双酚A在氧化石墨烯表面吸附的分子动力学模拟

双酚A(bisphenol A,BPA)是一种内分泌干扰物,会对机体多方面产生不良影响,包括生殖系统、神经系统、胚胎发育等.因此,在水环境中如何检测和去除BPA显得尤为重要.实验研究表明,氧化石墨烯(graphene oxide,GO)对BPA具有优异的吸附去除性能,但在分子层面的吸附机制尚不清楚.分子动力学模拟,能提供BPA在GO表面的动态吸附过程以及吸附构象等详细信息,可以弥补实验的不足.本文利用GROMACS分子动力学模拟软件,系统模拟了BPA在含GO的水溶液中的吸附过程,并计算了吸附自由能.结果显示:所有的BPA均被吸附在GO两侧,通过分析BPA的吸附构象以及与GO的相互作用,发现π-π疏水作用对吸附起主导作用,且显示出很好的稳定性,而静电和氢键作用增加了GO的吸附能力.通过自由能计算,BPA在GO表面的结合能达30 k J/mol,远大于水分子的5 k J/mol.这些结果进一步证实GO对BPA具有很强的吸附能力以及GO作为吸附剂在水溶液中去除BPA的可行性.     

氢化多孔石墨烯反渗透特性及机理分析

单层石墨烯凭借超薄的厚度和优异的力学化学防污性能,成为新一代纳滤膜材料的最佳选择之一.本文采用经典分子动力学方法,研究了氢化多孔石墨烯反渗透膜对盐水的反渗透特性.结果表明,水渗透量会随着驱动力、孔径和温度的增加而增加;而孔径大于水合半径的条件下,盐离子截留率会随驱动力和温度的增加而降低.当反渗透膜和盐水存在切向运动时,随着切向速度的增加可以有效提高盐离子截留率和减弱浓差极化现象,但也在一定程度上牺牲了水通量.通过分析水流沿渗透方向的能障分布、水分子的氢键分布和离子水合状态,解释了各参数变化对盐水在氢化多孔石墨烯中反渗透特性的影响机理.研究结果将提供基于单层多孔石墨烯反渗透特性的理论认识,并将为纳米级反渗透膜的设计提供帮助.     

石墨烯表面的特征水分子排布及其湿润透明特性的分子动力学模拟

石墨烯因其独特的分子构型、卓越的物理化学性能而受到广泛关注.本文首先利用分子动力学模拟比较了单层石墨烯、铜、二氧化硅三者表面的浸润性,除了接触角的比较,还分析了基底表面的水分子排布,得到石墨烯表面的特征水分子排布为:表面有两层密集的水分子层,其中靠近基底的密集水分子层中O—H键与垂直基底方向夹角集中在90°附近,并且基底表面的氢键几乎都垂直于基底.另一方面,本文研究了石墨烯浸润透明特性,发现在铜和二氧化硅上添加一层石墨烯,对铜的浸润性影响较小,对二氧化硅的浸润性影响很大,不仅使其上接触角显著增大,还使得基底表面的水分子排布呈现出类似单层石墨烯上的规律.本文使用分子动力学模拟方法从微观尺度验证了文献的实验结果,从基底表面水分子排布角度分析了石墨烯独特的浸润透明特性,为进一步开发石墨烯在微结构设计上的应用提供了理论指导.     

DFT study of graphene oxide reduction by a dopamine species

Recently a large interest has arisen for using less active reducers of graphene oxide, GO, that are friendly with the environment. In the present work, a DFT theoretical study on the reduction process of GO model surfaces is performed taking into account zwitterionic dopamine, ZDA, as reducing agent. Several periodic models representing epoxy and hydroxyl patches on GO basal plane are proposed. As the number of oxide groups in a patch of epoxies or hydroxyls on the surface of graphene increases from 1 to 5, these systems become more stable. Whereas the adsorption of ZDA on patches of GO with 5 epoxy groups is non-dissociative, that of ZDA on patches of GO with 5 hydroxyl groups is fundamentally dissociative, reducing the surface of graphene oxide. The H₂O molecule produced in the GO reduction becomes trapped to ZDA through a hydrogen bond. The ZDA binding to GO was analysed by considering electrostatic effects and attractive non-covalent contributions due to vdW interactions.     

不同尺度的蛋白质在纯石墨烯及氧化石墨烯表面的吸附比较

Using all-atom molecular dynamics (MD) simulations, we have investigated the adsorption stability and conformation change of different proteins on the surface of pristine graphene (PG) and graphene oxide (GO). We find that: (i) with the cooperation of the electrostatic interactions between proteins and oxygen-containing groups, GO shows better adsorption stability than PG; (ii) the peptide loses its secondary structure on both PG and GO surface, and the a-helix structure of the protein fragment is partially broken on PG surface, but is well preserved on GO surface, while the secondary structure of globular protein has no distinct change on both PG and GO surface. In general, GO presents better biocompatibility than PG. Our results are of significant importance to understand the interactions between proteins and PG/GO and the applications of PG/GO in biotechnology and biomedicine.     

Preparation of graphene oxides with different sheet sizes by temperature control

The sheet size of a graphene oxide(GO) can greatly influence its electrical, optical, mechanical, electrochemical and catalytic property. It is a key challenge to how to control the sheet size during its preparation in different application fields. According to our previous theoretical calculations of the effect of temperature on the oxidation process of graphene,we use Hummers method to prepare GOs with different sheet sizes by simply controlling the temperature condition in the process of the oxidation reaction of potassium permanganate(KMn O_4) with graphene and the dilution process with deionized water. The results detected by transmission electron microscopy(TEM) and atomic force microscopy(AFM)show that the average sizes of GO sheets prepared at different temperatures are about 1 μm and 7 μm respectively. The ultraviolet–visible spectroscopy(UV-vis) shows that lower temperature can lead to smaller oxidation degrees of GO and less oxygen functional groups on the surface. In addition, we prepare GO membranes to test their mechanical strengths by ultrasonic waves, and we find that the strengths of the GO membranes prepared under low temperatures are considerably higher than those prepared under high temperatures, showing the high mechanical strengths of larger GO sheets. Our experimental results testify our previous theoretical calculations. Compared with the traditional centrifugal separation and chemical cutting method, the preparation process of GO by temperature control is simple and low-cost and also enables large-size synthesis. These findings develop a new method to control GO sheet sizes for large-scale potential applications.     

Graphene resistive random memory — the promising memory device in next generation

Graphene-based resistive random access memory(GRRAM) has grasped researchers' attention due to its merits compared with ordinary RRAM. In this paper, we briefly review different types of GRRAMs. These GRRAMs can be divided into two categories: graphene RRAM and graphene oxide(GO)/reduced graphene oxide(r GO) RRAM. Using graphene as the electrode, GRRAM can own many good characteristics, such as low power consumption, higher density, transparency,SET voltage modulation, high uniformity, and so on. Graphene flakes sandwiched between two dielectric layers can lower the SET voltage and achieve multilevel switching. Moreover, the GRRAM with r GO and GO as the dielectric or electrode can be simply fabricated. Flexible and high performance RRAM and GO film can be modified by adding other materials layer or making a composite with polymer, nanoparticle, and 2D materials to further improve the performance. Above all,GRRAM shows huge potential to become the next generation memory.     

Adsorption dynamics of double-stranded DNA on a graphene oxide surface with both large unoxidized and oxidized regions

The adsorption dynamics of double-stranded DNA (dsDNA) molecules on a graphene oxide (GO) surface are important for applications of DNA/GO functional structures in biosensors, biomedicine and materials science. In this work, molecular dynamics simulations were used to examine the adsorption of different length dsDNA molecules (from 4 bp to 24 bp) on the GO surface. The dsDNA molecules could be adsorbed on the GO surface through the terminal bases and stand on the GO surface. For short dsDNA (4 bp) molecules, the double-helix structure was partially or totally broken and the adsorption dynamics was affected by the structural fluctuation of short dsDNA and the distribution of the oxidized groups on the GO surface. For long dsDNA molecules (from 8 bp to 24 bp) adsorption is stable. By nonlinear fitting of the contact angle between the axis of the dsDNA molecule and the GO surface, we found that a dsDNA molecule adsorbed on a GO surface has the chance of orienting parallel to the GO surface if the length of the dsDNA molecule is longer than 54 bp. We attributed this behavior to the flexibility of dsDNA molecules. With increasing length, the flexibility of dsDNA molecules also increases, and this increasing flexibility gives an adsorbed dsDNA molecule more chance of reaching the GO surface with the free terminal. This work provides a whole picture of adsorption of dsDNA molecules on the GO surface and should be of benefit for the design of DNA/GO based biosensors.     

Oxidation degree dependent adsorption of ssDNA onto graphene-based surface

DNA/GO composite plays a significant role in the research field of biotechnology and nanotechnology, and attracts a great deal of interest. However, it is still unclear how the oxidation degree of the graphene-based surface affects the adsorption process of single-strand DNA(ss DNA). In this paper, based on the molecular dynamics simulations, we find that ss DNA molecule is absorbed on the GO surface in the most stable state with the oxidation degree around 15%. The microscopic mechanism is attributed to the van Der Walls and the electrostatic interactions between the ss DNA molecule and the graphene-based surface, which is accompanied with the π–π stacking and hydrogen bond formation. The number of π–π stacking between ss DNA and GO reaches the maximum value when the oxidation degree is around 15% among all the GO surfaces. Our simulation results also reveal the coexistence of stretched and curved configurations as well as the adsorption orientation of ss DNA on the GO surface. Furthermore, it is found that the absorbed ss DNA molecules are more likely to move on the graphene-based surface of low oxidation degree, especially on pristine graphene. Our work provides the physics picture of ss DNA's physisorption dynamics onto graphene-based surface and it is helpful in designing DNA/GO nanomaterials.     

Quantification of the Particle Size and Stability of Graphene Oxide in a Variety of Solvents

The exceptional solution processing potential of graphene oxide (GO) is always one of its main advantages over graphene in terms of its industrial relevance in coatings, electronics, and energy storage. However, the presence of a variety of functional groups on the basal plane and edges of GO makes understanding suspension behavior in aqueous and organic solvents, a major challenge. Acoustic spectroscopy can also measure zeta potential to provide unique insight into flocculating, meta‐stable, and stable suspensions of GO in deionized water and a variety of organic solvents (including ethanol, ethylene glycol, and mineral oil). As expected, a match between solvent polarity and the polar functional groups on the GO surface favors stable colloidal suspensions accompanied by a smaller aggregate size tending toward disperse individual flakes of GO. This work is significant since it describes the characteristics of GO in solution and its ability to act as a precursor for graphene‐based materials.     

Dissimilar stability of proteins in graphene bilayer: a molecular dynamics study

In order to study protein stability on graphene surface and in a confined space simultaneously, two parallel graphene single layers were built and two structurally dissimilar protein molecules were placed in between. Molecular dynamics simulation results showed a significant denaturing effect of graphene layers on GA module, a 3-α helices bundle protein, while another α/β structure protein, protein G, kept its NMR structure intact throughout all simulations. Such extremely different denaturation behaviours of the proteins offer a good chance to investigate the mechanism of graphene toxicity. Further analysis showed Van der Waals interaction could be the main cause of the denaturing effect. Although the solvation effect can contribute, its contribution is not comparable with the Van der Waals interaction.     

Hydrothermal Preparation of Photoluminescent Graphene Quantum Dots Characterized Excitation‐Independent Emission and its Application as a Bioimaging Reagent

Zero‐dimensional photoluminescent (PL) graphene quantum dots (GQDs) that can be used as the cell‐imaging reagent are prepared by a hydrothermal route using the graphene oxide (GO) as the carbon source. Under the optimized hydrothermal conditions, an initial hydrogen peroxide concentration of 0.5 mg mL^?1 at 180 °C for 120 min, the GO sheets can be cut into nanocrystals with lateral dimensions in the range of 1.5–5.5 nm and an average thickness of around 1.1 nm. The as‐prepared GQDs exhibit an abundance of hydrophilic hydroxy and carboxyl groups and emit bright blue luminescence with up‐conversion properties in a water solution at neutral pH. Most interestingly, they indicate excitation‐independent emission characteristics, and the surface state is demonstrated to have a key role in the PL properties. The fluorescence quantum yield of the GQDs is tested to be around 6.99% using quinine sulfate as a standard. In addition, the as‐prepared GQDs can enter into HeLa cells easily as a fluorescent imaging reagent without any further functionalization, indicating they are aqueous stability, biocompatibility, and promising for potential applications in biolabeling and solution state optoelectronics.     

Oxygenated Functional Group Density on Graphene Oxide: Its Effect on Cell Toxicity

The association of cellular toxicity with the physiochemical properties of graphene‐based materials is largely unexplored. A fundamental understanding of this relationship is essential to engineer graphene‐based nanomaterials for biomedical applications. Here, an in vitro toxicological assessment of graphene oxide (GO) and reduced graphene oxide (RGO) and in correlation with their physiochemical properties is reported. GO is found to be more toxic than RGO of same size. GO and RGO induce significant increases in both intercellular reactive oxygen species (ROS) levels and messenger RNA (mRNA) levels of heme oxygenase 1 (HO1) and thioredoxin reductase (TrxR). Moreover, a significant amount of DNA damage is observed in GO treated cells, but not in RGO treated cells. Such observations support the hypothesis that oxidative stress mediates the cellular toxicity of GO. Interestingly, oxidative stress induced cytotoxicity reduces with a decreasing extent of oxygen functional group density on the RGO surface. It is concluded that although size of the GO sheet plays a role, the functional group density on the GO sheet is one of the key components in mediating cellular cytotoxicity. By controlling the GO reduction and maintaining the solubility, it is possible to minimize the toxicity of GO and unravel its wide range of biomedical applications.     

Influences of interfacial adhesion on gas barrier property of functionalized graphene oxide/ultra-high-molecular-weight polyethylene composites with segregated structure

The segregated graphene oxide(GO)/ultra-high-molecular-weight polyethylene (UHMWPE) composite films with various interfacial adhesion property were prepared by mechanical blending method from UHMWPE, GO, dodecyl amine (DA) functionalized graphene oxide(DA–GO) or uniform DA–GO/high density polyethylene (DA–GO/HDPE) powder. The results of XRD and XPS indicated that DA chain was successfully grafted onto GO sheets via a chemical method, which enhanced the interfacial adhesion between UHMWPE particles and GO sheets. The characterizations of POM and SEM proved that good segregated structure was only obtained in DA–GO/UHMWPE or DA–GO/HDPE/UHMWPE composite. Strong interfacial adhesion between fillers and matrix exhibits positive effect on gas barrier property. Compared to the GO/UHMWPE composite film, dramatic decrease in O₂ permeability coefficient by 42.2 and 48.1%, from 15.4 × 10^?14 to 8.9 × 10^?14 and 8.0 × 10^?14 cm³ cm cm^?2 s^?1 Pa^?1, is achieved upon the addition of only 0.5 wt% fillers, respectively. The DSC results demonstrated that the enhanced gas barrier performance was ascribed to the strong interfacial adhesion between DA–GO/HDPE and UHWMPE matrix, rather than the crystallinity of UHWMPE matrix. Additionally, the decrease in UHMWPE particle size might be conducive to improving the gas barrier property of composite films due to the formation of more isolation layers perpendicular to the film plane.     

水热法快速制备荧光氧化石墨烯量子点及其在细胞成像中的应用

作为一种新型荧光纳米材料,氧化石墨烯量子点(GO QDs)凭借其良好的水溶性和生物相容性得到广泛的关注。以氧化石墨烯为原料,过氧化氢为氧化剂,一步水热法在90 min内快速制备氧化石墨烯量子点,实现了快速、高效及绿色制备氧化石墨烯量子点。所制备得到的氧化石墨烯量子点分布均匀,透射电镜(TEM)图片表明氧化石墨烯量子点粒径分布在2.25～5.25 nm,傅里叶红外光谱(FTIR)和X射线电子能谱(XPS)显示氧化石墨烯量子点表面含有大量的羟基、羧基、羰基等含氧功能团,表明氧化石墨烯量子点具有很好的水溶性。荧光发射光谱(PL)表明氧化石墨烯量子点具有激发波长依赖性。基于其独特的纳米结构,良好的光学性能和生物相容性,氧化石墨烯量子点可替代传统荧光纳米材料应用于细胞成像。     

Synthesis of Blue‐, Green‐, Yellow‐, and Red‐Emitting Graphene‐Quantum‐Dot‐Based Nanomaterials with Excitation‐Independent Emission

A one‐pot method is described for the preparation of graphene quantum dots/graphene oxide (GQDs/GO) hybrid composites with emission in the visible region, through heteroatom doping and hydroxyl‐radical‐induced decomposition of GO. The NH₄OH‐ and thiourea‐mediated dissociation of H₂O₂ produces hydroxyl radicals. Treatment of GO with hydroxyl radicals results in the production of small‐sized GO sheets and GQDs, which self‐assemble to form GQDs/GO through strong π–π interactions. For example, the reaction of GO with a mixture of NH₄OH and H₂O₂ for 40, 120, and 270 min generates yellow‐emitting GQDs/GO (Y‐GQDs/GO), green‐emitting GQDs/GO, and blue‐emitting GQDs, while red‐emitting GQDs/GO (R‐GQDs/GO) are prepared by incubating GO with a mixture of thiourea and H₂O₂. From the analysis of these four GQD‐based nanomaterials by transmission electron microscopy, atomic force microscopy, and fluorescence lifetime spectroscopy, it is found that this tunable fluorescence wavelength results from the differences in particle size. All four GQD‐based nanomaterials exhibit moderate quantum yields (1–10%), nanosecond fluorescence lifetimes, and excitation‐independent emissions. Except for R‐GQDs/GO, the other three GQD‐based nanomaterials are stable in a high‐concentration salt solution (e.g., 1.6 m NaCl) and under high‐power irradiation, enabling the sensitive (high‐temperature resolution and large activation energy) and reversible detection of temperature change. It is further demonstrated that Y‐GQD/GO can be used to image HeLa cells.     

Electro‐optic switching with liquid crystal graphene

Graphene oxide (GO) particles in aqueous dispersions can form liquid crystal (LC) phases at extremely low concentrations due to the extremely high aspect ratio of the flakes and noticeably, they possess an extremely large Kerr coefficient attractive for low power consumption electro‐optic devices. Reduced graphene does not easily form LC phases in water due to its hydrophobic nature but here we show that stable dispersions of reduced graphene oxide can be realized with surfactants and that they exhibit birefringence upon shearing as well as under application of electric fields. The performance of the system is largely superior to GO LC possessing longer time stability and drastically improved electro‐optic properties with an induced birefringence twice as large at the same field strength thanks to the almost recovery of graphene properties upon reduction. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Assembly of Polypyrrole-Graphene Oxide Hydrogel Nanocomposites and Their Swelling Properties

An effective one-step strategy for the static assembly of hydrogels from polypyrrole (PPy) and graphene oxide (GO) is demonstrated. The static polymerization of pyrrole monomer was carried out in the presence of GO nanosheets, leading to the formation of PPy-GO hydrogels. During the static polymerization process, gelation takes place simultaneously by supramolecular interactions. The well-dispersed GO nanosheets in the polymer networks resulted in a significant improvement in water absorbencies. With only a very low loading of GO in the PPy-GO hydrogels, they exhibited significantly larger water uptake compared to a PPy hydrogel. Even in saline solutions, PPy-GO hydrogels also showed obvious water absorbency. Moreover, the PPy-GO hydrogels exhibited a better water retention ability compared with the control under the same conditions. This method is believed to provide possibilities to combine the extraordinary performances of GO with the multifunctional properties of conducting polymers, thus holding great potential for technical applications in the future.     

氧化石墨烯/壳聚糖复合薄膜材料的制备及其非线性光限幅效应的研究

石墨烯及其衍生物作为新型碳纳米结构,由于其优异的光限幅性能而受到广泛关注,但现有的工作多侧重于其在液相体系中光限幅效应及其起因研究.本文以壳聚糖为成膜基质,将氧化石墨烯(GO)与壳聚糖(CS)在液相中均匀共混后成膜,对比研究GO溶液和GO-CS复合膜的光限幅效应及其起因.结果表明在线性透过率相同的情况下,GO在固相基质中表现出比液相基质更强的光限幅效应和更弱的非线性散射.这说明不同于碳纳米管简单的非线性散射,在GO中可能存在多种非线性光学效应.     

Mechanical properties of thin films of graphene materials: A study on their structural quality and functionalities

Several studies have been done on physiochemical properties of thin films of graphene materials, but less on their mechanical properties. The mechanical properties such as tensile and storage modulus of films of graphene oxide (GO), different reduced graphene oxides (rGO), functionalised reduced graphene oxide (frGO) and a few layers graphene (graphene) were analysed in this study. During syntheses processes, a range of variations occurs due to different reducing agents and functionalising components used; this affects or changes the mechanical properties of the materials. In addition, it has become vital to comprehend the mechanical properties of these films as the potential applications such as sensor and electrodes demand extended life cycles or lifetime. It has been found that the ultimate tensile strength (UTS), tensile modulus, and storage modulus vary across all the samples that highly depend on nature/efficiency of reducing agent used, amount of impurities such as oxygen functional groups and defect density such as discrepancies/holes in the aromatic structure. The highest UTS and modulus have been identified with a few layers graphene and with hydroiodic acid reduced GO among the rGOs. The frGO shows almost similar properties to that of graphene.