Shoujun Zhu

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

Strongly green-photoluminescent graphene quantum dots for bioimaging applications

Strongly fluorescent graphene quantum dots (GQDs) have been prepared by one-step solvothermal method with PL quantum yield as high as 11.4%. The GQDs have high stability and can be dissolved in most polar solvents. Because of fine biocompatibility and low toxicity, GQDs are demonstrated to be excellent bioimaging agents.

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.

Common Origin of Green Luminescence in Carbon Nanodots and Graphene Quantum Dots

Carbon nanodots (C-dots) synthesized by electrochemical ablation and small molecule carbonization, as well as graphene quantum dots (GQDs) fabricated by solvothermally cutting graphene oxide, are three kinds of typical green fluorescence carbon nanomaterials. Insight into the photoluminescence origin in these fluorescent carbon nanomaterials is one of the important matters of current debates. Here, a common origin of green luminescence in these C-dots and GQDs is unraveled by ultrafast spectroscopy. According to the change of surface functional groups during surface chemical reduction experiments, which are also accompanied by obvious emission-type transform, these common green luminescence emission centers that emerge in these C-dots and GQDs synthesized by bottom-up and top-down methods are unambiguously assigned to special edge states consisting of several carbon atoms on the edge of carbon backbone and functional groups with C═O (carbonyl and carboxyl groups). Our findings further suggest that the competition among various emission centers (bright edge states) and traps dominates the optical properties of these fluorescent carbon nanomaterials.

Graphene quantum dots with controllable surface oxidation, tunable fluorescence and up-conversion emission

In this article, graphene quantum dots (GQDs) with tunable surface chemistry (increasing oxidation degree) were prepared by an efficient two-step method. The GQDs have tunable fluorescence induced by the degree of surface oxidation, fine solubility, high stability and applicable up-conversion photoluminescence (PL). The PL mechanism was investigated based on the surface structure and PL behaviors. More importantly, the GQDs have acid–base response property and can be applied as pH sensors.

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.

Self-assembled graphene quantum dots induced by cytochrome c: a novel biosensor for trypsin with remarkable fluorescence enhancement

On the basis of cytochrome c-induced self-assembled graphene quantum dots, we demonstrate a novel fluorescent biosensor for trypsin with remarkable fluorescence enhancement, as well as high selectivity and sensitivity.

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.

Bioinspired Silica Surfaces with Near-Infrared Improved Transmittance and Superhydrophobicity by Colloidal Lithography

In this paper, we report a kind of bioinspired high performance near-infrared improved transmittance silica surfaces with superhydrophobic properties by colloidal lithography, with transmittance about 99% from 1300 to 2000 nm. Meanwhile, the optical properties of such surfaces can be controlled by the antireflective structure morphologies resulting from the different reactive ion etching conditions. Using proper microspheres as mask, the high-performance near-infrared telecommunication optics can be achieved. Besides, the antireflective surfaces possess superhydrophobic properties after modified by fluorosilane. Such antireflective surfaces are promising for fabrication of highly light transmissive, antireflective, and superhydrophobic near-infrared optical materials to be used in many important fields.