Efficient Production of High‐Quality Polystyrene‐Functionalized Graphene via Graphite Exfoliation in Chloroform with a Heterobifunctional Hyperbranched Polyethylene as Stabilizer

Efficient production of high‐quality, functionalized graphene is highly desirable for large‐scale applications of graphene. Herein, a route for producing high‐quality, polystyrene (PS)‐functionalized graphene is demonstrated via graphite exfoliation in chloroform with a heterobifunctional hyperbranched polyethylene, HBPE@Py@PS, as stabilizer. The HBPE@Py@PS, possessing a pyrene‐functionalized hyperbranched polyethylene backbone and multiple PS side chains, is synthesized by combining chain walking polymerization and atom transfer radical polymerization techniques. It is confirmed that the HBPE@Py@PS can effectively promote graphite exfoliation in chloroform under sonication to render stable dispersions of high‐quality graphene, with an exfoliation efficiency high as 15% and a monolayer proportion, 61%. Meanwhile, it can irreversibly adsorb on the exfoliated graphene surface based on the π–π stacking interactions, concurrently rendering PS‐functionalized graphene that is fluorescent and highly dispersible in chloroform, with a film conductivity reaching 1100 S m^?1. The as‐produced graphene may find its applications as nanofiller for various PS‐based graphene nanocomposites.     

冬凌草甲素聚乙二醇功能化氧化石墨烯纳米粒的制备及抗结肠癌实验研究

目的制备负载冬凌草甲素(oridonin,ORI)的聚乙二醇功能化氧化石墨烯(PEGylated graphene oxide,GO-PEG)纳米粒(nanoparticles,NPs),并探讨其对结肠癌的抑制作用。方法利用酰胺化反应将端基为氨基的四臂聚乙二醇(PEG)连到氧化石墨烯(GO)上,并通过红外光谱(IR)和差示-热重联用热分析仪(TGA)等对其进行表征;再通过物理共混的方法在GO-PEG上负载抗肿瘤药物ORI,紫外光谱(UV)法测其包封率和载药率,MTT法测定载药体系对人结肠癌细胞SW620和HT29的增殖毒性,并建立荷瘤裸鼠模型考察其体内抗肿瘤活性。结果 IR和TGA测定结果表明PEG已成功偶联到GO上,UV法测得ORI-GO-PEG的包封率和载药率分别为95.81%和48.92%,且在各种生理溶液中具有良好的稳定性。体外细胞毒性实验结果表明,与ORI裸药相比,ORI-GO-PEG-NPs对结肠癌细胞的杀伤能力更强。体内抑瘤实验进一步发现,ORI-GO-PEG-NPs可以更好地抑制体内SW620肿瘤的生长。结论制得的ORI-GO-PEG-NPs具有优良的载药性能和较强的抗结肠癌作用,为今后开发抗肿瘤药物纳米给药系统提供了实验依据。     

Conductance enlargement in picoscale electroburnt graphene nanojunctions

Provided the electrical properties of electroburnt graphene junctions can be understood and controlled, they have the potential to underpin the development of a wide range of future sub-10-nm electrical devices. We examine both theoretically and experimentally the electrical conductance of electroburnt graphene junctions at the last stages of nanogap formation. We account for the appearance of a counterintuitive increase in electrical conductance just before the gap forms. This is a manifestation of room-temperature quantum interference and arises from a combination of the semimetallic band structure of graphene and a cross-over from electrodes with multiple-path connectivity to single-path connectivity just before breaking. Therefore, our results suggest that conductance enlargement before junction rupture is a signal of the formation of electroburnt junctions, with a picoscale current path formed from a single sp² bond.Graphene nanojunctions are attractive as electrodes for electrical contact to single molecules (1–7), due to their excellent stability and conductivity up to high temperatures and a close match between their Fermi energy and the HOMO (highest occupied molecular orbital) or LUMO (lowest unoccupied molecular orbit) energy levels of organic materials. Graphene electrodes also facilitate electrostatic gating due to their reduced screening compared with more bulky metallic electrodes. Although different strategies for forming nanogaps in graphene such as atomic force microscopy, nanolithography (8), electrical breakdown (9), and mechanical stress (10) have been used, only electroburning delivers the required gap-size control below 10 nm (11–13). This new technology has the potential to overcome the challenges of making stable and reproducible single-molecule junctions with gating capabilities and compatibility with integrated circuit technology (14) and may provide the breakthrough that will enable molecular devices to compete with foreseeable developments in Moore’s law, at least for some niche applications (15–17).One set of such applications is likely to be associated with room-temperature manifestations of quantum interference (QI), which are enabled by the small size of these junctions. If such interference effects could be harnessed in a single-molecule device, this would pave the way toward logic devices with energy consumption lower than the current state-of-the-art. Indirect evidence for such QI in single-molecule mechanically controlled break junctions has been reported recently in a number of papers (18), but direct control of QI has not been possible because electrostatic gating of such devices is difficult. Graphene electroburnt junctions have the potential to deliver direct control of QI in single molecules, but before this can be fully achieved, it is necessary to identify and differentiate intrinsic manifestations of room-temperature QI in the bare junctions, without molecules. In the present paper, we account for one such manifestation, which is a ubiquitous feature in the fabrication of picoscale gaps for molecular devices, namely an unexpected increase in the conductance before the formation of a tunnel gap.Only a few groups in the world have been able to implement electroburning method to form nanogap-size junctions. In a recent study of electroburnt graphene junctions, Barreiro et al. (19) used real-time in situ transmission electron microscopy (TEM) to investigate this conductance enlargement in the last moment of gap formation and ruled out the effects of both extra edge scattering and impurities, which reduce the current density near breaking. Also, they showed that the graphene junctions can be free of contaminants before the formation of the nanogap. Having eliminated these effects, they suggested that the enlargement may arise from the formation of the seamless graphene bilayers. Here we show that the conductance enlargement occurs in monolayer graphene, which rules out an explanation based on bilayers. Moreover, we have observed the enlargement in a large number of nominally identical graphene devices and therefore we can rule out the possibility of device- or flake-specific features in the electroburning process. An alternative explanation was proposed by Lu et al. (20), who observed the enlargement in few-layer graphene nanoconstrictions fabricated using TEM. They attributed the enlargement to an improvement in the quality of few-layer graphene due to current annealing, which was simply ruled out by our experiments on electroburnt single-layer graphene. They also attributed this to the reduction of the edge scattering due to the orientation of the edges (i.e., zigzag edges). However, such edge effects have been ruled out by the TEM images of Barreiro et al. (19). Therefore, although this enlargement appears to be a common feature of graphene nanojunctions, so far the origin of the increase remains unexplained.In what follows, our aim is to demonstrate that such conductance enlargement is a universal feature of electroburnt graphene junctions and arises from QI at the moment of breaking. Graphene provides an ideal platform for studying room-temperature QI effects (21) because, as well as being a suitable material for contacting single molecules, it can serve as a natural 2D grid of interfering pathways. By electroburning a graphene junction to the point where only a few carbon bonds connect the left and right electrodes, one can study the effect of QI in ring- and chain-like structures that are covalently bonded to the electrodes. In this paper, we perform feedback-controlled electroburning on single-layer graphene nanojunctions and confirm that there is an increase in conductance immediately before the formation of the tunnel junction. Transport calculations for a variety of different atomic configurations using the nonequilibrium Green’s function (NEGF) method coupled to density functional theory (DFT) show a similar behavior. To elucidate the origin of the effect, we provide a model for the observed increase in the conductance based on the transition from multipath connectivity to single-path connectivity, in close analogy to an optical double-slit experiment. The model suggests that the conductance increase is likely to occur whenever junctions are formed from any sp²-bonded material.     

Graphene supports in vitro proliferation and osteogenic differentiation of goat adult mesenchymal stem cells: potential for bone tissue engineering

Current treatments for bone loss injuries involve autologous and allogenic bone grafts, metal alloys and ceramics. Although these therapies have proved useful, they suffer from inherent challenges, and hence, an adequate bone replacement therapy has not yet been found. We hypothesize that graphene may be a useful nanoscaffold for mesenchymal stem cells and will promote proliferation and differentiation into bone progenitor cells. In this study, we evaluate graphene, a biocompatible inert nanomaterial, for its effect on in vitro growth and differentiation of goat adult mesenchymal stem cells. Cell proliferation and differentiation are compared between polystyrene‐coated tissue culture plates and graphene‐coated plates. Graphitic materials are cytocompatible and support cell adhesion and proliferation. Importantly, cells seeded on to oxidized graphene films undergo osteogenic differentiation in fetal bovine serum‐containing medium without the addition of any glucocorticoid or specific growth factors. These findings support graphene's potential to act as an osteoinducer and a vehicle to deliver mesenchymal stem cells, and suggest that the combination of graphene and goat mesenchymal stem cells provides a promising construct for bone tissue engineering. Copyright © 2014 John Wiley & Sons, Ltd.     

Reduction Expansion Synthesis as Strategy to Control Nitrogen Doping Level and Surface Area in Graphene

Graphene sheets doped with nitrogen were produced by the reduction-expansion (RES) method utilizing graphite oxide (GO) and urea as precursor materials. The simultaneous graphene generation and nitrogen insertion reactions are based on the fact that urea decomposes upon heating to release reducing gases. The volatile byproducts perform two primary functions: (i) promoting the reduction of the GO and (ii) providing the nitrogen to be inserted in situ as the graphene structure is created. Samples with diverse urea/GO mass ratios were treated at 800 °C in inert atmosphere to generate graphene with diverse microstructural characteristics and levels of nitrogen doping. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to study the microstructural features of the products. The effects of doping on the samples structure and surface area were studied by X-ray diffraction (XRD), Raman Spectroscopy, and Brunauer Emmet Teller (BET). The GO and urea decomposition-reduction process as well as nitrogen-doped graphene stability were studied by thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) analysis of the evolved gases. Results show that the proposed method offers a high level of control over the amount of nitrogen inserted in the graphene and may be used alternatively to control its surface area. To demonstrate the practical relevance of these findings, as-produced samples were used as electrodes in supercapacitor and battery devices and compared with conventional, thermally exfoliated graphene.     

Effect of Growth Pressure on Epitaxial Graphene Grown on 4H-SiC Substrates by Using Ethene Chemical Vapor Deposition

The Si(0001) face and C(000-1) face dependences on growth pressure of epitaxial graphene (EG) grown on 4H-SiC substrates by ethene chemical vapor deposition (CVD) was studied using atomic force microscopy (AFM) and micro-Raman spectroscopy (μ-Raman). AFM revealed that EGs on Si-faced substrates had clear stepped morphologies due to surface step bunching. However, This EG formation did not occur on C-faced substrates. It was shown by μ-Raman that the properties of EG on both polar faces were different. EGs on Si-faced substrates were relatively thinner and more uniform than on C-faced substrates at low growth pressure. On the other hand, D band related defects always appeared in EGs on Si-faced substrates, but they did not appear in EG on C-faced substrate at an appropriate growth pressure. This was due to the μ-Raman covering the step edges when measurements were performed on Si-faced substrates. The results of this study are useful for optimized growth of EG on polar surfaces of SiC substrates.     

Films of Carbon Nanomaterials for Transparent Conductors

The demand for transparent conductors is expected to grow rapidly as electronic devices, such as touch screens, displays, solid state lighting and photovoltaics become ubiquitous in our lives. Doped metal oxides, especially indium tin oxide, are the commonly used materials for transparent conductors. As there are some drawbacks to this class of materials, exploration of alternative materials has been conducted. There is an interest in films of carbon nanomaterials such as, carbon nanotubes and graphene as they exhibit outstanding properties. This article reviews the synthesis and assembly of these films and their post-treatment. These processes determine the film performance and understanding of this platform will be useful for future work to improve the film performance.     

Assessment of the toxic potential of graphene family nanomaterials

Graphene, a single-atom-thick carbon nanosheet, has attracted great interest as a promising nanomaterial for a variety of bioapplications because of its extraordinary properties. However, the potential for widespread human exposure raises safety concerns about graphene and its derivatives, referred to as graphene-family nanomaterials. This review summarizes recent findings on the toxicological effects and the potential toxicity mechanisms of graphene-family nanomaterials in bacteria, mammalian cells, and animal models. Graphene, graphene oxide, and reduced graphene oxide elicit toxic effects both in vitro and in vivo, whereas surface modifications can significantly reduce their toxic interactions with living systems. Standardization of terminology and the fabrication methods of graphene-family nanomaterials are warranted for further investigations designed to decrease their adverse effects and explore their biomedical applications.     

Comparative Investigation of Activated Carbon Electrode and a Novel Activated Carbon/Graphene Oxide Composite Electrode for an Enhanced Capacitive Deionization

Capacitive deionization is an emerging brackish water desalination technology whose principle lies in the utilization of porous electrodes (activated carbon materials) to temporarily store ions. Improving the properties of carbon material used as electrodes have been the focus of recent research, as this is beneficial for overall efficiency of this technology. Herein, we have synthesized a composite of activated carbon/graphene oxide electrodes by using a simple blending process in order to improve the hydrophilic property of activated carbon. Graphene oxide (GO) of different weight ratios was blended with commercial Activated carbon (AC) and out of all the composites, AC/GO-15 (15 wt.% of GO) exhibited the best electrochemical and salt adsorption performance in all operating conditions. The as prepared AC and AC/GO-x (x = 5, 10, 15 and 20 wt.% of GO) were characterized by cyclic voltammetry and their physical properties were also studied. The salt adsorption capacity (SAC) of AC/GO-15 at an operating window of 1.0 V is 5.70 mg/g with an average salt adsorption rate (ASAR) of 0.34 mg/g/min at a 400 mg/L salt initial concentration and has a capacitance of 75 F/g in comparison to AC with 3.74 mg/g of SAC, ASAR of 0.23 mg/g/min and a capacitance of 56 F/g at the same condition. This approach could pave a new way to produce a highly hydrophilic carbon based electrode material in CDI.