准二维金属硫属化合物类石墨烯结构的化学合成与组装

无机类石墨烯属于准二维纳米结构体系,因其具有比纯碳石墨烯本身更多的调控参数,比如带隙类型及其带隙宽度可调节等,在电子器件构筑和能量转化存储等领域有着重要的科学意义和广阔的应用前景．近年来,具有准二维特征的金属硫属化合物（metalchalcogenides,MCs）作为类石墨烯结构的重要材料体系受到了广泛关注．本文概述了近年来金属硫属化合物类石墨烯结构的化学制备方法及其可能的组装应用,提出了通过系列方法影响层间作用力及利用晶体各向异性等材料设计与合成策略来实现类石墨烯的化学合成,并展望了类石墨烯的组装结构在能量存储与智能传感领域的应用前景．     

Advances in Graphene/Graphene Composite Based Microbial Fuel/Electrolysis Cells

The modifications of electrodes using graphene and graphene composites in microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) have been widely applied for enhancing the electrochemical catalytic activity and performance of MFCs and MECs. Graphene as one of advanced materials has shown outstanding features for promoting practical applications of MFCs. This review summarizes the modification methods and characterization methods of graphene and related graphene composites on electrode surfaces in MFCs and MECs. The performance improvements of MFCs and MECs by various graphene related composites have been reviewed, which will provide an efficient guide for selecting suitable graphene material to modify electrodes in MFCs and MECs for improving their performance.     

电化学法制备石墨烯及其复合材料

石墨烯是一种具有优异物理和化学性质的新型二维碳纳米材料,大规模低成本制备高品质石墨烯的方法是其能够得到广泛实际应用的重要前提. 电化学方法可以快捷、绿色无污染、批量制备高质量的石墨烯及其复合材料. 本综述在对石墨烯各种制备方法进行简要比较之后,对近年来石墨烯、石墨烯/无机纳米复合材料、石墨烯/聚合物复合材料以及类石墨烯材料的电化学法制备进展进行介绍并作了展望.     

Selective graphene formation on copper twin crystals

Selective graphene growth on copper twin crystals by chemical vapor deposition has been achieved. Graphene ribbons can be formed only on narrow twin crystal regions with a (001) or high-index surface sandwiched between Cu crystals having (111) surfaces by tuning the growth conditions, especially by controlling the partial pressure of CH(4) in Ar/H(2) carrier gas. At a relatively low CH(4) pressure, graphene nucleation at steps on Cu (111) surfaces is suppressed, and graphene is preferentially nucleated and formed on twin crystal regions. Graphene ribbons as narrow as ～100 nm have been obtained in experiments. The preferential graphene nucleation and formation seem to be caused primarily by a difference in surface-dependent adsorption energies of reactants, which has been estimated by first principles calculations. Concentrations of reactants on a Cu surface have also been analyzed by solving a diffusion equation that qualitatively explains our experimental observations of the preferential graphene nucleation. Our findings may lead to self-organizing formation of graphene nanoribbons without reliance on top-down approaches in the future.     

Graphene Based Electrochemical Sensors and Biosensors: A Review

Graphene, emerging as a true 2‐dimensional material, has received increasing attention due to its unique physicochemical properties (high surface area, excellent conductivity, high mechanical strength, and ease of functionalization and mass production). This article selectively reviews recent advances in graphene‐based electrochemical sensors and biosensors. In particular, graphene for direct electrochemistry of enzyme, its electrocatalytic activity toward small biomolecules (hydrogen peroxide, NADH, dopamine, etc.), and graphene‐based enzyme biosensors have been summarized in more detail; Graphene‐based DNA sensing and environmental analysis have been discussed. Future perspectives in this rapidly developing field are also discussed.     

石墨烯在自供能传感系统中的应用

随着现代社会智能化的加速发展,传感系统中传感器的数量、密度和分布范围不断增加,传统的供能方式难以满足如此复杂多变的传感器供能需求,从周围环境中收集能量并转化为电能的自供能传感器件是解决这一难题的有效途径。石墨烯不仅具有优异的传感性能,而且在各种能源器件中有广泛的应用,这为基于石墨烯的自供能传感器件设计提供了便利。近年来,人们已经研究和发展了多种多样的石墨烯自供能传感器件。本文基于自供能器件的基本能量供给原理,包括电化学供能、光伏供能、摩擦电供能、水伏供能以及热电、压电、热释电等其它供能,分别介绍了石墨烯在自供能传感器件中的应用,并展望了基于石墨烯的自供能传感器件的未来发展、挑战和前景。     

Single and ternary nanocomposite electrodes of Mn3O4/TiO2/rGO for supercapacitors

Journal of Solid State Electrochemistry - Graphene (G) and ternary nanocomposites of Mn3O4, TiO2, and reduced graphene oxide(rGO) electrodes have been prepared for supercapacitor applications. The...     

Synthesis of a new class of ribose functionalized dinucleotide cap analogues for biophysical studies on interaction of cap-binding proteins with the 5' end of mRNA

mRNAs of primitive eukaryotes such as Caenorhabditis elegans and Ascaris summ possess two different caps at their 5' terminus. They have either a typical cap which consists of 7-methylguanosine linked via a 5',5'-triphosphate bridge to the first transcribed nucleotide (MMG cap) or an atypical hypermethylated form with two additional methyl groups at the N2 position (TMG cap). Studies on interaction between the 5' end of mRNA and proteins that specifically recognize its structure have been carried out for several years and they often require chemically modified cap analogues. Here, we present the synthesis of five novel dinucleotide MMG and TMG cap analogues designed for binding studies using biophysical methods such as electron spin resonance (ESR) and surface plasmon resonance (SPR). New analogues were prepared by derivatization of the 2',3'-cis diol of the second nucleotide in the cap structure with levulinic acid, and coupling of the obtained acetal through its carboxylic group with 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino TEMPO), ethylenediamine (EDA) or (+)-biotinyl-3,6,9-trioxaundecanediamine (amine-PEO(3)-biotin).     

PMo12-functionalized Graphene nanosheet-supported PtRu nanocatalysts for methanol electro-oxidation

Graphene nanosheets, synthesized by a modified Hummers method, have been functionalized by PMo₁₂, and used as the supports of the PtRu nanoparticles. The electrocatalytic properties of the resultant nanocatalysts (PtRu/PMo₁₂-Graphene) for methanol electro-oxidation have been evaluated by cyclic voltammetry and chronoamperometry. The micrograph and the elemental composition have also been investigated by transmission electron microscopy and energy dispersive X-ray spectroscopy. The results suggest that the addition of PMo₁₂ benefits the high dispersion of graphene nanosheets in the water and the uniform dispersion of the PtRu nanoparticles on the graphene nanosheets, and the PtRu/PMo₁₂-Graphene catalysts have higher electrocatalytic activity and better electrochemical stability for methanol oxidation compared to the PtRu/Graphene catalysts.     

Graphene materials-based chemiluminescence for sensing

Graphene has attracted considerable attention in multidisciplinary research fields and shown various promising applications due to its unique structure and extraordinary physicochemical properties. This review covers the latest advances in graphene materials-based chemiluminescence (CL) for sensing. Chemiluminescence resonance energy transfer and luminescence quenching of graphene materials are discussed. Graphene materials, such as graphene nanosheets, graphene quantum dots, graphene oxide, and reduced graphene oxide have been employed successfully in CL systems in recent years. Graphene materials can be utilized as catalysts, platforms, and energy acceptors to improve the performance of CL. Possible challenges and future perspective on this topic are also presented.     

Preparation,Characterization and Electrochemical Application of Graphene‐metallic Nanocomposites

Three different Graphene‐Metallic (Graphene‐Me) nanocomposites – Graphene‐Silver (Graphene‐Ag), Graphene‐Gold (Graphene‐Au) and Graphene‐Platinum (Graphene‐Pt) nanocomposites – were prepared and characterized. The electrochemical performances of these nanocomposites were tested by incorporating them with glassy carbon paste electrode (GCPE) and used them in biofuel cells (BFC) and as amperometric xanthine biosensor transducers. Present work contains the first application of Graphene‐Au and Graphene‐Ag nanocomposite in BFCs and also first application of these Graphene‐Me nanocomposites in xanthine biosensors. Considering BFC, power and current densities were calculated as 2.03 µW cm^?2 and 167.46 µA cm^?2 for the plain BFC, 3.39 µW cm^?2 and 182.53 µA cm^?2 for Graphene‐Ag, 4.43 µW cm^?2 and 230.15 µA cm^?2 for Grapehene‐Au and 6.23 µW cm^?2 and 295.23 µA cm^?2 for Graphene‐Pt nanocomposite included BFCs respectively. For the amperometric xanthine biosensor linear ranges were obtained in the concentration range between 5 µM and 50 µM with the RSD (n=3 for 30 µM xanthine) value of 4.28 % for plain xanthine biosensor, 3 µM and 50 µM with the RSD (n=3 for 30 µM xanthine) value of 9.37 % for Graphene‐Ag, 5 µM to 20 µM with the RSD (n=3 for 5 µM xanthine) value of 9.00 % and 30 µM to 70 µM with the RSD (n=3 for 30 µM xanthine) value of 8.80 % for Grapehene‐Au and 1 µM and 70 with the the RSD (n=3 for 30 µM xanthine) value of 2.59 % for Grapehene‐Pt based xanthine biosensors respectively.     

The pseudocapacitance mechanism of graphene/CoAl LDH and its derivatives:Are all the modifications beneficial?

Cobalt-Aluminum layered double hydroxide(CoAl LDH) is a hopeful electrode material due to the advantage of easy modifiability for preparing LDH-based derivatives.However,there is short of modification methods to prepare the Co-based derivatives from CoAl LDH and also short of an intuitive perspective to analyze the pseudocapacitance mechanism of CoAl LDH and its derivatives.Herein,Graphene/CoAl LDH and its derivatives including Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP were prepared by reasonably using alkali etching treatment,sulfofication and phosphorization.The specific capacitance of Graphene/CoAl LDH,Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP at1 A g^-1 are 260.7,371.3,440.8,61.4 and 122.2 F g^-1,especially.The pseudocapacitance mechanism of Graphene/CoAl LDH and its derivatives was analyzed.Due to the positive effect of sulfofication on the electrical conductivity of GO and cobalt sulfide,the Graphene/CoS and Graphene/CoS-1 exhibit the optimal electrochemical performance and superior rate capability.In addition,due to the repulsion effect between Graphene and OH-,the Graphene/CoAl LDH exhibits optimal cycling stability of 224.1% capacitance retention after 20000 cycles.Besides,the reason of terrible specific capacitance of Graphene/CoOOH is that the presence of H bond in interlayer of CoOOH inhibits the interaction between Co3+ and OHspecies.Hence,not all modifications will increase the specific capacitance of the electrode materials.Overall,this work provides us with a detailed analysis of the electrochemical mechanism and correlation of CoAl LDH and its derivatives from the perspective of crystal structure and composition.     

N-acetyl-N'-methylamide derivative of (2S,3S)-1-amino-2,3-diphenylcyclopropanecarboxylic acid: theoretical analysis of the conformational impact produced by the incorporation of the second phenyl group to the cyclopropane analogue of phenylalanine

The intrinsic conformational preferences of (2S,3S)-1-amino-2,3-diphenylcyclopropanecarboxylic acid, a phenylalanine cyclopropane analogue bearing two phenyl substituents, have been examined theoretically. For this purpose, its N-acetyl-N'-methylamide derivative, Ac-(2S,3S)c(3)diPhe-NHMe, has been investigated by using ab initio HF and DFT methods. Results have been compared with those previously reported for other cyclopropane analogues of phenylalanine, and with experimental data available for c(3)diPhe-containing peptides.     

石墨烯纤维：制备、性能与应用

石墨烯纤维是一种由石墨烯片层紧密有序排列而成的一维宏观组装材料。通过合理的结构设计和可控制备,石墨烯纤维能够将石墨烯在微观尺度的优异性能有效传递至宏观尺度,展现出优异的力学、电学、热学等性能,从而应用于功能织物、传感、能源等领域。目前,石墨烯纤维主要通过湿法纺丝、限域水热组装等方法制备得到,其性能可以通过对材料体系和制备工艺的优化而进一步提升。本文首先介绍了石墨烯纤维的制备方法,然后详细阐述了石墨烯纤维的性能,讨论了其性能提升策略,并总结了石墨烯纤维的应用,最后对石墨烯纤维的未来发展、挑战和前景进行了展望。     

Stabilization of the heavy methylene analogues, GeH2 and SnH2, within the coordination sphere of a transition metal

The heavy group 14 methylene analogues, EH2, (E = Ge and Sn) have been stabilized via efficient methods, thus enabling the chemistry of these novel inorganic hydrides to be explored in depth.     

New Cisplatin Analogues—On the Way to Better Antitumor Agents

The clinical success of cisplatin (cis -diamminedichloroplatinum(II )) in antitumor chemotherapy has encouraged an all-out search for analogues with lower toxicity, improved therapeutic index and increased activity. Literally thousands of analogues, obtained by replacement of the ammine- and chloro-ligands by other amines and anionic ligands, respectively, have been systematically screened for activity in experimental tumor models. Some of these analogues have been selected for clinical evaluation, but only very few of them appear to be promising antitumor agents. More recently, cisplatin analogues have been designed and synthesized on the basis of, inter alia, the following considerations: 1) platinum complexes with carrier molecules as ligands should prove useful for achieving increasing drug concentration in tumor tissues; 2) platinum complexes with chemotherapeutic agents as ligands could afford polyfunctional drugs with synergistic action; 3) complexes containing more than one platinum atom might be more effective than complexes containing only one platinum atom; 4) platinum complexes could be used as sensitizers in radiation therapy. In this paper, we shall give a brief account of the “traditional” analogues, and then critically discuss what we believe could be the new trends in the design of cisplatin analogues.     

Synthesis of 2′-aminoalkyl-1-benzylisoquinoline derivatives and medium sized ring analogues with mu opiod receptor binding activities

Novel 2′-aminoalkyl-1-benzylisoquinoline compounds and medium size ring analogues have been prepared using reductive alkylation methods. Four of these analogues were tested for biological activity across 48 different CNS receptors and were showed to have binding activities at the mu opiod receptor.     

Characterization of fatty acid esters of okadaic acid and related toxins in blue mussels (Mytilus edulis) from Norway

Marine algal toxins of the okadaic acid group can occur as fatty acid esters in blue mussels, and are commonly determined indirectly by transformation to their parent toxins by alkaline hydrolysis. Some data are available regarding the identity of the fatty acid esters, mainly of palmitic acid (16:0) derivatives of okadaic acid (OA), dinophysistoxin-1 (DTX1) and dinophysistoxin-2 (DTX2). Other fatty acid derivatives have been described, but with limited mass spectral data. In this paper, the mass spectral characterization of the [M-H](-) and [M+Na](+) ions of 16 fatty acid derivatives of each of OA, DTX1 and DTX2 is presented. The characteristic fragmentation of [M+Na](+) ions of OA analogues provided a useful tool for identifying these, and has not been described previously. In addition, a set of negative ion multiple reaction monitoring (MRM) methods was developed for direct determination of 16 fatty acid esters of OA, 16 fatty acid esters of DTX1 and 16 fatty acid esters of DTX2 in shellfish extracts. The MRM methods were employed to study the profiles of fatty acid esters of OA analogues in blue mussels and to compare these with fatty acid ester profiles reported for other groups of marine algal toxins.     

High-performance hybrid supercapacitor based on pure and doped Li4Ti5O12 and graphene

Journal of Solid State Electrochemistry - Graphene nanosheets (G) and pure, as well as doped Mg-, Mn-, V-Li4Ti5O12, spinel structure have been synthesized. As-prepared materials were characterized...     

克力托辛(Clitocine)及其类似物的合成与生物活性

克力托辛是一种从蘑菇Clitocybe inversa中分离出的天然核苷.它及其类似物具有很高的生物活性.综述了克力托辛及2'-脱氧克力托辛类似物、碱基修饰克力托辛类似物、5'-脱氧克力托辛类似物、碳环克力托辛类似物以及无环克力托辛类似物的合成方法,并对克力托辛及其类似物在农业害虫杀灭、腺苷激酶抑制剂、抗肿瘤、抗病毒等药物研究中的应用进行了概述.