Capping nanoparticles with graphene quantum dots for enhanced thermoelectric performance

Graphene quantum dots (GQDs) are shown to serve as phase transfer agents to transfer various types of nanoparticles (NPs) from non-polar to polar solvents. Thorough characterization of the NPs proves complete native ligand exchange. Pellets of this GQD–NP composite show that the GQDs limit the crystal size during spark plasma sintering, yielding enhanced thermoelectric performance compared with NPs exchanged with inorganic ions. A photoluminescence study of the GQD–NP composite also suggests energy transfer from GQDs to NPs.     

Synthesis of Fluorinated and Nonfluorinated Graphene Quantum Dots through a New Top‐Down Strategy for Long‐Time Cellular Imaging

Herein, a new strategy has been developed through combining a microwave‐assisted technique with hydrothermal treatment to reduce graphene waste and improve production yield of graphene quantum dots (GQDs) prepared by top‐down methods. By using fluorinated graphene oxide (FGO) as a raw material, fluorinated GQDs and nonfluorinated GQDs can be synthesized. Additionally, in the fluorinated GQDs, the protective shell supplied by fluorine improves the pH stability of photoluminescence and the strong electron‐withdrawing group, ?F, reduces the π‐ electron density of the aromatic structure; thus inhibiting reactivity toward singlet oxygen produced during irradiation and improving the photostability. Therefore, the as‐prepared fluorinated GQDs with excellent photo‐ and pH stability are suitable for long‐term cellular imaging.     

White‐Light‐Emitting Edge‐Functionalized Graphene Quantum Dots

Graphene quantum dots (GQDs) have received considerable attention for their potential applications in the development of novel optoelectronic materials. In the generation of optoelectronic devices, the development of GQDs that are regulated in terms of their size and dimensions and are unoxidized at the sp² surfaces is desired. GQDs functionalized with bulky Fréchet’s dendritic wedges at the GQD periphery were synthesized. The single‐layered, size‐regulated structures of the dendronized GQDs were revealed by atomic force microscopy. The edge‐functionalization of the GQDs led to white‐light emission, which is an uncommon feature.     

Thermodynamics of the Interaction Between Graphene Quantum Dots with Human Serum Albumin and γ-Globulins

As one of the newly emerged nanomaterials, graphene quantum dots (GQDs) have shown great application potential as tracking probes and drug carriers in biological areas. The GQDs synthesized via the nitric acid reflux method in this study turned out to quench the fluorescence of human serum albumin (HSA) and gamma globulin (γ-globulin) in two different functional ways. The fluorescence quenching effect of GQDs on HSA is a static pattern and the predominant interaction forces are hydrogen bonds and van der Waals forces. Distinct from HSA, the interaction between GQDs and γ-globulins belongs to dynamic quenching and is driven by electrostatic forces. Ultraviolet–visible (UV–vis) differential spectrometry and transient state fluorescence spectrometry were also utilized to further confirm their quenching types. Also, thermodynamics parameters, the enthalpy change (ΔH) and entropy change (ΔS) of reaction between GQDs and proteins were obtained through a series of calculations from the van’t Hoff equation. Furthermore, the effect of GQDs on the conformational structure of proteins was characterized by synchronous fluorescence spectra (SFS), three-dimensional (3D) fluorescence and circular dichroism (CD) spectra. In addition, the binding mechanism of GQDs with HSA and γ-globulins were proposed based on the obtained experimental results. The research on the reaction between GQDs with HSA and γ-globulins offers promising insight for the further application of nanomaterials in biomedical fields.     

Efficient Direct‐Methanol Fuel Cell Based on Graphene Quantum Dots/Multi‐walled Carbon Nanotubes Composite

Direct‐methanol fuel cells are proton‐exchange fuel cell in which methanol is used as the fuel. The important advantage of these fuel cells is the simplicity of transport and storage of methanol. In this study, methanol fuel cell electrocatalysts including graphene quantum dots (GQDs), functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and GQDs/f‐MWCNTs composite were synthesized. The structures of synthesized electrocatalysts were highlighted by scanning electron microscope (SEM), raman spectroscopy, UV–vis spectroscopy, fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS) and x‐ray diffraction (XRD) method. After that, the effective surface areas (ESA) of GQDs, f‐MWCNTs and GQDs/f‐MWCNTs were calculated. Finally, GQDs/f‐MWCNTs composite modified glassy carbon electrode (GQDs/f‐MWCNTs/GCE) showed highest current signals for methanol oxidation than those of comparable GQDs/GCE and f‐MWCNTs/GCE.     

A Time‐Dependent DFT Study of the Absorption and Fluorescence Properties of Graphene Quantum Dots

Absorption and fluorescence spectra of graphene quantum dots (GQDs) have been computed by using time‐dependent density functional theory (TDDFT). Different functionals, including PBE, TPSSh, B3LYP, PBE0, CAM‐B3LYP, and LC‐ωPBE, have been tested and B3LYP/6‐31G(d) has been proven to be the most accurate method for our work. The bulk solvent effects of toluene and dichloromethane have been assessed by using the polarizable continuum model (PCM). The absorption wavelength of GQDs in solvents is red‐shifted compared with that in the gas phase. Edge functionalization effects analysis shows that a small number of substituted groups on GQDs induce a small redshift whereas a large redshift occurs when the edges of GQDs are all decorated. Little difference in the fluorescent emission was observed in solvents and in the gas phase. Molecular orbital transition and transition density matrix analysis have been performed. The electronic transition mainly occurs in the middle part of the structure of C132. The strong absorption of C132 corresponds to a S₀→S₃ transition and the fluorescence emission is ascribed to a S₁→S₀ transition, which indicates that Kasha’s rule is obeyed.     

Effects of graphene quantum dot (GQD) on photoluminescence,mechanical, thermal and shape memory properties of thermoplastic polyurethane nanocomposites

A group of shape memory polyurethane‐based nanocomposites containing graphene quantum dot nanoparticles (GQDs) were prepared via in‐situ polymerization method. GQD nanoparticles were synthesized by a facile and rapid microwave‐assisted method and characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐ray diffraction pattern, field emission scanning microscopy, transmission electron microscopy, and fluorescence analysis. Chemical structure and hydrogen bonding index (HBI_[C=O]) of the nanocomposites were analyzed via FTIR spectra. The results show that the incorporation of GQDs in PU matrix reduces HBI_(C=O) of nanocomposites. Crystalline structure and thermal properties of the nanocomposites were investigated by differential scanning calorimetry. As results indicate, nucleation effect of GQDs raises crystallinity content of the samples. Mechanical examinations indicate that incorporation of GQDs improves Young's modulus of the nanocomposites, while their elongation at break values are reduced. In addition, shape memory analyses reveal that the presence of GQDs in PU matrix increases the shape fixity ratios in nanocomposites.     

绿色、低成本球磨-水热法制备石墨烯量子点及其应用研究

以绿色、简单、成本低的球磨方法制备的石墨烯为碳源,采用一步水热法成功制备了分散性好、尺寸分布均一、平均直径为(4.80 ± 0.20) nm、厚度为1~3层石墨烯烯量子点.分别采用高分辨透射电镜、原子力显微镜、傅里叶变换红外光谱、X射线光电子能谱、紫外-可见吸收光谱、荧光光谱等对石墨烯量子点进行形貌、结构以及荧光性能的表征. 合成的石墨烯量子点可用于Fe.3+的非标记、特异性检测,检测线性范围为2.0×10.-6~7.0×10.-4 mol/L,检出限为1.8×10.-6 mol/L(S/N=3),同时对检测机理进行了推断,证明此石墨烯量子点用于自来水中Fe.3+的检测的可行性;基于其低毒性和优良的生物相容性,所制备的石墨烯量子点可应用于细胞成像研究.本研究为碳纳米材料的制备提供了一种新途径,也为石墨烯量子点在生化分析、成像等方面的研究奠定了基础.     

Bottom‐Up Fabrication of Single‐Layered Nitrogen‐Doped Graphene Quantum Dots through Intermolecular Carbonization Arrayed in a 2D Plane

A single‐layered intermolecular carbonization method was applied to synthesize single‐layered nitrogen‐doped graphene quantum dots (N‐GQDs) by using 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB) as the only precursor. In this method, the gas produced in the pyrolysis of TATB assists with speeding up of the reactions and expanding the layered distance, so that it facilitates the formation of single‐layered N‐GQDs (about 80 %). The symmetric intermolecular carbonizations of TATB arrayed in a plane and six nitrogen‐containing groups ensure small, uniform sizes (2–5 nm) of the resulting products, and provide high nitrogen‐doping concentrations (N/C atomic ratio ca. 10.6 %). In addition to release of the produced gas, TATB is almost completely converted into aggregated N‐GQDs; thus, relatively higher production rates are possible with this approach. Investigations show that the as‐produced N‐GQDs have superior fluorescent characteristics; high water solubility, biocompatibility, and low toxicity; and are ready for potential applications, such as biomedical imaging and optoelectronic devices.     

Effects of Edge Oxidation on the Stability and Half‐Metallicity of Graphene Quantum Dots

A comprehensive first‐principles theoretical study of the electronic properties and half‐metallic nature of zigzag edge‐oxidized graphene quantum dots (GQDs) is carried out by using density functional theory (DFT) with the screened exchange hybrid functional of Heyd, Scuseria and Ernzerhof (HSE06). The oxidation schemes include ‐OH, ‐COOH and ‐COO groups. We identify oxidized GQDs whose opposite spins are localized at the two zigzag edges in an antiferromagnetic‐type configuration, showing a spin‐polarized ground state. Oxidized GQDs are more stable than the corresponding fully hydrogenated GQDs. The partially hydroxylated and carboxylated GQDs with the same size exhibit half‐metallic state under almost the same electric‐field intensity whereas fully oxidized GQDs behave as spin‐selective semiconductors. The electric‐field intensity inducing the half metal increases with the length of the partially oxidized GQDs, ranging from M=4 to 7.     

Graphene Quantum Dots Assembled with Metalloporphyrins for “Turn on” Sensing of Hydrogen Peroxide and Glucose

Noncovalent and multifunctional hybrids have been generated via π–π stacking and electrostatic interactions by combining the nanometer‐scale graphene structure of graphene quantum dots (GQDs) with Fe^III 5,10,15,20‐tetrakis(1‐methyl‐4‐pyridyl)porphine (FeTMPyP). The inner filter effect (IFE) of FeTMPyP on the GQDs results in substantial PL quenching of the GQDs. The quenched PL of GQDs by the FeTMPyP can be switched back “on” in response to the reaction between FeTMPyP and H₂O₂, which causes rupture of the cyclic tetrapyrrolic nucleus with consequential loss of iron from FeTMPyP, and then proceeds further to produce colorless dipyrroles and monopyrroles. This “turn on” system can be applied for simple and convenient H₂O₂ sensing and can be further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) through the oxidation of glucose and formation of H₂O₂. Because of the inherent synthetic control available for the design of metalloporphyrins, the GQDs‐based optical sensing approach described here has the potential to be highly versatile for other target analytes.     

Rational hydrothermal synthesis of graphene quantum dots with optimized luminescent properties for sensing applications

Hydrothermal synthesis using graphene oxide (GO) as a precursor has been used to produce luminescent graphene quantum dots (GQDs). However, such a method usually requires many reagents and multistep pretreatments, while can give rise to GQDs with low quantum yield (QY). Here, we investigated the concentration, the temperature of synthesis, and the pH of the GO solution used in the hydrothermal method through factorial design experiments aiming to optimize the QY of GQDs to reach a better control of their luminescent properties. The best synthesis condition (2 mg/mL, 175 °C, and pH = 8.0) yielded GQDs with a relatively high QY (8.9%) without the need of using laborious steps or dopants. GQDs synthesized under different conditions were characterized to understand the role of each synthesis parameter in the materials' structure and luminescence properties. It was found that the control of the synthesis parameters enables the tailoring of the amount of specific oxygen functionalities onto the surface of the GQDs. By changing the synthesis' conditions, it was possible to prioritize the production of GQDs with more hydroxyl or carboxyl groups, which influence their luminescent properties. The as-developed GQDs with tailored composition were used as luminescent probes to detect Fe³⁺. The lowest limit of detection (0.136 μM) was achieved using GQDs with higher amounts of carboxylic groups, while wider linear range was obtained by GQDs with superior QY. Thus, our findings contribute to rationally produce GQDs with tailored properties for varied applications by simply adjusting the synthesis conditions and suggest a pathway to understand the mechanism of detection of GQDs-based optical sensors.     

Graphene quantum dots with Zn2+ and Ni2+ conjugates can cleave supercoiled DNA

Graphene quantum dots (GQDs), inheriting the superb property of graphene oxide, possess smaller lateral size and high biocompatibility, thus having potential in biomedical applications. We previously discovered that GQDs, combining with Cu²⁺ ions, could cleave DNA primarily through an oxidative pathway; yet, oxidative DNA cleavage is not practically preferred in biology. In this work, we explore the DNA cleavage ability of GQDs with Zn²⁺ and Ni²⁺. Zn²⁺ and Ni²⁺ alone are incapable of cleaving supercoiled DNA, but when combining with the GQDs, Zn²⁺ and Ni²⁺ exhibit DNA cleavage activity. However, the activity of these two systems is much lower than that of GQDs/Cu²⁺, and GQDs/Ni²⁺ is less active than GQDs/Zn²⁺. The functional mechanism of GQDs/Ni²⁺ and GQDs/Zn²⁺ is different from that of GQDs/Cu²⁺. The GQDs play a key role in the two systems; the redox inactive Zn²⁺ and Ni²⁺ ions assist to generate the oxidative species that eventually lead to the DNA cleavage. The current results together with our previous result indicate that GQDs together with metal ions can cleave supercoiled DNA, and their cleavage activities depend on the properties of metal ions: for redox active metal ions, metal ions play key roles, for redox inactive metal ions, GQDs are dominant.     

Preparation of Excitation‐Independent Photoluminescent Graphene Quantum Dots with Visible‐Light Excitation/Emission for Cell Imaging

We report the first pyrrole‐ring surface‐functionalized graphene quantum dots (p‐GQDs) prepared by a two‐step hydrothermal approach under microwave irradiation in an ammonia medium. The most distinct feature of the functionalized GQDs is that both the excitation and emission wavelengths fall into the visible‐light region. The p‐GQDs are excited by visible light at λ_ex 490 nm (2.53 eV) to emit excitation‐independent photoluminescence at a maximum wavelength of λ_em 550 nm. This is thus far the longest emission wavelength reported for GQDs. Stable photoluminescence is achieved at pH 4–10 with an ionic strength of 1.2 mol L^?1 KCl. These features make the p‐GQDs excellent probes for bio‐imaging and bio‐labeling, which is demonstrated by imaging live HeLa cells.     

MWCNTs/Ionic Liquid/Graphene Quantum Dots Nanocomposite Coated with Nickel‐Cobalt Bimetallic Catalyst as a Highly Selective Non‐enzymatic Sensor for Determination of Glucose

In this work, a glassy carbon electrode (GCE) was modified with multiwall carbon nanotubes/ionic liquid/graphene quantum dots (MWCNTs/IL/GQDs) nanocomposite. Then, the nanocomposite was decorated with nickel‐cobalt nanoparticles (Ni?Co NPs), and it was used as a non‐enzymatic glucose sensor. Field emission scanning electron microscopy, X‐ray diffraction spectroscopy, and energy dispersive spectroscopy were employed to prove the electrodeposition of the Ni?Co NPs on the surface of MWCNTs/IL/GQDs/GCE. Also, cyclic voltammetric and amperometric methods were utilized for the investigation of the electrochemical behaviour of the Ni?Co NPs/MWCNTs/IL/GQDs/GCE for glucose oxidation. The novel amperometric sensor displayed two linear ranges from 1.0 to 190.0 μmol L^?1 and 190.0 to 4910 μmol L^?1 with a low detection limit of 0.3 μmol L^?1 as well as fast response time (2 s) and high stability. Also, the sensor showed good selectivity for glucose determination in the presence of ascorbic acid, citric acid, dopamine, uric acid, fructose, and sucrose, as potential interference species. Finally, the performance of the proposed sensor was investigated for the glucose determination in real samples. Ni?Co NPs/MWCNTs/IL/GQDs/GCE showed good sensitivity and excellent selectivity.     

Anticancer Photodynamic Therapy Properties of Sulfur‐Doped Graphene Quantum Dot and Methylene Blue Preparations in MCF‐7 Breast Cancer Cell Culture

Photodynamic therapy (PDT) is a field with many applications including chemotherapy. Graphene quantum dots (GQDs) exhibit a variety of unique properties and can be used in PDT to generate singlet oxygen that destroys pathogenic bacteria and cancer cells. The PDT agent, methylene blue (MB), like GQDs, has been successfully exploited to destroy bacteria and cancer cells by increasing reactive oxygen species generation. Recently, combinations of GQDs and MB have been shown to destroy pathogenic bacteria via increased singlet oxygen generation. Here, we performed a spectrophotometric assay to detect and measure the uptake of GQDs, MB and several GQD‐MB combinations in MCF‐7 breast cancer cells. Then, we used a cell counting method to evaluate the cytotoxicity of GQDs, MB and a 1:1 GQD:MB preparation. Singlet oxygen generation in cells was then detected and measured using singlet oxygen sensor green. The dye, H₂DCFDA, was used to measure reactive oxygen species production. We found that GQD and MB uptake into MCF‐7 cells occurred, but that MB, followed by 1:1 GQD:MB, caused superior cytotoxicity and singlet oxygen and reactive oxygen species generation. Our results suggest that methylene blue's effect against MCF‐7 cells is not potentiated by GQDs, either in light or dark conditions.     

MoS2/GQDs催化剂的制备及微生物电解池的产氢性能研究

通过水热法合成了一系列MoS₂/GQDs复合材料,并制成碳基复合电极。利用电化学测试手段挑选出最佳电极后用于微生物电解池（MEC）阴极的产氢性能研究。实验结果显示： Na₂MoO₄、半胱氨酸和GQDs的最佳原料配比为375:600:1,制备出的MoS₂/GQDs呈现明显的爆米花样纳米片结构,片层厚度在10 nm左右,当碳纸负载量为1.5 mg·cm^-2时,MoS₂/GQDs碳纸电极的析氢催化能力最佳。在MEC产氢实验中,MoS₂/GQDs阴极MEC的产气量、氢气产率、库仑效率、整体氢气回收率、阴极氢气回收率、电能回收率和整体能量回收率分别为51.15±3.15 mL·cycle^-1、0.401±0.032 m³H₂·m³d^-1、91.16±0.054%、66.64±5.39%、72.44±2.60%、217.26±7.42%和77.37±1.50%,均略高于Pt/C阴极MEC或与之媲美。另外,MoS₂/GQDs具有良好的长期稳定性,且价格便宜,有利于实际应用。     

Graphene quantum dot–based electrochemical biosensing for early cancer detection

Electrochemical biosensing systems coupled with graphene quantum dots (GQDs) have demonstrated suitability for cancer diagnostic strategies, particularly to identify the changes facilitating the early phases of tumorigenesis as well as to detect ultralow concentrations of biomarkers that distinguish between normal and malignant cells. GQDs, known as a novel class of zero-dimensional semiconductor nanocrystals, are tiny graphene particles arranged in a honeycomb structure with a size range of 1–50 nm. The size of these GQDs is comparable with the size of biomolecules, thereby providing an ideal platform to study biomolecules such as proteins, cells, and viruses. GQDs are a superior platform for specific and sensitive recognition of cancer biomarkers; they are highly synergistic with electrochemical sensors. This review will shed light on the recent advancements made in the field of GQD-based electrochemical sensors for early cancer detection, with the aim of highlighting the prospects for further development in cancer diagnostics.     

基于柠檬酸的石墨烯量子点的制备及其应用

石墨烯量子点（GQDs）是一种新型碳基准零维材料,不但具有石墨烯的独特平面结构,同时具备碳点的量子限制效应和边界效应。GQDs具有独特的光学性质、低毒性、高荧光稳定性和高生物相容性,被广泛应用于检测、传感、催化、细胞成像、药物递送和污染治理等领域。GQDs的合成分为自上而下法和自下而上法,前者将大尺寸的石墨烯、石墨、碳材料切割成纳米级的量子点,后者使用不同的前驱体,通过水热法、热裂解法等方法合成石墨烯量子点。柠檬酸（CA）是一种重要的有机酸,室温下是白色结晶状粉末,是自下而上法合成GQDs的一种常用前驱体,近年来有许多关于以CA为前驱体合成不同GQDs的研究,以CA为前驱体合成的GQDs（CA-GQDs）在生物医药、荧光检测、成像等领域均有应用,具有较好的应用前景。对近年来基于CA的合成方法和具体应用进行了总结和回顾,旨在将现有CA-GQDs的相关成果尽可能汇总和展现,以对相关领域研究工作者提供一定参考,并对未来CA-GQDs较有前景的研究方向进行了展望。     

Recent advances in synthesis and biological applications of graphene quantum dots

Graphene quantum dots (GQDs) are becoming imperative functional carbon-based nanomaterials for use in a wide range of biological applications due to the unique optical and optoelectronic properties and also for having physical and chemical stable carbon network structure. Low toxicity, edge functionalization, tunable size, and photoluminescence properties of GQDs have attracted worldwide interests in recent years from academic and industrial point of view. The strong photoluminescence, good water solubility, and high drug loading capacity make GQDs useful for biosensing, bioimaging, and drug delivery. In this review, we have focused on the recent development in the synthesis methodologies and biological applications of GQDs.