富勒烯及其衍生物的表征技术

富勒烯C_(60)是一类由12个五元环和若干六元环组成的笼状分子。C_(60)最初是在激光解析飞行时间质谱上被发现的,随后其大量的衍生物被合成和应用。现代分析表征技术对深入研究C_(60)及其衍生物的生成机理具有重要意义。本文以C_(60)及其衍生物为对象,重点评述了质谱(MS)、紫外可见近红外吸收光谱(UV-VisNIR)、红外光谱(IR)、拉曼光谱(Raman)、X射线衍射法(XRD)、核磁共振(NMR)和电子显微术等表征技术的应用。最后对C_(60)及其衍生物的表征技术和研究趋势进行了展望。     

富勒烯和富勒烯衍生物中的Stone-Wales旋转

Stone-Wales旋转是富勒烯异构化的基本方式,了解其特征和规律对于理解富勒烯和富勒烯衍生物的形成至关重要.本文采用密度泛函理论方法系统研究了富勒烯和富勒烯衍生物的Stone-Wales旋转.结果显示,富勒烯异构体趋向于从高B55键(两个五元环共用的边)结构向低B55结构转化,满足独立五元环原则的结构或具有低B55键数的异构体在热力学上更为有利.相反,对于富勒烯衍生物,具有更多B55的异构体不仅在热力学上更有利,而且从动力学角度讲,从满足独立五元环原则的结构向不满足的结构的转变比相反过程更容易.这些结果可以解释目前的相关实验事实,暗示了富勒烯衍生物可能是先衍生化后异构化而形成.     

新型富勒烯衍生物的激光质谱结构表征

对3种电化学方法合成的新型结构富勒烯衍生物进行了激光质谱表征,确认了1,2加成以及[5,6]开环富勒烯衍生物结构.质谱结果发现了富勒烯以及富勒烯衍生物与氧的结合峰,核磁共振结果进一步证明了富勒烯衍生物的结构,为含有C60结构衍生物的研究提供了有力的表征手段.     

富勒烯吡咯烷衍生物的应用研究进展

综述了近几年来富勒烯吡咯烷衍生物的应用研究,着重从生物活性、分子磁性和光电材料等几个方面介绍了富勒烯吡咯烷衍生物研究的最新进展。参考文献54篇。     

水溶性金属富勒烯衍生物的合成和表征

Three water-soluble metallofullerene derivatives have been synthesized.IRand XPSanalysis indicate that they have average compositions of Gd@C₈₂(OH)₂₂, Gd@C₈₂(OH)₆(NHCH₂CH₂SO₃H)₈and Gd@C₈₂(OH)₅(NHCH₂COOH)₉, respectively.They are particularly interesting in medical application.     

氟化富勒烯的研究进展

介绍了近几年来氟化富勒烯的合成、分离和一般性能.     

富勒烯衍生物引发的富勒烯末端封端聚己内酯的合成

利用带活性羟基的N-取代3,4-富勒烯吡咯烷作为引发剂,引发ε-己内酯开环聚合,制备了一种具有新型结构的富勒烯末端封端聚己内酯,通过核磁共振(1H NMR,13C NMR)、红外光谱(FTIR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)等手段对产物进行了结构表征,并用热重(TG)分析和差示扫描量热(DSC)分析的方法进行了热学性能分析.结果表明,与聚己内酯相比产物热稳定性增加.     

富勒烯衍生物纳米颗粒水悬液对细菌生长的抑制作用

富勒烯纳米颗粒的生物学效应受到了广泛关注。本文首次测定了二加成亚甲基富勒烯[60]二膦酸四乙酯(bis-methanophosphonate fullerene, BMPF)的纳米水悬液（nano-BMPF）和富勒醇纳米水悬液（nano-fullerol）对细菌生长的影响。结果显示,nano-BMPF和nano-fullerol在黑暗条件下可抑制革兰氏阳性菌金黄色葡萄球菌的生长,且呈现浓度梯度依赖性,半抑制浓度IC50值分别为9.1 μM和4.2 μM;nano-fullerol对金黄色葡萄球菌生长的抑制可能与活性氧无关, nano-BMPF对金黄色葡萄球菌生长的抑制则可能与超氧阴离子自由基(O2.-)有关。在黑暗条件下二者对革兰氏阴性菌大肠杆菌的生长无影响。以上结果表明,这2种富勒烯衍生物纳米颗粒作为抗生素在生物医用领域具有潜在的应用前景。     

基于富勒烯衍生物修饰玻碳电极的DNA电化学传感器

以富勒烯C₆₀, L-苏氨酸及对苯二甲醛为原料, 在氮气保护下反应得到含醛基官能团的2-(4-醛基苯基)-5-(1-羟乙基)富勒烯吡咯烷衍生物(C₆₀-CHO). 将该材料修饰于玻碳电极表面, 并利用醛基与氨基之间温和、高效的缩合反应, 将5-氨基修饰的寡聚核苷酸共价固定到了C₆₀-CHO修饰的玻碳电极表面, 构建了一种新型的电化学DNA传感器. 以[Fe(CN)₆]^3−/4−为电活性探针, 采用电化学阻抗法对转基因植物CaMV35S启动子基因特征片段进行检测. 实验结果表明, 杂交前后的电子传递电阻差值(DR_et)与目标序列浓度对数(lg C_S2)在1.0×10^－13～1.0×10^－9 mol/L浓度范围内呈良好的线性关系, 线性回归方程为DR_et/(10³ Ω)＝3.471 lg (C_S2/mol/L)＋50.425 (r＝0.9977), 检测限为1.5×10⁻¹⁴ mol/L. 杂交特异性实验进一步表明该传感器对完全互补、碱基错配和非互补序列具有良好的识别能力.     

富勒烯功能高分子材料的制备与性能研究

对富勒烯功能高分子材料的制备、表征及其性能研究已成为光前国际上的前沿领域之一。从合成角度考虑,以不同的方法对Ｃ６０进行高分子修饰可得到结构、性质各异的富勒烯高分子衍生物,对于研究如何更好地控制Ｃ６０高分子衍生物的结构,探讨了有Ｃ６０参与的聚合反应的机理以及Ｃ６０在高分子衍生物中的作用无疑是很有帮助的。从应用角度考虑,Ｃ６０引入高分子中必将导致新型聚合物的产生。这些新型聚合物表现出许多独特而极具应用     

Fabrication of Flowerlike Supramolecular Architectures of Fullerene Derivatives Bearing a Small Nitrophenyl Substituent

Flowerlike supramolecular architectures were fabricated from fulleropyrrolidincs bearing a small para-, meta-, or ortho-nitrophenyl group. The self-assembled architectures were characterized by scanning electron micro-scopy（SEM） and X-ray diffraction（XRD）. It was found that these flowerlike architectures were assembled from na- noplatcs that formed from fundamental subunit of interdigitated lamellar bilayer structure.     

Classical Valence Similarity in Fullerene Derivatives

Summary.  The generalized Pauling bond order was enumerated in the C₆₀ fullerene cage molecule (truncated icosahedral symmetry). This index measures chemical similarity in fullerene derivatives such as dihydrofullerene (C₆₀H₂), anionized monohydrofullerene (C₆₀H⁻), N-substituted monohydrofullerene (C₅₉NH), the fullerene dimer ((C₆₀)₂), and the dianionic fullerene dimer ((C₆₀)₂ ²⁻). It is also useful in judging the chemical stability of isomers. Received October 9, 2001. Accepted November 9, 2001     

Fullerene graphs have exponentially many perfect matchings

A fullerene graph is a planar cubic 3-connected graph with only pentagonal and hexagonal faces. We show that fullerene graphs have exponentially many perfect matchings.     

Solvent-free Synthesis of Dihydrofuran-fused [60]Fullerene Derivatives by High-speed Vibration Milling

Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.…     

Neuron models.

The nervous system is made up of several kinds of cells which should ideally be examined separately in biochemical studies. Since we are not yet able to isolate the different kinds of cells, use is made of cell lines derived from a single cell which are isolated from tumors of the nervous system and which can be reproduced at will in the same way as bacteria. They include cell lines isolated from a mouse neuroblastoma which exhibit some of the properties of nerve cells. Hybrid cells obtained by fusion of mouse neuroblastoma cells with rat glioma cells display even more characteristics of nerve cells. This article considers properties which justify our regarding the hybrid cells as neuron models. Application of the cells to problems of the nervous system is then demonstrated: (1) processing of information arriving in the form of mutually opposing hormonal signals; (2) mode of action of morphine.     

富勒烯[60]的光化学反应研究

从光物理出发,综述了近几年富勒烯「６０」的光化学反应研究进展。Ｃ６０能发生诸多的光化学反应：（１）光氧化;（２）光氢化还原;（３）「２＋２」光环化加成;（４）与叔胺的光加成;（５）与氨基酸的光加成;（６）与金属有机化合物的光加成。     

SynthesisofFullereneC＿（60）DerivativesbyOne－potProcedure

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碳笼烯(C60)在高分子领域中的研究进展

综述了碳笼烯（Ｃ６０）在高分子领域中的研究进展,包括碳笼烯的高分子化、与聚合物形成电荷转移复合物以及作为催化聚合反应的催化剂。