Yubin Song

Highly Photoluminescent Carbon Dots for Multicolor Patterning, Sensors, and Bioimaging

Fluorescent carbon-based materials have drawn increasing attention in recent years owing to exceptional advantages such as high optical absorptivity, chemical stability, biocompatibility, and low toxicity. These materials primarily include carbon dots (CDs), nanodiamonds, carbon nanotubes, fullerene, and fluorescent graphene. The superior properties of fluorescent carbon-based materials distinguish them from traditional fluorescent materials, and make them promising candidates for numerous exciting applications, such as bioimaging, medical diagnosis, catalysis, and photovoltaic devices. Among all of these materials, CDs have drawn the most extensive notice, owing to their early discovery and adjustable parameters. However, many scientific issues with CDs still await further investigation. Currently, a broad series of methods for obtaining CD-based materials have been developed, but efficient one-step strategies for the fabrication of CDs on a large scale are still a challenge in this field. Current synthetic methods are mainly deficient in accurate control of lateral dimensions and the resulting surface chemistry, as well as in obtaining fluorescent materials with high quantum yields (QY). Moreover, it is important to expand these kinds of materials to novel applications. Herein, a facile and highoutput strategy for the fabrication of CDs, which is suitable for industrial-scale production (yield is ca. 58%), is discussed. The QY was as high as ca. 80%, which is the highest value recorded for fluorescent carbon-based materials, and is almost equal to fluorescent dyes. The polymer-like CDs were converted into carbogenic CDs by a change from low to high synthesis temperature. The photoluminescence (PL) mechanism (high QY/PL quenching) was investigated in detail by ultrafast spectroscopy. The CDs were applied as printing ink on the macro/micro scale and nanocomposites were also prepared by polymerizing CDs with certain polymers. Additionally, the CDs could be utilized as a biosensor reagent for the detection of Fe in biosystems. The CDs were prepared by a hydrothermal method, which is described in the Supporting Information (Figure 1a; see also the Supporting Information, Figure S1). The reaction was conducted by first condensing citric acid and ethylenediamine, whereupon they formed polymer-like CDs, which were then carbonized to form the CDs. The morphology and structure of CDs were confirmed by analysis. Figure 1b shows transmission electron microscopy (TEM) images of the CDs, which can be seen to have a uniform dispersion without apparent aggregation and particle diameters of 2–6 nm. The sizes of CDs were also measured by atomic force microscopy (AFM; Figure S2), and the average height was 2.81 nm. From the high-resolution TEM, most particles are observed to be amorphous carbon particles without any lattices; rare particles possess well-resolved lattice fringes. With such a low carbon-lattice-structure content, no obvious D or G bands were detected in the Raman spectra of the CDs (Figure S3). The XRD patterns of the CDs (Figure 1c) also displayed a broad peak centered at 258 (0.34 nm), which is also attributed to highly disordered carbon atoms. Moreover, NMR spectroscopy (H and C) was employed to distinguish sp-hybridized carbon atoms from sp-hybridized carbon atoms (Figure S4). In the H NMR spectrum, sp carbons were detected. In the C NMR spectrum, signals in the range of 30–45 ppm, which correspond to aliphatic (sp) carbon atoms, and signals from 100–185 ppm, which are indicative of sp carbon atoms, were observed. Signals in the range of 170– 185 ppm, which correspond to carboxyl/amide groups, were also present. In the FTIR analysis of CDs, the following were observed: stretching vibrations of C OH at 3430 cm 1 and C H at 2923 cm 1 and 2850 cm , asymmetric stretching vibrations of C-NH-C at 1126 cm , bending vibrations of N H at 1570 cm , and the vibrational absorption band of C=O at 1635 cm 1 (Figure S5). Moreover, the surface groups were also investigated by XPS analysis (Figure 1d). C1s analysis revealed three different types of carbon atoms: graphitic or aliphatic (C=C and C C), oxygenated, and nitrous (Table S1). In the UV/Vis spectra, the peak was focused on 344 nm in an aqueous solution of CDs. In the fluorescence spectra, CDs have optimal excitation and emission wavelengths at 360 nm and 443 nm, and show a blue color under a hand-held UV lamp (Figure 2a). Excitation-dependent PL behavior was [*] S. Zhu, Q. Meng, Prof. J. Zhang, Y. Song, Prof. K. Zhang, Prof. B. Yang State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun, 130012 (P. R. China) E-mail: byangchem@jlu.edu.cn

The photoluminescence mechanism in carbon dots (graphene quantum dots, carbon nanodots, and polymer dots): current state and future perspective

At present, the actual mechanism of the photoluminescence (PL) of fluorescent carbon dots (CDs) is still an open debate among researchers. Because of the variety of CDs, it is highly important to summarize the PL mechanism for these kinds of carbon materials; doing so can guide the development of effective synthesis routes and novel applications. This review will focus on the PL mechanism of CDs. Three types of fluorescent CDs were involved: graphene quantum dots (GQDs), carbon nanodots (CNDs), and polymer dots (PDs). Four reasonable PL mechanisms have been confirmed: the quantum confinement effect or conjugated π-domains, which are determined by the carbon core; the surface state, which is determined by hybridization of the carbon backbone and the connected chemical groups; the molecule state, which is determined solely by the fluorescent molecules connected on the surface or interior of the CDs; and the crosslink-enhanced emission (CEE) effect. To give a thorough summary, the category and synthesis routes, as well as the chemical/physical properties for the CDs, are briefly introduced in advance.

Bioimaging based on fluorescent carbon dots

Nanosized fluorescent carbon particles, namely, carbon dots (CDs), are a kind of fluorescent material that has drawn increasing attention in recent years. CDs have size-, surface chemistry-, and wavelength-dependent luminescence emission, which is different from traditional semiconductor-based quantum dots. Moreover, with excellent chemical stability, good biocompatibility, low toxicity, up-conversion emission, resistance to photo bleaching, as well as easy chemical modifications, CDs are promising for substantial applications in numerous areas: bioimaging, sensors, and energy-related devices. Herein, three kinds of fluorescent dots are reviewed: graphene quantum dots (GQDs), carbon nanodots (CNDs) and polymer dots (PDs). After the first reported CDs prepared from electrophoretic analysis and purification of fluorescent carbon nanotube fragments, there were hundreds of publications focusing on fluorescent CDs. Bioimaging was one of the most common applications of the CDs; therefore, in this review, most of the chosen reference papers were related to bioimaging based on CDs.

Investigation from chemical structure to photoluminescent mechanism: a type of carbon dots from the pyrolysis of citric acid and an amine

Carbon dots (CDs) are one of the advancing fluorescent materials, which draw increasing attention in both theoretical research and practical applications. However, the clear chemical structure and photoluminescence (PL) mechanism of CDs is still an open debate, which limits the development of CDs. Because of the diversity of CDs, it is highly important to clarify this issue for specific CDs models. Herein, a type of CDs, made from citric acid with extremely high quantum yield, is investigated. Through the separation of the CDs, a type of bright blue fluorophore (IPCA) was discovered. IPCA and its derivatives were investigated and they were proven to contribute to the molecular state PL. Other components in the CDs were related to the carbon core state PL, which included polymer clusters and nanosized carbon cores. We conclude that this type of CDs contained complex components and multiple PL centers and that an independent fluorophore strongly affects the PL properties of the CDs. These two conclusions can potentially be true for similar CDs.

A general route to make non-conjugated linear polymers luminescent

Photoluminescent polymer dots (PDs) were prepared by a moderate hydrothermal treatment of poly(vinyl alcohol) (PVA). A single excited state was established in the PL mechanism by ultrafast spectroscopy. Moreover, the applied method be used to prepare fluorescent polymer dots from other non-conjugated polymers, and shows general universality.

Non‐Conjugated Polymer Dots with Crosslink‐Enhanced Emission in the Absence of Fluorophore Units

A new type of fluorescent material is presented, which is called non-conjugated polymer dots (NCPDs). The NCPDs only possess sub-fluorophores (which are groups such as C=O, C=N, N=O) instead of typical conjugated fluorophore groups, and thus these materials should not have strong photoluminescence (PL) in the usual sense. Nevertheless, the PL of these sub-fluorophores can be enhanced by chemical crosslinking or physical immobilization of polymer chains, which is named the crosslink-enhanced emission (CEE) effect. The significant advances achieved by us and other groups on both experimental and theoretical aspects are discussed, and the covalent-bond CEE, rigidity-aggregated CEE, or supramolecular CEE in NCPDs is elaborated. Moreover, synthetic strategies, unique optical properties, and the promise of NCPDs in bio-related fields, such as bioimaging and drug delivery, are systematically discussed.

Photoluminescent graphene quantum dots for in vitro and in vivo bioimaging using long wavelength emission

Graphene quantum dots (GQDs), due to their ultrasmall size, excellent optical properties, chemical stability, biocompatibility, anti-photobleaching as well as low toxicity, have been widely used as fluorescent bio-probes. In this study, we used the top-down “nano-cutting” route to prepare fluorescent GQDs. The as-prepared GQDs possessed ca. 4 nm diameter with 0.218 nm crystal lattice constant, and they had outstanding solubility as many oxygen and nitrogen based groups were present on them. The GQDs were exploited in bioimaging in vitro and in vivo. Using rat Schwann cells as the model system, the time-dependent cellular uptake of the GQDs was tested by a fluorescence activated cell sorter (FACS) and confocal laser scanning microscope (CLSM), and it reached the saturation point after 24 h. Benefiting from the excitation-dependent PL of the GQDs, multi-color cell labeling was achieved, and the GQDs were proved to be mainly distributed in the cytoplasm and lysosomes. Furthermore, using long wavelength emission (620 nm), in vivo imaging was realized in nude mice.

Insight into the effect of functional groups on visible-fluorescence emissions of graphene quantum dots

Graphene quantum dots (GQDs) with a variety of functional groups are studied by adjusting the pH of the solvents and through reduction using chemical methods. Our study suggests that the –CO–OH and –CO–N(CH3)2 groups could contribute to the green fluorescence emission (peak at 500–520 nm), and the –CO–N(CH3)2 group could form the green fluorescence emission state more effectively. Additionally, –OH groups and free zigzag sites may contribute to the blue fluorescence emission (peak at around 420 nm). The edge states and functional groups commonly constitute fluorescence emission centers. Additionally, both blue and green fluorescence emission centers corresponding to the molecule-like states could be quenched using the electron acceptor methyl viologen, which barely affects the intrinsic state of the carbon honeycomb flat structure.

Full‐Color Emission Polymer Carbon Dots with Quench‐Resistant Solid‐State Fluorescence

Abstract Polymer carbon dots (PCDs) represent a new class of carbon dots (CDs) possessing sub‐fluorophores and unique polymer‐like structures. However, like small molecule dyes and traditional CDs, PCDs often suffer from self‐quenching effect in solid state, limiting their potential applications. Moreover, it is hard to prepare PCDs that have the same chemical structure, exhibiting full‐color emission under one fixed excitation wavelength by only modulating the concentration of the PCDs. Herein, self‐quenching‐resistant solid‐state fluorescent polymer carbon dots (SSFPCDs) are prepared, which exhibit strong red SSF without any other additional solid matrices, while having a large production yield (≈89%) and a considerable quantum yield of 8.50%. When dispersed in water or solid matrices in gradient concentrations, they can exhibit yellow, green, and blue fluorescence, realizing the first SSFPCDs with the same chemical structure emitting in full‐color range by changing the ratio of SSFPCDs to the solid matrices.

Thermal responsive fluorescent nanocomposites based on carbon dots

Currently, a broad series of methods to obtain photoluminescent (PL) carbon dots (CDs) have been developed. CDs are novel fluorescent materials with the advantages of easy chemical modifications, chemical stability, biocompatibility as well as low toxicity. As a result, nanocomposites based on CDs have great potential for functional applications. In this paper, poly(N-isopropylacrylamide) (PNIPAM)/CDs composites have been used as a temperature sensor. The detection signal is luminescence which possesses high sensitivity, improved facility and provides the possibility for visual detection. With the temperature increasing, the fluorescence intensity of the composites decreased sharply at around 32 °C with the existence of PNIPAM. The composites show perfect reversibility after 12 heating and cooling processes. Moreover, compared with CDs, the CD composites also show good UV resistance at high power UV exposure.