
gregates [63].
The coupling of surface states between adjacent CDs have been
Fig. 4. Exciton band energy diagram for a monomer (middle), and its J-
aggregate (left) and H-aggregate (right). Left: The “head-to-tail” arrangement of
adjacent monomers (here: CDs) in a J-type aggregate results in the splitting of
excited energy levels where the electronic transitions to lower excited level are
allowed. Right: “side-by-side” arrangement of adjacent monomers (here: CDs)
in an H-type aggregates results in the splitting of excited energy levels where
the electronic transitions to higher level are allowed. Absorption (Abs) and
subsequent fluorescence (Fluo) processes are represented by upward and
downward arrows, respectively; possible internal conversion (IC) is also shown
as dashed downward arrows. θ is the angle between the transition moment of
the monomer and the line joining the monomer centers, which equals to 0◦ in
ideal J-type arrangement, and 90◦ in ideal H-type arrangement. Reproduced
with permission [81]. Copyright 2019, American Chemical Society.
5
Chemical Engineering Journal 454 (2023) 140069
shown to induce narrow band electron transitions in CD aggregates [83].
Li et al. constructed supra-CDs with a strong visible to near-infrared
(NIR) absorption band centered at 700 nm via assembly of UV-
absorbing CDs with spatially separated surface energy levels. The
coupled surface energy levels of adjacent CDs in the assembly contrib­
uted to the narrow band absorption of supra-CDs [44]. Similar phe­
nomenon was reported by Shen et al [84], who observed a broad visible-
NIR absorption band with maximum at 600 nm after assembly of UV-
absorbing CDs under acidic environment. In the report of Wu et al.,
solvothermal post-treatment of CDs resulted in the formation of supra-
CDs through interparticle dehydration [55]; different from CDs with
absorption tail extending over visible spectral range, additional ab­
sorption bands covering the spectral region of 550–700 nm arose in
supra-CDs, originating from the fused interfaces of CD building blocks.
In supra-CDs constructed by crosslinking between amine groups on
surface of CDs and aldehyde groups of glutaraldehyde [56], the imine
bonds introduced additional chromophore centers with absorption
bands in yellow and red regions, which was different to individual CDs
absorbing in the UV-blue region.
4.2. Photoluminescence
4.2.1. Photoluminescence in assembled state
Intermolecular interactions play important role in the PL properties
of aggregated fluorophores [85,86]. Aggregation-caused PL quenching
is a common phenomenon for many fluorophores, including CDs
[87,88]. In other cases, specific interactions of CD building blocks have
influenced PL characteristics of the supra-CDs, eventually resulted in the
appearance of aggregation induced emission (AIE) [89,90].
Concerning CDs assembled into J- or H-aggregates as illustrated in
Fig. 4, Devi et al. proposed that the excitation-dependent emission of
CDs could indeed be a consequence of the existence of J-aggregates, H-
aggregates, and higher-order assemblies including HH-, HJ-, JH-, and JJ-
aggregates [81]. Sharma et al. reported that the main excitation band
(at ~ 350 nm) of CDs split into concomitant blue-shifted and red-shifted
excitation bands with increasing concentration of CDs [91]. Meanwhile,
their temperature-dependent PL spectra revealed a strong decrease in
intensity with temperature for the high energy emission at 450 nm, in
contrast to the low energy emission at ~ 530 nm, whose intensity was
not obviously affected by temperature change. This behavior was
explained in terms of assembly of CDs into weak and strong H-aggre­
gates simultaneously existing in solution. In the report of Song et al., CD
assembly through the formation of H-bonds was found to occur in the
concentrated CD solution [92]. The emerging excitation bands with
maxima at 465 and 520 nm were ascribed to the formation of H-ag­
gregates and J-aggregates respectively, which facilitated the surface
energy transfer and thus gave rise to the long-wavelength emission in
yellow and red region. In another case, CDs assembled into J-aggregates
with the assistance of melamine via H-bonding [82]; yellow emission
was detected in the J-aggregates while individual CDs exhibited blue
emission. Wang’s group reported supra-CDs assembled from CDs pre­
pared from aromatic precursors, and ascribed their redshifted emissions
in NIR region to the formation of J-aggregates [59,63]. As stated in Ref.
[73], when compared to individual CDs, J-aggregates made of CDs with
short surface polymer chains displayed red-shifted absorption and
enhanced fluorescence intensity, whereas CDs with longer surface
polymer chains assembled into H-aggregates with blue-shifted absorp­
tion and quenched fluorescence.
In some other cases, AIE mechanism has been found to be deter­
mining the PL properties of supra-CDs. Yang et al. synthesized hydro­
phobic CDs with blue emission in dispersed state, and red emission in
aggregated state (Fig. 5A) [93]. These CDs could form J-aggregates after
addition of water, and as a result, the blue emission originated from the
carbonized cores was quenched due to π–π stacking, while the surface-
related red emission was turned on due to restriction of intra­
molecular rotation of symmetrical heterocycles around the disulfide
D. Li et al.
Fig. 5. (A) Formation of CD monomers and their aggregates (disulfide bond in dithiosalicylic acid is highlighted in yellow). (B) Responsible interactions and the
proposed structure of CD’s core and surface; the colors of glowing edges represent their PL color. Reproduced with permission under a Creative Commons
Attribution-NonCommercial-NoDerivs 4.0 International License [93]. Copyright 2019, Springer Nature.
bonds on the surfaces (Fig. 5B) [93]. CD assemblies with green emission
were formed upon increasing concentration of blue emissive CDs in
solution [94]; their close packing induced restriction of π–π interactions,
and caused electron redistribution and distortion of oxygen-related
surface groups, which was responsible for the observed redshift of the
emission band. The CD assembled microscopic crystals featured an
intense PL with a maximum at 542 nm, while the PL of random CD
aggregates was quenched [47]. This was because the molecular rota­
tions within monolayers were suppressed by ordered and dense packing
6
Chemical Engineering Journal 454 (2023) 140069
structure of crystals, which restricted the intermolecular energy transfer
and thus enhanced the emission. Another kind of supra-CDs displayed a
red-shifted PL peak at 596 nm in DMF/water mixture with an enhanced
PL intensity when their crystallization proceeded, as compared with
individual CDs emitting at 425 nm in DMF [46]. Interactions with
melamine–formaldehyde induced CD assembly allowing their encapsu­
lation within polymer microspheres. The blue emission of individual
CDs decreased while new emission bands covering 500–700 nm
increased because of the aggregation of CDs in the microspheres, which
Fig. 6. (A) Schematic illustration of the synthesis
and crosslinking structure of supra-CDs. Reproduced
with permission [56]. Copyright 2019, Royal Society
of Chemistry. (B) Assembly of the green emissive CDs
into fused supra-CDs via solvothermal treatment. (C)
Absorption and PL spectra of CDs and supra-CDs
(635 nm laser signal is removed and replaced with
dots). (D) Energy diagrams of CDs and supra-CDs,
which illustrate how the long-wavelength absorp­
tion and emission of supra-CDs are originated from
the fused interface (FI) structure. G0 represents the
ground state, and S(Cor) and S(FI) are energy states of
the cores of CDs and fused interfaces in supra-CDs,
respectively. Reproduced with permission under a
Creative Commons CC BY license [55]. Copyright
2021, John Wiley & Sons.
D. Li et al. Chemical Engineering Journal 454 (2023) 140069

broadened their PL spectrum into white emission [95]. CDs assembled
into supra-CDs via the interaction between the negative CDs and the
positive amino compounds during the reaction with polyethyleneimine
showed photoluminescence quantum yield (PL QY) increasing from 15
% to 23 % [96]. Supra-CDs produced by Gd2+ induced CD assembly
exhibited PL intensity 6 times higher than for individual CDs, because of
the strengthened inter-cluster aurophilic interactions and reduced non-
radiative transitions in assembled structures [51]. Similar PL enhance­
ment occurred in Cd2+ induced CD assemblies due to metal-induced
aggregation-induced enhanced emission effect [53]. In yet another
related study [71], supra-CDs were composed of electron-accepting
groups modified CDs (CD-A) and electron-donating groups modified
CDs (CD-D). The optical characteristics of these supra-CDs were domi­
nated by CD-A, due to the interactions of CD-A and CD-D in the hier­
archical assembly.
Crosslinking of amine functionalized CDs and glutaraldehyde resul­
ted in formation of supra-CDs with multiple emission bands in blue,
green and red [56]. Compared to the original blue emission (454 nm)
from individual CDs, additional emission bands in green (559 nm) and
red (656 nm) originated from the imine bonds in a condensed envi­
ronment (Fig. 6A). PL properties of these supra-CDs could be modulated
by varying the amine compounds or aldehyde linkers. Ultra-small CDs
with diameters of ~ 0.5 nm assembled into supra-CDs exhibited white
fluorescence [97], originating from widely distributed surface-state
emissive centers. Chen et al. synthesized CDs capped with fatty acids,
which self-assembled into blue-, green-, yellow-, and red-emissive CD
aggregates with increasing diameters by tuning the amount of those
acids [98]. In another example, interparticle dehydration of green
emissive CDs at a high concentration produced supra-CDs featuring long
wavelength absorption band and efficient deep red emission in DMF,
with PL QY of 15.6 % (Fig. 6B-C) [55]. The fused interfaces of CDs
(Fig. 6B) endowed interactions of their surface electron-withdrawing
and electron-donating groups, which resulted in narrow-bandgap elec­
tron transitions and thus an appearance of deep red PL, as illustrated in
Fig. 6D.
4.2.2. Photoluminescence quenching or enhancement
As we discussed above, emission of individual CDs can be quenched
or enhanced upon formation of supra-CDs, while it can return to the
original state when supra-CDs disaggregate into well dispersed CDs. This
aggregation-dependent optical behavior makes the PL of supra-CDs
sensitive to the external stimuli which trigger their formation, struc­
ture evolution, and eventual disassembly; this may lead to applications
of supra-CDs in sensing and encryption. Chen et al. used yellow-green
emissive CDs with thiol groups at the surface to expose them to H2O2,
which resulted in the oxidation of the latter to -S–S- bonds; this induced
the CD assembly and resulted in the PL quenching [99]. The authors
used this assembly for the glucose detection with a rather low detection
limit (0.03 μM) and high selectivity, because glucose-oxidase catalyzed
oxidation of glucose resulted in the generation of H2O2. Lou et al.
assembled amphiphilic CDs into supra-CDs which was accompanied
with the PL quenching in toluene [41]. When these supra-CDs were
treated with water, their PL band located at ca. 500 nm was enhanced,
with PL QY increasing from 6 % to 40 %. This happened because water
triggered the decomposition of supra-CDs into CDs in dispersed state
(Fig. 7A schematically shows how does this happen between the paper
fibrils), so that after water spraying on the paper the emission of CDs
became turned on (Fig. 7B). On this basis, water-jet printing and sweat-
pore mapping of fingerprints could be demonstrated using supra-CD-
coated paper, as illustrated in Fig. 7C-F. Fig. 7C shows a photograph
of a fingerprint appearing on a supra-CD-coated paper under UV irra­
diation, with the fluorescence microscopy image of the magnified
fingerprint area marked in (C) provided in Fig. 7D. The green lumines­
cent dots result from the disassembly of supra-CDs into CDs triggered by
water secreted from sweat pores. The respective superimposed image of
contrast-enhanced luminescent CDs (in red) on a digital fingertip image
and its magnified image are shown in Fig. 7E and 7F, respectively. The
locations of sweat pores (black microdots) in the digital fingertip image
match well with the luminescent dots.
In other cases, supra-CDs with suppressed PL were constructed by
using anti-solvent treatment [60], or in situ self-assembly driven by non-
covalent interactions during the CD synthesis [78]. Similar to what has
been described above, these supra-CDs could be disassembled into in­
dividual CDs in a good solvent, which resulted in PL recovery. As re­
ported by Liu et al., amphiphilic CDs which have formed reversed
micelle-like assemblies in alkane solution exhibited yellow and blue PL

Fig. 7. (A) Schematic presentation of the water-induced disassembly of supra-CDs confined between the paper fibrils. (B) Changes in the emission spectra of a paper
coated by supra-CDs (excitation at 405 nm) happening upon water spraying. (C) Photograph of a fingerprint image printed on supra-CD-coated paper (scale bar: 5
mm). (D) Fluorescence microscopy image of the magnified fingerprint area marked in (C), whose green fluorescence signals are imaged in red pseudo-color here
(scale bar: 2 mm). (E) Superimposed image of contrast-enhanced luminescent CDs on a digital fingertip image (scale bar: 2 mm). (F) Magnified image of the marked
area in (E) (scale bar: 0.5 mm). Reproduced with permission [41]. Copyright 2015, John Wiley & Sons.

7
D. Li et al. Chemical Engineering Journal 454 (2023) 140069

bands corresponding to carboxylic and amide groups, respectively [42].

PL QY of the yellow emission (33 %) was stronger than of the blue one
(12 %), because the rotation/stretching of –COOH groups were limited
by the formation of H-bonds, and also because the energy transfer pro­
cess from the blue to yellow fluorophores was effective in the aggregated
state. Once dissolved in protic solvents, CDs appeared in the dispersed
state, and the blue emission became dominate alongside with an obvious
decrease of the yellow one, caused by the absence of H-bonding and
diminished energy transfer. Cho et al. embedded CDs into polyacrylic
acid block of polystyrene-b-polyacrylic acid, which then formed micelles
either in water or in toluene [100]. The micelles in water had a
strawberry-like shape with CDs appearing as patches on the polyacrylic
acid corona surface, while those in toluene had a reversed arrangement
with CDs in the micelle core. The PL intensity of micelles in water was
approximately twice as strong as in toluene, because π− π interactions of
closely packed CDs in the core induced PL quenching in the latter. Op­
tical characteristics of CDs in NIR region also varied upon formation and
uncoiling of supra-CD nanorolls [54]. Thanks to their compact rolled
structure which protected emissive centers from environment and thus
suppressed nonradiative recombination, carbon nanorolls showed
enhanced NIR emission with a maximum at 695 nm and PL QY of 9.2 %,
which was significantly higher than of individual CDs with PL QY of 2.8
%. Irradiation with a 655 nm laser triggered unrolling of carbon nano­
rolls into carbon nanobelts, which was accompanied with significantly
decreased NIR emission and appearance of green and red emissions.
Taking advantage of this morphology depended emission changes,
multilevel luminescence encryptions has been realized on paper stam­
ped with carbon nanorolls based ink [54].
Wang et al. designed a ratiometric fluorescent probe by making use
of dual luminescent centers in supra-CDs sensitive to external temper­
ature [45]. Supra-CDs with dual emission at 440 and 590 nm were
fabricated via electrostatic assembly of oppositely charged CDs with
blue and orange PL bands. The orange PL band at 590 nm of supra-CDs
showed reversible response to external temperatures in the range of
15–85 ◦ C depending on the configuration of surface amide bonds, while
the blue PL was insensitive to temperature in this range, and thus could
be conveniently used as an internal reference. Consequently, these
supra-CDs were employed as a fluorescence nanothermometer for Fig. 8. (A) A sketch illustrating the emission anisotropy of carbon nanorods,
cellular temperature imaging. and (B), (C) their blue and orange PL spectra recorded with parallel (//) and
perpendicular (⊥) excitation and emission polarizer settings under excitation at
4.2.3. Polarized photoluminescence and optical chirality 365 nm (B) and 450 nm (C). Reproduced with permission [67]. Copyright 2019,
Optical properties of CDs such as linearly polarized PL, circular di­ American Chemical Society.
chroism, and circularly polarized luminescence, have attracted growing
attention in recent years, as they may extend their potential applications and porphyrins [110]. To realize the CPL, an effective strategy is to
to liquid crystal displays, detectors, optical data storage, chirality confine CDs within chiral templates. Co-assembly of the cellulose
sensing, life sciences and catalysis [101–105]. Anisotropic morphology, nanocrystals (CNC) and CDs resulted in formation of helical super­
internal structure and geometrical arrangement in different kinds of structures with left-handed chiral nematic orientation, which could
supra-CDs could influence the light-matter interactions and thus induce transform spontaneous emission of CDs to right-handed CPL [105,111].
chirality or polarized emission. As an example for the latter, the struc­ The wavelength-tunable CPL of CNC/CD assemblies was influenced by
tural anisotropy of carbon nanorods illustrated in Fig. 8A (which were intrinsic helical organization and optical properties of CDs, and showed
introduced earlier in this review, see Fig. 2A) resulted in the dual high degree of CPL with a dissymmetry factor (glum) of − 0.2 [111] and
polarized emission changing from blue (460 nm) to yellow (565 nm) − 0.74 [105]. In other cases, supramolecular assemblies of CDs and
upon excitation at 365 nm and 450 nm, respectively (Fig. 8B-C) [67]. organic lipid gel enantiomers showed circularly polarized multi-color
The emission of these nanorods originated from the POSS-interlinked and white emissions with glum reaching ~ 0.01 [112,113]. In a recent
polyaromatic hydrocarbon (PAH) domains incorporated within supra- study, Zhang et al. prepared achiral CDs which were self-assembled into
CD framework, and was polarized due to selective excitation of PAH helical structures with two diverse assembly modes (P and M) in
domains oriented along the excitation path. The anisotropy of emission different bi-solvent systems. As a result, the CD assemblies exhibited P-
of supra-CDs depended on the excitation wavelength and reached a chirality and R-CPL in ethanol-water bi-solvent system, and M-chirality
relatively high value of up to 0.3. and L-CPL in acetonitrile-water bi-solvent system [114].
Chiral CDs have been produced by exploiting chiral precursors or Overall, the formation of supra-CDs should have a significant impact
surface modification with chiral ligands [102,106], which endows the on the core and surface states of CD building blocks based on different
chiral optical activity on CDs, evidenced by the appearance of circular structures, geometrical arrangements, and interparticle interactions,
dichroism and, in some cases, circularly polarized luminescence (CPL) resulting in the occurrence of versatile optical properties. The local
[101,107]. The reported chiral CD assemblies could either retain the confined environment of cores in assemblies, for example, could induce
chirality in self-assembled hydrogels [108], or facilitate chirality PL quenching via π− π interactions or energy transfer, or PL enhance­
transfer from the chiral CDs to organic molecules such as pyrene [109] ment via restriction of intramolecular motions, or red/blue shift of the

8
D. Li et al.
absorption/PL bands due to the formation of J-/H-aggregates. Inter­
particle interactions may also quench or activate the surface PL signals,
as well as introduce new fluorescent centers. Furthermore, formation of
anisotropic supra-structures may induce optical anisotropy which was
absent in individual CDs. Thus, the formation of supra-CDs may have a
complex and diverse impact on the core/surface state of CDs due to the
diversity of core and surface structures of CDs and different assembly
approaches. As a result, studying the optical properties of supra-CDs and
the underlying mechanisms necessitates a case-by-case analysis.
9
Chemical Engineering Journal 454 (2023) 140069
5. Application in photothermal conversion and
photosensitization
5.1. Photothermal conversion
As already outlined above, interactions of CDs in a CD assembly can
induce their long-wavelength absorption. Upon excitation with a long-
wavelength light, especially within the NIR region, excited electrons
can relax to the ground state via nonradiative transitions, accompanied
with an increased temperature of the sample and the environment. This
ability of supra-CDs allows us to employ them for the photothermal
conversion, and makes supra-CDs with a long-wavelength absorbance
Fig. 9. (A) Schematics of the structure, energy
alignment, absorption pathways (shown by violet
arrows) and photothermal conversion process
through the nonradiative deactivation of the
electrons within the coupled surface energy
levels in the form of heat (shown by wavy red
arrows). Blue and yellow horizontal bars repre­
sent the surface energy levels; red jagged lines
represent the NIR laser irradiation. (B) Absorp­
tion spectra (normalized at the absorption max­
ima in the UV region) of supra-CDs and
individual CDs they were built from. (C) Tem­
perature elevations of supra-CD aqueous disper­
sions with different concentrations under 808 nm
laser irradiation, compared with a pure water.
Reproduced with permission under a Creative
Commons Attribution-NonCommercial-NoDerivs
4.0 International License [44]. Copyright 2016,
Springer Nature. (D) IR thermal images of a
mouse taken at different time intervals under
655 nm laser irradiation at the tumor region after
intratumor (i.t.) injection of supra-CDs. PA B-
scan images of tumors in mice after intratumor
injection of supra-CDs (E), and after intravenous
injection of supra-CDs at different time points
(F). Reproduced with permission [115]. Copy­
right 2018, John Wiley & Sons.
D. Li et al.
attractive for applications in photothermal therapy (PTT)
[55,62,84,115], photoacoustic imaging (PAI) [116,117] and solar water
evaporation [118,119].
5.1.1. Photothermal therapy
PTT is dealing with the light-to-thermal energy conversion and
subsequent thermal ablation of cancer cells. Photoabsorbing agents are
critical in PTT, and should exhibit large extinction coefficient in NIR
region, high photothermal conversion efficiency, low toxicity, and
tumor-homing ability. Supra-CDs introduced by Li et al. [44] had strong
NIR absorption band peaked at 700 nm (Fig. 9A-B), and their photo­
thermal conversion ability (Fig. 9C) reached a noticeable efficiency of
53 %, when measured under 808 nm laser irradiation. Inhomogeneously
distributed positive and negative surface groups on individual CDs
evoked spatially separated surface state energy levels, but electron
transitions between them were forbidden in individual CDs. After for­
mation of supra-CDs driven by electrostatic interactions and hydrogen
bonding between the charged surfaces, the surface energy levels of
adjacent CDs overlapped spatially, and electron transitions through the
coupled surface energy levels occurred and contributed to their narrow
band absorption. The photothermal conversion process was ascribed to
the nonradiative deactivation of excited electrons within the coupled
surface energy levels of adjacent CDs (Fig. 9A). Because of their small
dimensions, supra-CDs could accumulate in tumor sites via passive
targeting, and were further used as imaging and therapeutic agents in
PAI (vide infra) and PTT [115]. After intratumor injection of supra-CDs
(500 µg mL− 1, 200 µL), in vivo tumor PTT was conducted under 655 nm
laser irradiation (1 W cm− 2). The local tumor temperature reached 65 ◦ C
within 300 s (Fig. 9D), which resulted in eradication of the tumor. PTT
conducted after intravenous injection and subsequent tumor accumu­
lation of supra-CDs inhibited the tumor growth and prolonged the life
span of mice. Other visible-NIR absorbing supra-CDs (maximum ab­
sorption at 600 nm) offered photothermal conversion with an efficiency
of 41.7 % under excitation of 808 nm laser [84], and their subsequent
surface modification with mitochondria- and cancer cell-targeting pep­
tides improved the cancer cell subcellular organelle specificity without
influencing the efficiency. Consequently, these supra-CDs could be used
as active targeting agent which precisely induced cancer cells ablation in
PTT. Supra-CDs with fused interfaces introduced in Ref.[55] possessed
an absorption band in the range of 550–700 nm and exhibited photo­
thermal conversion in water under 655 nm excitation, with an efficiency
of 26 %. In vivo tumor PTT was realized via intratumor injection of
supra-CDs (800 µg mL− 1, 100 μL), and the temperature of tumor site
increased to 70 ◦ C within 5 min under 655 nm laser irradiation (0.5 W
cm− 2). As reported by Hou et al. [62], supra-CDs showed red-shifted (by
ca. 30 nm) absorption with an enhanced absorption tail in the 600–800
nm spectral range, which resulted in photothermal conversion efficiency
of over 43 %, as compared with 38.5 % for individual CDs, under 671 nm
irradiation. We can conclude that supra-CDs showed better performance
than individual CDs during in vitro PTT, because of the enhanced
cellular uptake and photothermal effect.
5.1.2. Photoacoustic imaging
Photoacoustic imaging (PAI) is a hybrid biomedical imaging method
which involves photon absorption, photothermal conversion, thermo­
elastic expansion (with generation of acoustic waves), and ultrasound
detection; it offers high contrast and high spatial resolution. CDs with a
good photothermal conversion performance are commonly explored as
photoacoustic imaging contrast agents alongside with PTT. Bu et al.
prepared CD assemblies using a covalent click reaction between the
surface functionalized CDs in a W/O emulsion system, which exhibited
enhanced NIR absorption as compared with individual CDs, and showed
a photothermal conversion efficiency up to 32.3 %. Acting as a PAI
contrast agent, these CD assemblies generated significant PA signals,
which increased linearly with concentration, under excitation with an
808 nm laser [116]. Jana et al. prepared supra-CDs with NIR absorption
10
Chemical Engineering Journal 454 (2023) 140069
at ~ 705 nm via self-assembly of CDs with 1,2-distearoyl-sn-glycero-3-
phosphoethanolamine-poly(ethylene glycol), which exhibited a
concentration-dependent linear increment of photoacoustic amplitude
under excitation with a 700 nm pulse laser, and revealed the passive
targeting ability of supra-CDs based on the strongest photoacoustic
signal in a tumor region at 9 h post-injection [117]. Xu et al. investigated
the in vivo PAI performance of supra-CD contrast agents after their
intratumor and intravenous injection, as mentioned above in relation to
Ref.[115]. After intratumor injection, strong PA signals were observed
from the tumor area (Fig. 9E), while increasing PA signals were recorded
from the tumor tissue over time after intravenous injection, peaking at 5
h post-injection (Fig. 9F).
5.1.3. Solar water evaporation
Solar-driven water evaporation can be also realized via photo­
thermal conversion process. Hou et al. found out that increasing the
concentration of CD suspension could induce the formation of branch-
shaped supra-CDs [118]. Comparing with individual CDs, the supra-
CDs showed enhanced absorbance over the entire UV–vis region with
obviously red-shifted absorption edge and thus good photothermal
conversion ability corresponding to the nonradiative recombination
within the coupled surface levels. Using supra-CDs as a photothermal
layer and a balsa wood with microchannels as a heat barrier layer, supra-
CDs@wood composites exhibited good performance in solar water
evaporation, with a water evaporation rate of 2.27 kg m− 2 h− 1 and en­
ergy efficiency of solar vapor generation reaching 92.5 %. Hang et al.
produced supra-CDs via co-assembly of CDs and molecular fluorophore
by-products simultaneously formed during the preparation of CDs
[119]. These supra-CDs exhibited a broad absorption covering the whole
UV–vis–NIR spectral region in solid state, and a high internal solar-to-
heat conversion efficiency of 98.8 %. The interfacial water evapora­
tion system based on those supra-CDs exhibited an evaporation rate of
2.1 kg m− 2h− 1 and solar-to-vapor energy efficiency of 133.9 % under
one sun irradiation, and a good salt-rejection performance.
5.2. Photosensitization
In several other systems, intersystem crossing of the excited electrons
to triplet state permitted energy transfer from supra-CDs to ground state
of oxygen, which generated singlet oxygen (1O2), which can be used for
photodynamic therapy. Also here, enhancement of absorption in the
long wavelength region enabled excitation with deep red/NIR light
sources. Several kinds of supra-CDs able to generate 1O2 with consid­
erable yield were developed and employed as photosensitizers by
Wang’s group [59,63,120]. As an example, assembly of CDs resulted in a
significant red-shift (by ca. 50 nm) of absorption peak as illustrated in
Fig. 10A, allowing activation of the 1O2 generation with a QY of ca. 45 %
under 671 nm excitation [63]. As a result, CD nanospheres could be used
as efficient photosensitizers for tumor ablation under 671 nm laser
irradiation (Fig. 10B-C), which improved the survival rate of the treated
mice (Fig. 10D). In another study [59], CDs synthesized with an aid of
manganese(II) phthalocyanine assembled into supra-CDs with a red-
shifted absorption, which generated 1O2 with QY of 40 % under 635
nm excitation. Integrating their NIR emission (at 745 nm) and para­
magnetism, the supra-CDs were applied as a smart contrast agent in NIR
fluorescence (FL) and T1-weighted magnetic resonance dual mode im­
aging, and as an effective agent for photodynamic therapy, which could
ameliorate tumor hypoxia due to Mn(II) catalyzed H2O2 decomposition
(Fig. 10E). Moreover, the use of supra-CDs could promote enhanced
tumor accumulation of therapeutic agents and improve the targeted
anti-tumor therapy [50,51].
6. Conclusions and outlook
As rather recently evolved materials within the booming research
field of CDs, the variety of demonstrated supra-CDs is growing. Control
D. Li et al.
of the assembly processes of CDs and the related understanding of op­
tical properties of resulting supra-CDs strongly rely on identification of
the geometrical arrangements and interactions of CD building blocks.
Among the topics we discussed in this review, the versatile morphology
of supra-CDs, rearrangement of the energy bands, tunability of PL
spectra in the assembled state, structure- and environment-responsive
PL emission, polarized PL, and charge and energy transfer are among
advantages of CD assemblies which may be absent in individual CD
building blocks and can promote their applications in areas of biomed­
icine, imaging, energy conversion, sensing and photocatalysis. Thus, the
development of supra-CDs with versatile assembly-guided optical
properties might unlock novel research perspectives and enrich the
family of the existing CDs.
In order to inspire further development of supra-CDs, some issues
inherently related to the CDs, such as determination of their exact in­
ternal structures, mechanisms of PL emission, as well as the reliable
synthesis and thorough purification/separation procedures should be
11
Chemical Engineering Journal 454 (2023) 140069
Fig. 10. (A) Absorption spectra of individual CD
and CD nanospheres (denoted as “CDNS”)
assembled thereof. (B) Photographs of tumor-
bearing mice which underwent 4 kinds of treat­
ments (irradiation with 671 nm laser; laser irra­
diation in the presence of CDs or CDNS; and
treatment with CDNS only), at day 0 and day 14.
(C) Time-dependent tumor growth curves and (D)
survival curves of mice which have received the
mentioned treatments. Reproduced with permis­
sion [63]. Copyright 2016, John Wiley & Sons.
(E) Schematic illustration of the formation of
supra-CDs, and their applications as a contrast
agent in fluorescence / magnetic resonance (MR)
imaging and as an acidic H2O2-driven oxygen­
erator to enhance the anticancer efficiency of
photodynamic therapy (PDT; the related chemi­
cal reactions are illustrated on zoom-in frames) in
a solid tumor. Reproduced with permission [59].
Copyright 2018, John Wiley & Sons.
properly addressed, because they play key roles in the formation of CD
assemblies and comprehensive understanding of the related physico­
chemical properties. The numerous precursors and methodologies for
the preparation of CDs available in literature make it somewhat hard to
choose the most appropriate synthetic pathway. In this respect, bottom-
up chemical synthesis of molecular nanocarbon structures (such as
hexabenzocoronene units) [121–123] starting from small organic mol­
ecules might be a useful tool for precisely controlling inner structure and
functionalization of CDs on a molecular level. Based on the remarkable
research progress on supra-CDs, controllable construction of supra-CDs
in terms of the morphology, size and shape, energy-level alignment,
and excited state processes is of special importance for the development
of supra-CDs, and deserves increasing research efforts. We anticipate
several main directions in this area, as summarized below. (i) Supra-CDs
with anisotropic morphology can be produced via oriented assembly of
CDs, which could induce both anisotropic absorption and polarized
emission. Currently, our ability to fabricate optically anisotropic CDs is
D. Li et al.
still in its early stage, and constructing supra-CDs with shape-controlled
optical properties could be a viable approach towards these interesting
optical materials. (ii) Availability of CDs with absorption and emission
wavelengths extending over 800 nm, and especially into the NIR-II
window (1000–1700 nm) is still scarce, so that design and fabrication of
supra-CDs with desired energy level alignments and interparticle elec­
tron transition or charge transfer might result in the appearance of long
wavelength (>800 nm) absorption and emission bands, which will in
turn ensure their increasing use in bioimaging and phototherapy. (iii)
Some supra-CDs are expected to possess room-temperature phospho­
rescence and thermally activated delayed fluorescence, because the
interparticle interactions and local confined environment in such as­
semblies can stabilize the triplet excited states and thus determine
appropriate excited-state recombination processes; those materials can
further be explored in time-gated bioimaging. (iv) Supra-CDs with a
rapid and reversible stimuli-responsive assembly behavior and the cor­
responding switchable PL signals deserve attention for development of
CD-based smart sensors. (v) Extending architectures of supra-CDs into
bulk 3D ordered structures for the use as electrode materials could be
attractive and offers a lot of room for further exploration. Moreover, the
research on other features of supra-CDs, such as possible magnetic
properties, is encouraged in order to gain deeper understanding of
related mechanisms and open up novel application possibilities.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
The authors acknowledge the support from the National Natural
Science Foundation of China (61975200, 61922091 and 51972136),
Jilin Province Science and Technology Research Projects
(20180101190JC and 20170101191JC), the Science and Technology
Development Fund of Macau SAR (0007/2021/AKP, 0128/2020/A3
and 0073/2019/AMJ), Fund from the University of Macau (MYRG2020-
00164-IAPME), Shenzhen-Hong Kong-Macao Science and Technology
Innovation Project (Category C) (SGDX20210823103803021), the Sci­
ence Technology and Innovation Committee of Shenzhen Municipality
(JCYJ20190808181201899), the Research Grant Council of Hong Kong
S.A.R. (CityU 11306619) and the Fundamental Research Funds for the
Central Universities, JLU.
References
[1] V. Georgakilas, J.A. Perman, J. Tucek, R. Zboril, Broad family of carbon
nanoallotropes: Classification, chemistry, and applications of fullerenes, carbon
dots, nanotubes, graphene, nanodiamonds, and combined superstructures, Chem.
Rev. 115 (11) (2015) 4744–4822.
[2] G. Ragazzon, A. Cadranel, E.V. Ushakova, Y. Wang, D.M. Guldi, A.L. Rogach, N.
A. Kotov, M. Prato, Optical processes in carbon nanocolloids, Chem 7 (3) (2021)
606–628.
[3] B. Wang, S. Lu, The light of carbon dots: From mechanism to applications, Matter
5 (1) (2022) 110–149.
[4] J. Liu, R. Li, B. Yang, Carbon dots: A new type of carbon-based nanomaterial with
wide applications, ACS Cent. Sci. 6 (12) (2020) 2179–2195.
[5] G.E. LeCroy, S.-T. Yang, F. Yang, Y. Liu, K.A.S. Fernando, C.E. Bunker, Y. Hu, P.
G. Luo, Y.-P. Sun, Functionalized carbon nanoparticles: Syntheses and
applications in optical bioimaging and energy conversion, Coord. Chem. Rev.
320–321 (2016) 66–81.
[6] F. Yuan, S. Li, Z. Fan, X. Meng, L. Fan, S. Yang, Shining carbon dots: Synthesis and
biomedical and optoelectronic applications, Nano Today 11 (5) (2016) 565–586.
12
Chemical Engineering Journal 454 (2023) 140069
[7] Y. Yan, J. Gong, J. Chen, Z. Zeng, W. Huang, K. Pu, J. Liu, P. Chen, Recent
advances on graphene quantum dots: From chemistry and physics to applications,
Adv. Mater. 31 (21) (2019) 1808283.
[8] L. Ðorđević, F. Arcudi, M. Cacioppo, M. Prato, A multifunctional chemical
toolbox to engineer carbon dots for biomedical and energy applications, Nat.
Nanotechnol. 17 (2) (2022) 112–130.
[9] D. Li, E.V. Ushakova, A.L. Rogach, S. Qu, Optical properties of carbon dots in the
deep-red to near-infrared region are attractive for biomedical applications, Small
17 (43) (2021) 2102325.
[10] T.C. Wareing, P. Gentile, A.N. Phan, Biomass-based carbon dots: Current
development and future perspectives, ACS Nano 15 (10) (2021) 15471–15501.
[11] M. Semeniuk, Z. Yi, V. Poursorkhabi, J. Tjong, S. Jaffer, Z.-H. Lu, M. Sain, Future
perspectives and review on organic carbon dots in electronic applications, ACS
Nano 13 (6) (2019) 6224–6255.
[12] M.C. Biswas, M.T. Islam, P.K. Nandy, M.M. Hossain, Graphene quantum dots
(GQDs) for bioimaging and drug delivery applications: A review, ACS Mater. Lett.
3 (6) (2021) 889–911.
[13] Q. Zeng, T. Feng, S. Tao, S. Zhu, B. Yang, Precursor-dependent structural diversity
in luminescent carbonized polymer dots (CPDs): The nomenclature, Light Sci.
Appl. 10 (1) (2021) 142.
[14] Y. Xiong, J. Schneider, E.V. Ushakova, A.L. Rogach, Influence of molecular
fluorophores on the research field of chemically synthesized carbon dots, Nano
Today 23 (2018) 124–139.
[15] A. Stergiou, N. Tagmatarchis, Interfacing carbon dots for charge-transfer
processes, Small 17 (48) (2021) 2006005.
[16] A. Pal, M.P. Sk, A. Chattopadhyay, Recent advances in crystalline carbon dots for
superior application potential, Mater. Adv. 1 (4) (2020) 525–553.
[17] X.-T. Tian, X.-B. Yin, Carbon dots, unconventional preparation strategies, and
applications beyond photoluminescence, Small 15 (48) (2019) 1901803.
[18] H. Ding, S.-B. Yu, J.-S. Wei, H.-M. Xiong, Full-color light-emitting carbon dots
with a surface-state-controlled luminescence mechanism, ACS Nano 10 (1) (2016)
484–491.
[19] Y. Sun, X. Zhang, J. Zhuang, H. Zhang, C. Hu, M. Zheng, B. Lei, Y. Liu, The room
temperature afterglow mechanism in carbon dots: Current state and further
guidance perspective, Carbon 165 (2020) 306–316.
[20] K. Jiang, S. Sun, L. Zhang, Y. Lu, A. Wu, C. Cai, H. Lin, Red, green, and blue
luminescence by carbon dots: Full-color emission tuning and multicolor cellular
imaging, Angew. Chem. Int. Ed. 54 (18) (2015) 5360–5363.
[21] S. Zhu, Y. Song, X. Zhao, J. Shao, J. Zhang, B. Yang, The photoluminescence
mechanism in carbon dots (graphene quantum dots, carbon nanodots, and
polymer dots): Current state and future perspective, Nano Res. 8 (2) (2015)
355–381.
[22] L. Wang, Y. Wang, X. Sun, G. Zhang, S. Dong, J. Hao, Versatile self-assembly and
biosensing applications of DNA and carbon quantum dots coordinated cerium
ions, Chem.–Eur. J. 23 (43) (2017) 10413–10422.
[23] Y. Lin, R. Chapman, M.M. Stevens, Integrative self-assembly of graphene
quantum dots and biopolymers into a versatile biosensing toolkit, Adv. Funct.
Mater. 25 (21) (2015) 3183–3192.
[24] K. Holá, M.V. Pavliuk, B. Németh, P. Huang, L. Zdražil, H. Land, G. Berggren,
H. Tian, Carbon dots and [FeFe] hydrogenase biohybrid assemblies for efficient
light-driven hydrogen evolution, ACS Catal. 10 (17) (2020) 9943–9952.
[25] J.B. Essner, R.N. McCay, C.J. Smith Ii, S.M. Cobb, C.H. Laber, G.A. Baker,
A switchable peroxidase mimic derived from the reversible co-assembly of
cytochrome c and carbon dots, J. Mater. Chem. B 4 (12) (2016) 2163–2170.
[26] X. Li, S. Zhu, B. Xu, K. Ma, J. Zhang, B. Yang, W. Tian, Self-assembled graphene
quantum dots induced by cytochrome c: A novel biosensor for trypsin with
remarkable fluorescence enhancement, Nanoscale 5 (17) (2013) 7776–7779.
[27] S. Deshmukh, A. Deore, S. Mondal, Ultrafast dynamics in carbon dots as
photosensitizers: A review, ACS Appl. Nano Mater. 4 (8) (2021) 7587–7606.
[28] F. Khakbaz, M. Mahani, Micro-RNA detection based on fluorescence resonance
energy transfer of DNA-carbon quantum dots probes, Anal. Biochem. 523 (2017)
32–38.
[29] L. Vallan, R. Canton-Vitoria, H.B. Gobeze, Y. Jang, R. Arenal, A.M. Benito, W.
K. Maser, F. D’Souza, N. Tagmatarchis, Interfacing transition metal
dichalcogenides with carbon nanodots for managing photoinduced energy and
charge-transfer processes, J. Am. Chem. Soc. 140 (41) (2018) 13488–13496.
[30] T. Skaltsas, A. Stergiou, D.D. Chronopoulos, S. Zhao, H. Shinohara,
N. Tagmatarchis, All-carbon nanosized hybrid materials: Fluorescent carbon dots
conjugated to multiwalled carbon nanotubes, J. Phys. Chem. C 120 (16) (2016)
8550–8558.
[31] T. Skaltsas, M. Goulielmaki, A. Pintzas, S. Pispas, N. Tagmatarchis, Carbon
quantum dots/block copolymer ensembles for metal-ion sensing and bioimaging,
J. Mater. Chem. B 5 (27) (2017) 5397–5402.
[32] A. Cadranel, V. Strauss, J.T. Margraf, K.A. Winterfeld, C. Vogl, L. Đorđević,
F. Arcudi, H. Hoelzel, N. Jux, M. Prato, D.M. Guldi, Screening supramolecular
interactions between carbon nanodots and porphyrins, J. Am. Chem. Soc. 140 (3)
(2018) 904–907.
[33] F. Arcudi, V. Strauss, L. Đorđević, A. Cadranel, D.M. Guldi, M. Prato, Porphyrin
antennas on carbon nanodots: Excited state energy and electron transduction,
Angew. Chem. Int. Ed. 56 (40) (2017) 12097–12101.
[34] A. Ferrer-Ruiz, T. Scharl, P. Haines, L. Rodríguez-Pérez, A. Cadranel,
M.Á. Herranz, D.M. Guldi, N. Martín, Exploring tetrathiafulvalene–carbon
nanodot conjugates in charge transfer reactions, Angew. Chem. Int. Ed. 57 (4)
(2018) 1001–1005.
[35] V. Strauss, J.T. Margraf, K. Dirian, Z. Syrgiannis, M. Prato, C. Wessendorf,
A. Hirsch, T. Clark, D.M. Guldi, Carbon nanodots: Supramolecular electron
D. Li et al.
donor–acceptor hybrids featuring perylenediimides, Angew. Chem. Int. Ed. 54
(28) (2015) 8292–8297.
[36] A. Ferrer-Ruiz, T. Scharl, L. Rodríguez-Pérez, A. Cadranel, M.Á. Herranz,
N. Martín, D.M. Guldi, Assessing the photoinduced electron-donating behavior of
carbon nanodots in nanoconjugates, J. Am. Chem. Soc. 142 (48) (2020)
20324–20328.
[37] V. Strauss, J.T. Margraf, T. Clark, D.M. Guldi, A carbon–carbon hybrid –
immobilizing carbon nanodots onto carbon nanotubes, Chem. Sci. 6 (12) (2015)
6878–6885.
[38] A. Cadranel, J.T. Margraf, V. Strauss, T. Clark, D.M. Guldi, Carbon nanodots for
charge-transfer processes, Acc. Chem. Res. 52 (4) (2019) 955–963.
[39] C. Xia, S. Zhu, T. Feng, M. Yang, B. Yang, Evolution and synthesis of carbon dots:
From carbon dots to carbonized polymer dots, Adv. Sci. 6 (23) (2019) 1901316.
[40] L. Xiao, H. Sun, Novel properties and applications of carbon nanodots, Nanoscale
Horiz. 3 (6) (2018) 565–597.
[41] Q. Lou, S. Qu, P. Jing, W. Ji, D. Li, J. Cao, H. Zhang, L. Liu, J. Zhao, D. Shen,
Water-triggered luminescent “nano-bombs” based on supra-(carbon nanodots),
Adv. Mater. 27 (8) (2015) 1389–1394.
[42] Y. Liu, D.-M. Sun, Z.-Y. Zhang, L. Zhang, S.-D. Nie, J.-P. Xiao, Y.S. Chung, H. Choi,
S. Kim, C.-Y. Liu, Amphiphilic carbon dots with excitation-independent double-
emissions, Part. Part. Syst. Char. 37 (7) (2020) 2000146.
[43] F. Xi, J. Zhao, C. Shen, J. He, J. Chen, Y. Yan, K. Li, J. Liu, P. Chen, Amphiphilic
graphene quantum dots as a new class of surfactants, Carbon 153 (2019)
127–135.
[44] D. Li, D. Han, S.-N. Qu, L. Liu, P.-T. Jing, D. Zhou, W.-Y. Ji, X.-Y. Wang, T.-
F. Zhang, D.-Z. Shen, Supra-(carbon nanodots) with a strong visible to near-
infrared absorption band and efficient photothermal conversion, Light Sci. Appl.
5 (7) (2016) e16120.
[45] C. Wang, T. Hu, T. Thomas, S. Song, Z. Wen, C. Wang, Q. Song, M. Yang, Surface
state-controlled C-dot/C-dot based dual-emission fluorescent nanothermometers
for intra-cellular thermometry, Nanoscale 10 (46) (2018) 21809–21817.
[46] S. Kim, Y. Song, M.J. Heller, Polymorphic architectures of graphene quantum
dots, Adv. Mater. 29 (31) (2017) 1701845.
[47] R. Xiong, X. Zhang, M. Krecker, S. Kang, M.J. Smith, V.V. Tsukruk, Large and
emissive crystals from carbon quantum dots onto interfacial organized templates,
Angew. Chem. Int. Ed. 59 (45) (2020) 20167–20173.
[48] I.P. Hamilton, B. Li, X. Yan, L.-S. Li, Alignment of colloidal graphene quantum
dots on polar surfaces, Nano Lett. 11 (4) (2011) 1524–1529.
[49] Z.-B. Qu, W.-J. Feng, Y. Wang, F. Romanenko, N.A. Kotov, Diverse
nanoassemblies of graphene quantum dots and their mineralogical counterparts,
Angew. Chem. Int. Ed. 59 (22) (2020) 8542–8551.
[50] Q. Chen, S. Sun, H. Lin, Z. Li, A. Wu, X. Liu, F.-G. Wu, W. Zhang, Supra-carbon
dots formed by Fe3+-driven assembly for enhanced tumor-specific photo-
mediated and chemodynamic synergistic therapy, ACS Appl. Bio Mater. 4 (3)
(2021) 2759–2768.
[51] Y. Liu, X. Zhi, W. Hou, F. Xia, J. Zhang, L. Li, Y. Hong, H. Yan, C. Peng, J.M. de la
Fuentea, J. Song, D. Cui, Gd3+-ion-induced carbon-dots self-assembly aggregates
loaded with a photosensitizer for enhanced fluorescence/MRI dual imaging and
antitumor therapy, Nanoscale 10 (40) (2018) 19052–19063.
[52] Q. Li, B. Chen, B. Xing, Aggregation kinetics and self-assembly mechanisms of
graphene quantum dots in aqueous solutions: Cooperative effects of pH and
electrolytes, Environ. Sci. Technol. 51 (3) (2017) 1364–1376.
[53] Y. Xu, C. Wang, T. Jiang, G. Ran, Q. Song, Cadmium induced aggregation of
orange–red emissive carbon dots with enhanced fluorescence for intracellular
imaging, J. Hazard. Mater. 427 (2022), 128092.
[54] T. Liang, E. Liu, M. Li, E.V. Ushakova, S.V. Kershaw, A.L. Rogach, Z. Tang, S. Qu,
Morphology control of luminescent carbon nanomaterials: From dots to rolls and
belts, ACS Nano 15 (1) (2021) 1579–1586.
[55] J. Wu, J.H. Lei, B. He, C.-X. Deng, Z. Tang, S. Qu, Generating long-wavelength
absorption bands with enhanced deep red fluorescence and photothermal
performance in fused carbon dots aggregates, Aggregate 2 (6) (2021) e139.
[56] Y. Liu, Z.-Y. Zhang, S.-D. Nie, C.-Y. Liu, Luminescence modulation of carbon dots
assemblies, J. Mater. Chem. C 7 (21) (2019) 6337–6343.
[57] S. Hu, Y. Ding, Q. Chang, A. Trinchi, K. Lin, J. Yang, J. Liu, Self-assembly of
fluorescent carbon dots in a N, N-dimethylmethanamide solution via Schiff base
reaction, Nanoscale 7 (10) (2015) 4372–4376.
[58] P. Elvati, E. Baumeister, A. Violi, Graphene quantum dots: Effect of size,
composition and curvature on their assembly, RSC Adv. 7 (29) (2017)
17704–17710.
[59] Q. Jia, J. Ge, W. Liu, X. Zheng, S. Chen, Y. Wen, H. Zhang, P. Wang,
A magnetofluorescent carbon dot assembly as an acidic H2O2-driven
oxygenerator to regulate tumor hypoxia for simultaneous bimodal imaging and
enhanced photodynamic therapy, Adv. Mater. 30 (13) (2018) 1706090.
[60] X. Zhang, D. Li, D. Zhou, P. Jing, W. Ji, D. Shen, S. Qu, Dual-encryption based on
facilely synthesized supra-(carbon nanodots) with water-induced enhanced
luminescence, RSC Adv. 6 (83) (2016) 79620–79624.
[61] Y. Ding, H. Cheng, C. Zhou, Y. Fan, J. Zhu, H. Shao, L. Qu, Functional
microspheres of graphene quantum dots, Nanotechnology 23 (25) (2012),
255605.
[62] C. Hou, M. Wang, L. Guo, Q. Jia, J. Ge, Carbon dot assemblies for enhanced
cellular uptake and photothermal therapy in vitro, ChemistrySelect 2 (33) (2017)
10860–10864.
[63] Q. Jia, J. Ge, W. Liu, L. Guo, X. Zheng, S. Chen, M. Chen, S. Liu, L. Zhang,
M. Wang, H. Zhang, P. Wang, Self-assembled carbon dot nanosphere: A robust,
near-infrared light-responsive, and vein injectable photosensitizer, Adv. Healthc.
Mater. 6 (12) (2017) 1601419.
13
Chemical Engineering Journal 454 (2023) 140069
[64] J. Gao, C. Xu, Y. Hu, F. Zhao, C. Shao, Y. Zhao, S. Chen, L. Qu, Unusual assembly
and conversion of graphene quantum dots into crystalline graphite nanocapsules,
Chem.– Asian J. 12 (12) (2017) 1272–1276.
[65] S. Sarkar, S. Dinda, P. Choudhury, P. Kumar Das, Self-assembly of surface
functionalized amphiphilic carbon dots: Tuning in morphological manifestations,
Soft Matter 15 (13) (2019) 2863–2875.
[66] S. Nandi, S. Kolusheva, R. Malishev, A. Trachtenberg, T.P. Vinod, R. Jelinek,
Unilamellar vesicles from amphiphilic graphene quantum dots, Chem.–Eur. J. 21
(21) (2015) 7755–7759.
[67] Y. Xiong, X. Zhang, A.F. Richter, Y. Li, A. Döring, P. Kasák, A. Popelka,
J. Schneider, S.V. Kershaw, S.J. Yoo, J.-G. Kim, W. Zhang, W. Zheng, E.
V. Ushakova, J. Feldmann, A.L. Rogach, Chemically synthesized carbon nanorods
with dual polarized emission, ACS Nano 13 (10) (2019) 12024–12031.
[68] V. Singh, M.R. Zoric, G.N. Hargenrader, A.J.S. Valentine, O. Zivojinovic, D.
R. Milic, X. Li, K.D. Glusac, Exciton coherence length and dynamics in graphene
quantum dot assemblies, J. Phys. Chem. Lett. 11 (1) (2020) 210–216.
[69] H. Cheng, Y. Zhao, Y. Fan, X. Xie, L. Qu, G. Shi, Graphene-quantum-dot
assembled nanotubes: A new platform for efficient raman enhancement, ACS
Nano 6 (3) (2012) 2237–2244.
[70] H. Hou, L. Shao, Y. Zhang, G. Zou, J. Chen, X. Ji, Large-area carbon nanosheets
doped with phosphorus: A high-performance anode material for sodium-ion
batteries, Adv. Sci. 4 (1) (2017) 1600243.
[71] I. Srivastava, J.S. Khamo, S. Pandit, P. Fathi, X. Huang, A. Cao, R.T. Haasch,
S. Nie, K. Zhang, D. Pan, Influence of electron acceptor and electron donor on the
photophysical properties of carbon dots: A comparative investigation at the bulk-
state and single-particle level, Adv. Funct. Mater. 29 (37) (2019) 1902466.
[72] W. Chen, G. Lv, Q. Zhou, J. Shen, J. Cao, X. Liu, Z. Dai, Synthesis of graphene
quantum dots for their supramolecular polymorphic architectures, Nano Res. 14
(4) (2021) 1228–1231.
[73] N. Maity, P. Chakraborty, A.K. Nandi, Influence of chain length on the self-
assembly of poly(ε-caprolactone)-grafted graphene quantum dots, Langmuir 33
(46) (2017) 13384–13393.
[74] Y.-L. Wang, B. Liu, J.-L. Yang, X.-H. Cao, Y.-Z. Yang, Q. Yang, A. Greiner, J.-T. Xu,
X.-H. Zhang, Hyperbranched fractal nanocarbons for bright photoluminescence in
solid state, Adv. Opt. Mater. 7 (18) (2019) 1900659.
[75] X. Zhang, Z. Zhang, F. Hu, D. Li, D. Zhou, P. Jing, F. Du, S. Qu, Carbon-dots-
derived 3D highly nitrogen-doped porous carbon framework for high-
performance lithium ion storage, ACS Sustain. Chem. Eng. 7 (11) (2019)
9848–9856.
[76] H. Hou, C.E. Banks, M. Jing, Y. Zhang, X. Ji, Carbon quantum dots and their
derivative 3D porous carbon frameworks for sodium-ion batteries with ultralong
cycle life, Adv. Mater. 27 (47) (2015) 7861–7866.
[77] G. Chen, S. Wu, L. Hui, Y. Zhao, J. Ye, Z. Tan, W. Zeng, Z. Tao, L. Yang, Y. Zhu,
Assembling carbon quantum dots to a layered carbon for high-density
supercapacitor electrodes, Sci. Rep. 6 (1) (2016) 19028.
[78] B. Fresco-Cala, M.L. Soriano, A. Sciortino, M. Cannas, F. Messina, S. Cardenas,
One-pot synthesis of graphene quantum dots and simultaneous nanostructured
self-assembly via a novel microwave-assisted method: Impact on triazine removal
and efficiency monitoring, RSC Adv. 8 (52) (2018) 29939–29946.
[79] A. Pal, A. Bhakat, A. Chattopadhyay, Zinc ion-induced assembly of crystalline
carbon dots with excellent supercapacitor performance, J. Phys. Chem. C 123
(32) (2019) 19421–19428.
[80] M. Kasha, H. Rawls, M. El-Bayoumi, The exciton model in molecular
spectroscopy, Pure Appl. Chem. 11 (1965) 371–392.
[81] J.S. Anjali Devi, R.S. Aparna, R.R. Anjana, J. Nebu, S.M. Anju, S. George, Solvent
effects: A signature of J- and H-aggregate of carbon nanodots in polar solvents,
J. Phys. Chem. A 123 (34) (2019) 7420–7429.
[82] J. Bai, G. Yuan, Z. Huang, L. Zhang, Y. Zhu, X. Wang, L. Ren, Regulation of
fluorescence emission of carbon dots via hydrogen bonding assembly, Inorg.
Chem. Commun. 126 (2021), 108500.
[83] Z. Zhou, P. Tian, X. Liu, S. Mei, D. Zhou, D. Li, P. Jing, W. Zhang, R. Guo, S. Qu, A.
L. Rogach, Hydrogen peroxide-treated carbon dot phosphor with a bathochromic-
shifted, aggregation-enhanced emission for light-emitting devices and visible
light communication, Adv. Sci. 5 (8) (2018) 1800369.
[84] Y. Shen, X. Zhang, L. Liang, J. Yue, D. Huang, W. Xu, W. Shi, C. Liang, S. Xu,
Mitochondria-targeting supra-carbon dots: Enhanced photothermal therapy
selective to cancer cells and their hyperthermia molecular actions, Carbon 156
(2020) 558–567.
[85] Q. Peng, H. Ma, Z. Shuai, Theory of long-lived room-temperature
phosphorescence in organic aggregates, Acc. Chem. Res. 54 (4) (2021) 940–949.
[86] H. Zhang, Z. Zhao, A.T. Turley, L. Wang, P.R. McGonigal, Y. Tu, Y. Li, Z. Wang, R.
T.K. Kwok, J.W.Y. Lam, B.Z. Tang, Aggregate science: From structures to
properties, Adv. Mater. 32 (36) (2020) 2001457.
[87] A. Xu, G. Wang, Y. Li, H. Dong, S. Yang, P. He, G. Ding, Carbon-based quantum
dots with solid-state photoluminescent: Mechanism, implementation, and
application, Small 16 (48) (2020) 2004621.
[88] J. Birks, Photophysics of aromatic molecules, Wiley, New York, 1970.
[89] C. Kang, S. Tao, F. Yang, B. Yang, Aggregation and luminescence in carbonized
polymer dots, Aggregate 3 (2) (2022) e169.
[90] X. Li, M. Li, M. Yang, H. Xiao, L. Wang, Z. Chen, S. Liu, J. Li, S. Li, T.D. James,
“Irregular” aggregation-induced emission luminogens, Coord. Chem. Rev. 418
(2020), 213358.
[91] A. Sharma, T. Gadly, S. Neogy, S.K. Ghosh, M. Kumbhakar, Molecular origin and
self-assembly of fluorescent carbon nanodots in polar solvents, J. Phys. Chem.
Lett. 8 (5) (2017) 1044–1052.
D. Li et al.
[92] T. Song, Y. Zhao, K. Matras-Postolek, P. Yang, Color-tunable carbon dots via
control the degree of self-assembly in solution at different concentration,
J. Lumin. 212 (2019) 69–75.
[93] H. Yang, Y. Liu, Z. Guo, B. Lei, J. Zhuang, X. Zhang, Z. Liu, C. Hu, Hydrophobic
carbon dots with blue dispersed emission and red aggregation-induced emission,
Nat. Commun. 10 (1) (2019) 1789.
[94] X.-X. Ba, L. Zhang, Y.-L. Yin, F.-L. Jiang, P. Jiang, Y. Liu, Luminescent carbon dots
with concentration-dependent emission in solution and yellow emission in solid
state, J. Colloid Interface Sci. 565 (2020) 77–85.
[95] Y. Wu, H. Zhang, A. Pan, Q. Wang, Y. Zhang, G. Zhou, L. He, White-light-emitting
melamine-formaldehyde microspheres through polymer-mediated aggregation
and encapsulation of graphene quantum dots, Adv. Sci. 6 (2) (2019) 1801432.
[96] L. Li, L. Chen, Y. Lu, B. Li, R. Hu, L. Huang, T. Zhang, X. Wei, Z. Yang, C. Mao,
Aggregated carbon dots-loaded macrophages treat sepsis by eliminating
multidrug-resistant bacteria and attenuating inflammation, Aggregate (2022),
https://doi.org/10.1002/agt2.20.
[97] S. Lu, R. Cong, S. Zhu, X. Zhao, J. Liu, J.S. Tse, S. Meng, B. Yang, pH-dependent
synthesis of novel structure-controllable polymer-carbon nanodots with high
acidophilic luminescence and super carbon dots assembly for white light-emitting
diodes, ACS Appl. Mater. Interfaces 8 (6) (2016) 4062–4068.
[98] T.-H. Chen, W.-L. Tseng, Self-assembly of monodisperse carbon dots into high-
brightness nanoaggregates for cellular uptake imaging and iron(iii) sensing, Anal.
Chem. 89 (21) (2017) 11348–11356.
[99] J. Chen, J. Yan, B. Dou, Q. Feng, X. Miao, P. Wang, Aggregatable thiol-
functionalized carbon dots-based fluorescence strategy for highly sensitive
detection of glucose based on target-initiated catalytic oxidation, Sens. Actuators
B-Chem. 330 (2021), 129325.
[100] M.-J. Cho, S.-Y. Park, Preparation of poly(styrene)-b-poly(acrylic acid)-coupled
carbon dots and their applications, ACS Appl. Mater. Interfaces 9 (28) (2017)
24169–24178.
[101] A. Döring, E. Ushakova, A.L. Rogach, Chiral carbon dots: Synthesis, optical
properties, and emerging applications, Light Sci. Appl. 11 (1) (2022) 75.
[102] Y. Ru, L. Ai, T. Jia, X. Liu, S. Lu, Z. Tang, B. Yang, Recent advances in chiral
carbonized polymer dots: From synthesis and properties to applications, Nano
Today 34 (2020), 100953.
[103] F. Li, Y. Li, X. Yang, X. Han, Y. Jiao, T. Wei, D. Yang, H. Xu, G. Nie, Highly
fluorescent chiral N-S-doped carbon dots from cysteine: Affecting cellular energy
metabolism, Angew. Chem. Int. Ed. 57 (9) (2018) 2377–2382.
[104] L. Hu, H. Li, C.a. Liu, Y. Song, M. Zhang, H. Huang, Y. Liu, Z. Kang, Chiral
evolution of carbon dots and the tuning of laccase activity, Nanoscale 10 (5)
(2018) 2333-2340.
[105] H. Zheng, B. Ju, X. Wang, W. Wang, M. Li, Z. Tang, S.-X.-A. Zhang, Y. Xu,
Circularly polarized luminescent carbon dot nanomaterials of helical
superstructures for circularly polarized light detection, Adv. Opt. Mater. 6 (23)
(2018) 1801246.
[106] A. Das, I.A. Arefina, D.V. Danilov, A.V. Koroleva, E.V. Zhizhin, P.S. Parfenov, V.
A. Kuznetsova, A.O. Ismagilov, A.P. Litvin, A.V. Fedorov, E.V. Ushakova, A.
L. Rogach, Chiral carbon dots based on L/D-cysteine produced via room
temperature surface modification and one-pot carbonization, Nanoscale 13 (17)
(2021) 8058–8066.
14
Chemical Engineering Journal 454 (2023) 140069
[107] M. Prato, S. Di Noja, F. Amato, F. Zinna, L. Di Bari, G. Ragazzon, Transfer of axial
chirality to the nanoscale endows carbon nanodots with circularly polarized
luminescence, Angew. Chem. Int. Ed. 61 (26) (2022) e202202397.
[108] A. Ghosh, B. Parasar, T. Bhattacharyya, J. Dash, Chiral carbon dots derived from
guanosine 5′ -monophosphate form supramolecular hydrogels, Chem. Commun.
52 (74) (2016) 11159–11162.
[109] M. Vázquez-Nakagawa, L. Rodríguez-Pérez, M.A. Herranz, N. Martín, Chirality
transfer from graphene quantum dots, Chem. Commun. 52 (4) (2016) 665–668.
[110] X. Liu, J. Lu, J. Chen, M. Zhang, Y. Chen, F. Xing, L. Feng, Chiral self-assembly of
porphyrins induced by chiral carbon dots, Front. Chem. 8 (2020) 670.
[111] R. Xiong, S. Yu, M.J. Smith, J. Zhou, M. Krecker, L. Zhang, D. Nepal, T.J. Bunning,
V.V. Tsukruk, Self-assembly of emissive nanocellulose/quantum dot
nanostructures for chiral fluorescent materials, ACS Nano 13 (8) (2019)
9074–9081.
[112] A. Li, D. Zheng, M. Zhang, B. Wu, L. Zhu, Chirality transfer in carbon dot-
composited sol–gel systems for excitation-dependent circularly polarized
luminescence, Langmuir 36 (30) (2020) 8965–8970.
[113] Y. Ru, L. Sui, H. Song, X. Liu, Z. Tang, S.-Q. Zang, B. Yang, S. Lu, Rational design
of multicolor-emitting chiral carbonized polymer dots for full-color and white
circularly polarized luminescence, Angew. Chem. Int. Ed. 60 (25) (2021)
14091–14099.
[114] Z. Zhang, C. Yang, Y. Dai, X. Zhang, J. Chen, L. Feng, Circularly polarized
luminescence of achiral carbon dots in bi-solvent systems triggered by
supramolecular self-assembly, Chem.–Eur. J. (2022), https://doi.org/10.1002/
chem.202202589.
[115] G. Xu, X. Bao, J. Chen, B. Zhang, D. Li, D. Zhou, X. Wang, C. Liu, Y. Wang, S. Qu,
In vivo tumor photoacoustic imaging and photothermal therapy based on supra-
(carbon nanodots), Adv. Healthc. Mater. 8 (2) (2019) 1800995.
[116] X. Bu, H. Wang, F. Zhang, Q. Li, J. Zhu, J. Ding, J. Sun, Y. Liu, T. Jiang, Covalent
assembly of clickable carbon nanodots in water-in-oil emulsion for enhanced
antibacterial photothermal therapy, ACS Appl. Nano Mater. 5 (8) (2022)
11447–11457.
[117] D. Jana, D. Wang, P. Rajendran, A.K. Bindra, Y. Guo, J. Liu, M. Pramanik, Y. Zhao,
Hybrid carbon dot assembly as a reactive oxygen species nanogenerator for
ultrasound-assisted tumor ablation, JACS Au 1 (12) (2021) 2328–2338.
[118] Q. Hou, C. Xue, N. Li, H. Wang, Q. Chang, H. Liu, J. Yang, S. Hu, Self-assembly
carbon dots for powerful solar water evaporation, Carbon 149 (2019) 556–563.
[119] N.T. Nhat Hang, N. Van Canh, N.H. Hoa, P.D. Du, P.H. Le, V. Nguyen, Co-
assembled hybrid of carbon nanodots and molecular fluorophores for efficient
solar-driven water evaporation, Carbon 199 (2022) 462–468.
[120] Y. Wen, Q. Jia, F. Nan, X. Zheng, W. Liu, J. Wu, H. Ren, J. Ge, P. Wang,
Pheophytin derived near-infrared-light responsive carbon dot assembly as a new
phototheranotic agent for bioimaging and photodynamic therapy, Chem.–Asian J.
14 (12) (2019) 2162–2168.
[121] L.-S. Li, X. Yan, Colloidal graphene quantum dots, J. Phys. Chem. Lett. 1 (17)
(2010) 2572–2576.
[122] M.R. Zoric, V. Singh, S. Warren, S. Plunkett, R.R. Khatmullin, B.P. Chaplin, K.
D. Glusac, Electron transfer kinetics at graphene quantum dot assembly
electrodes, ACS Appl. Mater. Interfaces 11 (49) (2019) 46303–46310.
[123] Y. Segawa, H. Ito, K. Itami, Structurally uniform and atomically precise carbon
nanostructures, Nat. Rev. Mater. 1 (1) (2016) 15002.