石墨烯和铂/石墨烯的合成及其表征

以天然鳞状石墨为原料,采用化学氧化法合成氧化石墨,在此基础上采用低温热解膨胀结合微波加热乙二醇还原法合成石墨烯(Gr)以及铂/石墨烯(Pt/Gr)复合材料。SEM和TEM显示所制备的石墨烯为层状结构的半透明薄膜。采用X射线光电子能谱(XPS)和傅立叶转换红外光谱(FTIR)分别确定氧化石墨、膨胀石墨及石墨烯表面含氧官能团的数量和性质。以所制备的碳氧原子比5.94的石墨烯作为载体制备出可用于质子交换膜燃料电池的高负载量的Pt/Gr催化剂,在铂载量高达60%时,表面铂粒子依然具有高分散性,平均粒径为3.8 nm。     

基于石墨烯功能复合材料的DNA电化学生物传感器

石墨烯(Gr)是一类由单层碳原子组成的二维碳质材料,利用它独特的结构和良好的物理、化学性能,可构筑出在电催化、电化学传感器和生物传感器等领域有着巨大应用潜力的新型Gr功能复合材料。基于Gr功能复合材料的DNA电化学传感器与常规DNA传感器相比,具有明显的特色和优势,已被应用于特异DNA靶序列的识别和传感领域。本文就基于Gr功能复合材料的DNA电化学传感器的近期进展作简要评述,包括Gr与Gr基金属、金属氧化物、高分子、生物分子复合材料的电化学性能及其在DNA电化学传感中的应用,并对该类DNA电化学传感器的发展方向和应用前景进行了展望。     

石墨烯量子点的制备

作为石墨烯家族的最新一员,石墨烯量子点(GQDs)除了具有石墨烯的优异性能,还因量子限制效应和边界效应而展现出一系列新的特性,因此吸引了化学、物理、材料和生物等各领域科学家的广泛关注。仅近两三年内,关于这种新型零维材料的研究,在实验和理论方面均取得了极大进展。本文主要介绍制备GQDs的两大类方法——自上而下和自下而上的方法。前者包括水热法、电化学法和化学剥离碳纤维法,后者则主要介绍溶液化学法、超声波法和微波法、可控热解多环芳烃法。另外还对一些制备条件较为苛刻的制备方法如电子束刻蚀法和钌催化富勒烯C60开笼法也作了简要介绍,并对GQDs的应用前景进行了展望。     

磷酸钙纳米结构材料的微波辅助液相合成

微波加热作为一种新兴热源具有加热速率快、制备时间短、节能等优点,已经被广泛应用于合成包括磷酸钙在内的多种无机纳米材料.磷酸钙作为典型的生物材料,其制备新方法的探索、结构/尺寸/形貌调控、性能研究和应用探索是生物材料领域的一个重要研究方向.本文阐述了微波辅助合成法用于制备纳米材料的优势,并综述了微波辅助液相快速合成磷酸钙纳米结构材料的进展.采用微波液相合成技术,可以制备出包括颗粒、一维、二维和三维结构在内的多种磷酸钙纳米结构材料,同时还可以通过功能性组分的掺杂/复合对磷酸钙纳米材料进行功能化.预期未来微波液相合成法在包括磷酸钙在内的多种无机纳米材料的合成领域将得到快速发展和广泛应用;另外,微波液相合成的磷酸钙纳米结构材料在药物递送和控释、蛋白吸附、金属离子吸附、生物成像及骨缺损修复等众多领域具有良好的应用前景.     

单分散磁性Fe3O4纳米粒子修饰石墨烯的制备及应用

通过油相热分解法在石墨烯(Gr)的表面修饰单分散的Fe3O4纳米颗粒,然后将二亚乙基三胺五乙酸(DTPA)通过多巴胺(DPA)化学键合到到Gr复合物表面,制备了新型磁性纳米复合材料Gr@Fe3O4-DPA-DTPA,采用X射线衍射、透射电镜、振动样品磁强计、傅里叶红外、拉曼和紫外光谱等技术对该材料进行了表征。结果表明,材料对水中的芳香族化合物和重金属离子具有很强的吸附能力,对水中的萘和Cu2+的吸附容量分别达到207.9和72.2mg/g。     

多孔石墨烯材料

多孔石墨烯是指在二维基面上具有纳米级孔隙的碳材料,是近年来石墨烯缺陷功能化的研究热点。多孔石墨烯不仅保留了石墨烯优良的性质,而且相比惰性的石墨烯表面,孔的存在促进了物质运输效率的提高,特别是原子级别的孔可以起到筛分不同尺寸的离子、分子的作用。更重要的是,孔的引入还有效地打开了石墨烯的能带隙,促进了石墨烯在电子器件领域的应用。本文阐述了多孔石墨烯的一些基本性质和特性,并对其理论研究、制备方法和应用的研究进展进行了评述。其中,多孔石墨烯的制备方法主要包括光刻法、催化刻蚀法、化学气相沉积法、湿法刻蚀、碳热还原法、溶剂热法和自由基攻击法。多孔石墨烯优异的特性使其在能源储存与转换材料(锂离子电池、超级电容器、燃料电池等)、DNA分子检测、化学传感器、场效应晶体管、分子筛和海水淡化等领域具有非常广阔的应用前景。     

石墨烯/纳米银复合材料的制备及其应用研究进展

石墨烯/纳米银复合材料由于两种纳米材料产生的协同效应,使其具有多种优异的性能,从而在许多领域表现出巨大的应用潜能.以石墨烯/纳米银复合材料为综述对象,详细的介绍了它的制备方法,包括微波辐射法、液相合成法、热还原法、化学还原法、电沉积法和电子束辐射法等,以及在电化学、生物检测、抑菌抗菌、催化剂和环境治理方面的应用,并对其今后的研究方向和发展前景进行了展望.     

层间共价增强石墨烯材料的构筑、性能与应用

大批量石墨烯可控制备技术的逐渐成熟为实现其宏观组装和应用提供了基础。在众多的组装策略中,调节石墨烯层间的界面相互作用可以直接影响组装体的力学、电学、热学以及渗透等性质,具有重要的意义。石墨烯片层间以共价键连接的层间共价石墨烯材料以其可调的层间距、较强的层间作用力、丰富的功能化、以及可能的原子构型重排等特性,受到了广泛的关注和深入的研究。相比于其他非共价的键合手段,共价连接是一种更为牢固的枢纽。本文中我们将总结讨论层间共价石墨烯材料的构筑方法、性能以及应用。在构筑方法中,依据石墨烯本身的制备方法分为氧化还原法以及化学气相沉积法,而在氧化还原法中,以其宏观材料的形貌分为纸状和纤维状来讨论。接着,我们重点介绍了层间共价对其力学和电学性能的影响,并概述了此类宏观组装体材料的应用。层间共价石墨烯材料继承了石墨烯自身优异的特性,同时也具有宏观组装所赋予的性能,有望在多个领域得到广泛的应用。     

含石墨烯的聚乳酸复合纳米纤维的制备及细胞相容性

利用电纺丝技术制备了聚乳酸(PLLA)-石墨烯(Gr)复合纳米纤维.通过SEM、TEM及拉曼光谱观察和分析了该复合纳米纤维的形貌及Gr在PLLA中的分散状态,通过DSC、TG、力学拉伸及接触角测试等表征方法研究了PLLA-Gr复合纳米纤维的热性能、力学性能、亲水性等物理性能,最后,通过MTT法检测一种神经胶质细胞——雪旺细胞(SCs)在该复合纳米纤维支架上的生长和增殖行为,评价其细胞相容性.结果表明:低含量的Gr能较好地分散在PLLA纳米纤维中,且随着m(Gr)∶m(PLLA)从0增加到2.0％,所得到的纤维直径呈现先减小后增加的趋势.当m(Gr)∶m(PLLA)增加到1.0％时,PLLA Gr纳米纤维的直径达到最小,为(0.50±0.19) μm,对应的拉伸强度较未添加Gr时增加也最大达50％.PLLA-Gr纳米纤维膜的结晶度与Gr的含量和分散性有关.细胞培养1、4、7d后的MTT检测结果表明PLLA-Gr复合纳米纤维能促进SCs的黏附和生长.PLLA-Gr复合纳米纤维具有较好的细胞相容性.     

三维多孔泡沫石墨烯的制备与应用研究进展

泡沫石墨烯是一种新型的碳基化工材料,具有独特的三维连通网络结构和优异的力学、热学、电学和化学稳定性能。本文综述了三维多孔泡沫石墨烯的制备与应用研究进展,主要介绍其水热法和化学气相沉淀制备法以及其作为催化材料、检测材料及电极材料的应用研究现状,并探讨了该领域亟待解决的重要问题和未来发展前景。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.