Capture of double-stranded DNA in stacked-graphene: giving new insight into the graphene/DNA interaction

Colloidal chemically converted graphene sheets (CCGs) are able to contact with each other to form stable self-assembled stacked-CCGs via salt "invasion", which can serve as powerful building blocks for capturing double-stranded DNA.     

Unique chemical reactivity of a graphene nanoribbon's zigzag edge

The zigzag edge of a graphene nanoribbon possesses a unique electronic state that is near the Fermi level and localized at the edge carbon atoms. The authors investigate the chemical reactivity of these zigzag edge sites by examining their reaction energetics with common radicals from first principles. A "partial radical" concept for the edge carbon atoms is introduced to characterize their chemical reactivity, and the validity of this concept is verified by comparing the dissociation energies of edge-radical bonds with similar bonds in molecules. In addition, the uniqueness of the zigzag-edged graphene nanoribbon is further demonstrated by comparing it with other forms of sp2 carbons, including a graphene sheet, nanotubes, and an armchair-edged graphene nanoribbon.     

功能化石墨烯材料：定义、分类及制备策略

自2004年被成功制备后,石墨烯因其独特迷人的性质在近十几年来备受关注,同时也引发了二维纳米材料的研究热潮。单原子层厚度的二维结构赋予石墨烯非同寻常的光学、电子学、磁学及力学等性质,使得石墨烯在生物学、医学、化学、物理学和环境科学等多个领域展现出极大的应用潜力。制得注意的是,石墨烯在应用时通常需要进行功能化,调节其组成、大小、形状和结构等,以便于加工处理或满足不同的应用需求。石墨烯功能化方法多样,功能化产物也是种类繁多。然而,到目前为止,石墨烯功能化产物并没有系统全面的分类和精确的定义。因此,本文在系统总结现有石墨烯功能化研究的基础上,给出了石墨烯功能化产物的系统分类、各类的精确定义和相应的制备策略,并通过典型示例进行了详细地阐述。石墨烯功能化的产物统称为“功能化石墨烯材料”,分为两类：“功能化石墨烯”和“功能化石墨烯复合材料”。功能化石墨烯材料的制备可由“自上而下”和“自下而上”两种策略实现。制备策略的选择取决于应用需求。系统分类、精确命名和制备策略的归纳必将有助于功能化石墨烯材料的进一步发展。     

Epitaxial Growth of Crystalline Polyaniline on Reduced Graphene Oxide

Due to its unique electronic properties, graphene has already been identified as a promising material for future carbon based electronics. To develop graphene technology, the fabrication of a high quality P‐N junction is a great challenge. Here, we describe a general technique to grow single crystalline polyaniline (PANI) films on graphene sheets using in situ polymerization via the oxidation‐reduction of aniline monomer and graphene oxide, respectively, to fabricate a high quality P‐N junction, which shows diode‐like behavior with a remarkably low turn‐on voltage (60 mV) and high rectification ratio (1880:1) up to a voltage of 0.2 V. The origin of these superior electronic properties is the preferential growth of a highly crystalline PANI film as well as lattice matching between the d‐values [∼2.48 Å] of graphene and {120} planes of PANI.

     

石墨烯导热研究进展

石墨烯具有目前已知材料中最高的热导率,在电子器件、信息技术、国防军工等领域具有良好的应用前景。石墨烯导热的理论和实验研究具有重要意义,在最近十年间取得了长足的发展。本文综述了石墨烯本征热导率的研究进展及应用现状。首先介绍应用于石墨烯热导率测量的微纳尺度传热技术,包括拉曼光谱法、悬空热桥法和时域热反射法。然后展示了石墨烯热导率的理论研究成果,并总结了石墨烯本征热导率的影响因素。随后介绍石墨烯在导热材料中的应用,包括高导热石墨烯膜、石墨烯纤维及石墨烯在热界面材料中的应用。最后对石墨烯导热研究的成果进行总结,提出目前石墨烯热传导研究中存在的机遇与挑战,并展望未来可能的发展方向。     

Dynamic Electrosorption Analysis as an Effective Means to Characterise the Structure of Bulk Graphene Assemblies

Restacking of graphene sheets to a graphite‐like structure is a prevailing problem that is known to compromise the performance of individual graphene sheets in an assembled bulk form. To address this common problem efficiently and monitor the structure and quality of graphene products comprehensively, it is highly desirable to develop reliable metrology techniques for characterising graphene‐based materials on a bulk assembly level and in a quantitative manner. Here, by revisiting the physicochemical principle of electrosorption, we propose a simple electrochemical approach, namely dynamic electrosorption analysis (DEA), as an easily accessible and effective technique for evaluation of the self‐stacking behaviour of graphene. Taking multilayered chemically converted graphene films as a model, we demonstrate that the DEA technique can effectively reveal very subtle variation in accessible surface area and pore size of graphene assemblies in the liquid phase and thus can provide useful insights to the experimental design relating to restacking control. This work also reveals the huge effect some routine processing conditions, such as heat treatment and drying, can have on the structure and performance of graphene‐based bulk materials, providing useful guidance for future manufacturing of this class of materials.     

基于CiteSpace的实验队伍研究热点和趋势

将文献计量和知识图谱用于分析实验队伍的研究热点,使用CiteSpace软件分析相关文章的作者、单位、期刊、关键词等信息,研究实验队伍研究的热点和变化趋势. 研究表明,相关研究数量整体呈上升趋势. 全国该领域研究单位和学者众多,但缺乏权威核心研究团队. 近些年“科研仪器”“开放共享”“绩效考核”等关键词已经取代“实验室”“管理体制”“实验教学”等关键词成为了新的研究热点. 实验队伍的研究与“科研仪器”“开放共享”密不可分. 相比于科研仪器的增长,实验队伍仍存在数量不足和质量不强的问题.     

Graphene and graphene like 2D graphitic carbon nitride: Electrochemical detection of food colorants and toxic substances in environment

Excessive consumption of substances such as food colorants, exposure to doses of metal ions, antibiotic residues and pesticides residues above maximum tolerance limit have a detrimental effect on human health. Hence in detecting these harmful substances, the development of sensitive, selective and convenient analytical tools is an essential step. Graphene and graphene like 2D graphitic carbon nitride have shown great promise in the development of electrochemical sensors for determining the levels of these substances in different samples. In this paper, graphene and graphene like 2D graphitic carbon nitride applications on the determination of various food colorants in foods and drinks such as azo dyes (tartrazine, allura red, amaranth, carmine and sunset yellow); metal ions contaminants, antibiotic and pesticide residues in the environment are reviewed.     

In vivo toxicity screening programs using metabonomics

Metabonomics is an emerging technology that enables rapid in vivo screening for toxicity, disease state, or drug efficacy. The technology combines the power of high-resolution nuclear magnetic resonance (NMR) techniques with statistical data analysis methods to rapidly evaluate the metabolic "status" of an animal. Complimentary to other profiling technologies like proteomics and genomics, metabonomics provides a fingerprint of the small-molecules contained in a given biofluid through the time course of a study. This article reviews the steps in implementing a metabonomics-based screening program from study design through data analysis. While metabonomics is still a relatively new technology in comparison to the other "omics", published results from metabonomics studies demonstrate its potential impact in the drug discovery process by enabling the incorporation of safety endpoints much earlier in the drug discovery process, reducing the likelihood (and cost) of later stage attrition.     

金属衬底在石墨烯化学气相沉积生长中的作用

以过渡金属为催化衬底的化学气相沉积法(Chemical Vapor Deposition，CVD)已经可以制备与机械剥离样品相媲美的石墨烯，是实现石墨烯工业应用的关键技术之一。原子尺度理论研究能够帮助我们深刻理解石墨烯生长机理，为实验现象提供合理的解释，并有可能成为将来实验设计的理论指导。本文从理论计算的角度，总结了各种金属衬底在石墨烯CVD生长过程中的各种作用与相应的机理，包括在催化碳源裂解、降低石墨烯成核密度等，催化加快石墨烯快速生长，修复石墨烯生长过程中产生的缺陷，控制外延生长石墨烯的晶格取向，以及在降温过程中石墨烯褶皱与金属表面台阶束的形成过程等。在本文最后，我们对当前石墨烯生长领域中亟需解决的理论问题进行了深入探讨与展望。     

7-N,7'-N'-(1",2"-Dithianyl-3",6"-dimethylenyl)bismitomycin C: synthesis and nucleophilic activation of a dimeric mitomycin

Dimeric alkylating agents that modify complementary DNA strands have engendered significant interest. We have prepared the novel dimeric mitomycin, 7-N,7'-N'-(1",2"-dithianyl-3",6"-dimethylenyl)bismitomycin C (9), in which the mitomycins are bridged by a dithiane unit. Dimer 9, like the clinically tested acyclic disulfides KW-2149 (3) and BMS-181174 (4), was designed to activate under nucleophilic and reductive conditions. Successive nucleophile-mediated disulfide cleavage transformations of 9 are expected to generate thiol species ideally positioned to render the two mitomycin systems vulnerable to nucleophilic attack and permit DNA interstrand cross-link formation. The dithiane linker, strategically positioned between the two mitomycins, distinguished 9 from 3 and 4. Nucleophilic activation of this cyclic disulfide permitted both activated mitomycins to remain tethered to one another. We report the synthesis of 9, and show that the nucleophile Et(3)P markedly enhances the activation and consumption of 9, compared with the reference compound 7-N, 7"-N'-(cyclohexanyl-trans-1",4"-dimethylenyl)bismitomycin C (27). We further demonstrated that provides higher levels of DNA interstrand cross-links than either the dimeric reference compounds, and 7-N,7-N'-(2",5"-dihydroxy-1",6"-hexanediyl)bismitomycin C (28), or the monomeric mitomycins, 1 and 3, when Et(3)P is added to solutions containing EcoRI-linearized pBR322 DNA.     

Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry

Polymeric graphitic carbon nitride materials (for simplicity: g-C(3)N(4)) have attracted much attention in recent years because of their similarity to graphene. They are composed of C, N, and some minor H content only. In contrast to graphenes, g-C(3)N(4) is a medium-bandgap semiconductor and in that role an effective photocatalyst and chemical catalyst for a broad variety of reactions. In this Review, we describe the "polymer chemistry" of this structure, how band positions and bandgap can be varied by doping and copolymerization, and how the organic solid can be textured to make it an effective heterogenous catalyst. g-C(3)N(4) and its modifications have a high thermal and chemical stability and can catalyze a number of "dream reactions", such as photochemical splitting of water, mild and selective oxidation reactions, and--as a coactive catalytic support--superactive hydrogenation reactions. As carbon nitride is metal-free as such, it also tolerates functional groups and is therefore suited for multipurpose applications in biomass conversion and sustainable chemistry.     

Polycyclic aromatic hydrocarbons in the graphene era

Polycyclic aromatic hydrocarbons(PAHs) have been the subject of interdisciplinary research in the fields of chemistry, physics,materials science, and biology. Notably, PAHs have drawn increasing attention since the discovery of graphene, which has been regarded as the "wonder" material in the 21 st century. Different from semimetallic graphene, nanoscale graphenes, such as graphene nanoribbons and graphene quantum dots, exhibit finite band gaps owing to the quantum confinement, making them attractive semiconductors for next-generation electronic applications. Researches based on PAHs and graphenes have expanded rapidly over the past decade, thereby posing a challenge in conducting a comprehensive review. This study aims to interconnect the fields of PAHs and graphenes, which have mainly been discussed separately. In particular, by selecting representative examples, we explain how these two domains can stimulate each other. We hope that this integrated approach can offer new opportunities and further promote synergistic developments in these fields.     

基于“学习金字塔理论”的物理化学实验教学模式改革实践

介绍了东北林业大学物理化学实验课程教学中基于"学习金字塔理论"进行教学模式改革实践的情况。在实施实验教学过程中,通过增加"学生通过在线实验视频预习""学生为学生讲解实验""操作前学生小组讨论"和"操作后学生小组总结讨论"等学习环节,建立了一种有效的"以学生为中心"的实验教学模式,促进了学生综合素质和创新能力的培养,取得了良好的教学效果。     

One‐Step Pyrolysis Preparation of 1.1.1 Oriented Gold Nanoplatelets Supported on Graphene and Six Orders of Magnitude Enhancement of the Resulting Catalytic Activity

Pyrolysis of chitosan films containing Au³⁺ renders 1.1.1 oriented Au nanoplatelets (20 nm lateral size, 3–4 nm height) on a few layers of N‐doped graphene ( /fl‐G), while the lateral sides were 0.0.1 oriented. Comparison of the catalytic activity of /fl‐G films with powders of unoriented Au NPs supported on graphene showed that /fl‐G films exhibit six orders of magnitude enhancement for three gold‐catalyzed reactions, namely, Ullmann‐like homocoupling, C? N cross coupling, and the oxidative coupling of benzene to benzoic acid. This enhancement is the result of the defined morphology, facet orientation of Au nanocrystals, and strong gold‐graphene interaction.     

Fabrication of small-sized silver NPs/graphene sheets for high-quality surface-enhanced Raman scattering

In this paper, small-sized and highly dispersed Ag nanoparticles (NPs) supported on graphene nanosheets are fabricated via a strategy for etching a copper template with Ag(+). Firstly, big-sized Cu NPs are supported on graphene, and then the small-sized and highly dispersed Ag NPs are supported on graphene by replacement reaction, mainly making use of graphene passing electrons between Cu and Ag(+). The graphene used in the experiment is prepared by in situ self-generating template and has good dispersion, excellent crystallinity and little defects. Thus, in the process of Ag/graphene synthesis, there is no any intervention of surfactant, which ensures that SERS activity sites have not been passivated. And, the little defects of graphene benefit the excellent conductivity of graphene and ensured the replacement reaction between Cu and Ag(+). The obtained material exhibits significant high-quality and distinctive SERS activity. Especially, a serial new peak of p-aminothiophenol (PATP) is observed, this is suggested two reasons: one is "surface geometry" of the PATP on small-sized Ag NPs and another is the charge-transfer between Ag and graphene.     

Chemical Bonding of Transition‐Metal Co13 Clusters with Graphene

We carried out density functional calculations to study the adsorption of Co₁₃ clusters on graphene. Several free isomers were deposited at different positions with respect to the hexagonal lattice nodes, allowing us to study even the hcp 2d isomer, which was recently obtained as the most stable one. Surprisingly, the Co₁₃ clusters attached to graphene prefer icosahedron‐like structures in which the low‐lying isomer is much distorted; in such structures, they are linked with more bonds than those reported in previous works. For any isomer, the most stable position binds to graphene by the Co atoms that can lose electrons. We find that the charge transfer between graphene and the clusters is small enough to conclude that the Co–graphene binding is not ionic‐like but chemical. Besides, the same order of stability among the different isomers on doped graphene is kept. These findings could also be of interest for magnetic clusters on graphenic nanostructures such as ribbons and nanotubes.     

仿鲍鱼壳石墨烯多功能纳米复合材料

石墨烯具有力学性能高、电导率优异等特点,然而单层石墨烯纳米片在组装成为宏观纳米复合材料的过程中,往往会出现片层团聚、界面作用弱、无规取向等问题,导致宏观石墨烯纳米复合材料性能远低于单片石墨烯。因此,如何将微观石墨烯纳米片层的高性能在宏观纳米复合材料中体现出来,是目前研究的热点和难点。本专论结合目前石墨烯纳米复合材料的研究现状,简要讨论了受天然鲍鱼壳的“砖-泥”结构的启发,仿生构筑高性能石墨烯纳米复合材料的最新研究进展。并对本课题组在仿鲍鱼壳石墨烯多功能纳米复合材料领域近年来的工作进行介绍,包括石墨烯纤维、薄膜和块材等多种宏观石墨烯纳米复合材料,系统总结构筑仿鲍鱼壳结构和反鲍鱼壳结构两种策略,在一定程度上解决了石墨烯在组装过程中的科学问题。同时,详细阐述了仿鲍鱼壳石墨烯多功能纳米复合材料的增强增韧机制和功能化策略,分析了今后研究工作中可能遇到的问题,并展望了未来的发展趋势。     

3,5—二甲氧基苯乙醛和丙二酸单乙酯的Knoevenagel缩合

从３,５－二甲基苯乙醛和丙二酸单乙酯的Ｋｎｏｅｖｅｎａｇｅｌ缩合反应得到２个产物,其一经证实是重排生成的４－（３,５－二甲氧苯基）－３－丁烯酸乙酯,另一个是２＇,４＇,２″,４″－四甲氧基－２,３：６,７－二苯并－９－氧杂双环［３．３．１］壬－２,６－二烯。经元素分析、ＩＲ、ＮＭＲ、ＭＳ、和Ｘ射线衍射证实前者不发生可逆重排为其２－烯酸酯异构体的反应。