富勒烯及其改性衍生物在催化燃料电池领域的研究进展

富勒烯因其独有的结构,优异的光学、电学等性能而被作为催化剂载体,应用于燃料电池等诸多方面.文章综述了以C60为代表的富勒烯的结构、理化性质,并阐述了富勒烯及其衍生物作为贵金属催化剂载体的应用,最后对富勒烯的未来发展进行了展望.     

C60RuCl2(phCH2Pph2)2的合成与表征

富勒烯金属配合物具有特殊的物理和化学性质.本实验在氮气氛中采用配体取代法合成了富勒烯Ru金属配合物C60RuCl2(phCH2Pph2)2,并利用元素分析、红外光谱、紫外可见光谱、光电子能谱、X射线多晶粉末衍射对配合物的组成、结构等进行了表征.结果表明,C60以σ──π配位方式与Ru形成了稳定的η2型C60金属配合物C60RuCl2(phCH2Pph2)2.     

三种纳米材料C_(70),C_(60)Cl_6和C_(60)Ph_6引起细胞自噬的现象

为了进一步研究富勒烯家族及其衍生物引起细胞自噬的现象,运用荧光显微镜、透射电子显微镜、蛋白免疫印迹等技术,对水溶性的纳米C70,C60Cl6和C60Ph6诱导的细胞自噬现象进行了初步探讨.实验结果显示,C70,C60Cl6和C60Ph6稳定分散于水中形成的纳米颗粒,均能诱导HeLa细胞产生自噬现象,揭示了富勒烯家族及其衍生物在生物医药领域更广泛的研究和应用价值.     

四噻吩与富勒烯(C60、C70、C84)间光致电子转移效率的研究

借助荧光猝灭可以观测和研究导电聚合物与富勒烯之间的电子转移效率及机理.文章通过对四噻吩/富勒烯相关原始数据的校正处理,排除了竞争吸收与重吸收对荧光谱值的影响,获得了能真实体现四噻吩与富勒烯(C60、C70、C84)之间荧光猝灭率的数据.     

富勒烯及其衍生物动物实验的研究进展

<正>1985年,Kroto等由于成功地发现了以C60为代表的富勒烯[1],而共同分享了1996年度的诺贝尔化学奖。自1990年Krstschmer等找到了合成克量级C60的方法以来[2],许多生物学家就开始了对富勒烯及其衍生物的研究。富勒烯及其衍生物的生物学效应包括酶活性的抑制、DNA选择性剪切作用、抗菌     

富勒烯(C60/C70)与 N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚电荷转移复合物的特征

用激光光解方法研究了富勒烯(C60 / C70)与N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚电荷转移复合物的特征. 通过观察在近红外区瞬间吸收带,富勒烯(C60 / C70)激发三线态,富勒烯(C60 / C70)阴离子自由基和N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚阳离子自由基的出现,测定了在苯腈溶液中从N,N,N′,N′-四-(对甲基苯)-4,4′-二胺-1,1′-二苯碲醚到富勒烯(C60 / C70)激发三线态的量子转化产率和电子转移常数.     

水溶性富勒烯分子囊泡在二维DNA晶体上的有序自组装

C60-N,N-二甲基吡咯是一种水溶性富勒烯的衍生物,在水体系中会聚集成分子囊泡.C60分子囊泡的直径范围为20~120 nm,其中70%的直径小于60 nm.在本实验中,把这种水溶性富勒烯衍生物的分子囊泡和磷酸化的2D DNA晶体在一定条件下静止,原子力扫描显微镜可以观察到在DNA晶体表面,富勒烯的分子囊泡形成了珍珠串状的有序排列.通过对原子力扫描显微镜的图片分析,初步推断了富勒烯的分子囊泡在DNA晶体上进行自组装的机理.     

荧光光谱法研究六噻吩与富勒烯的相互作用

文章采用荧光光谱法研究在六嚷吩(6T)/富勒烯(C60,C70和C84)混合液中由电子转移所引起的荧光猝灭现象,并由Stern-Volmer方程分别确定了6T/C60、6T/C70和6T/C84混合液中的双分子猝灭速率常数.结果表明,双分子猝灭速率常数与富勒烯的电子亲和力相关,对6T/C60、6T/C70和6T/C84...     

富勒烯新结构的研究进展

富勒烯Cn是一类由12个五元环和若干六元环组成的笼状全碳分子.根据碳笼表面是否含相邻分布的五元环,富勒烯可分为IPR富勒烯和非IPR富勒烯.25年来,人们在发展富勒烯合成新方法和寻找富勒烯新结构方面做了大量的工作,富勒烯家族得到了很大的扩充,越来越多的富勒烯新结构被陆续发现和分离出来.迄今为止,已分离、表征了C20~C104的60余种富勒烯新结构,包括40余种IPR富勒烯结构,以及通过笼外化学修饰或内嵌原子(或原子簇)的稳定化策略合成的20余种违反IPR规则的富勒烯.详细总结了这些迄今为止已报道的各种富勒烯新结构,并对今后富勒烯研究的重点和内容进行了预测.     

低能He@C_60 He@C_60碰撞的动力学研究

建立了基于半经验势的分子动力学模型,研究了不同入射能量下C60 C60和He@C60 He@C60的对心碰撞动力学性质,并比较了富勒烯内嵌He原子的存在对碰撞的影响.发现随着入射能量的不同,形成的碰撞产物的二聚体结构不同,并呈现出自组装的性质.He原子在能量较高时对碰撞产物的结构影响较大,在一定程度上能够增强富勒烯二聚体结构的稳定性。     

富勒烯[ 60] 与电子给体电荷转移络合物的特性

通过毫微秒激光光解作用研究了富勒烯[60]电荷转移络合物的特性，在苯腈溶液中，从电子给体(TTF)到富勒烯[60]激发三线态的电子转移反应已被观察到，富勒烯[60]激发三线态的消失和富勒烯[60]阴离子自由基的出现，通过瞬态吸收光谱得到证实。     

Influence of organic acids on UV-Vis spectra of pyrrolidino-[60]fullerene derivatives

A pyrrolidino[60]fullerene 1 with pyrrolidine group was synthesized and characterized. The UV-Vis spectra showed that the blue shift of absorption peaks was first observed when strong organic acids such asp-toluene sulfonic or trifluoroacetic acid were added to the solution of pyrrolidino[60]fullerene 1 in dichloromethane. The results indicated that the pyrrolidino[60]fullerene derivatives without pyrrolidine group also possess the same phenomenon. Experiments and computation with the MOPAC 7.0 semi-empirical PM3 method demonstrated the reason that some energy gaps on [60] fullerene skeleton were increased because electronic charges on [60] fullerene framework transferred to pyrrolidine ring when strong organic acids were added into pyrrolidino[60]fullerene derivatives’ solution; as the result, the complexes could be formed and some absorption wavelengths blue shifted in the UV-Vis spectrum.     

2-(4-羟基苯基)[60]富勒烯吡咯烷衍生物的合成研究

利用1,3-偶极环加成反应,合成分离得到了一种C60吡咯烷衍生物:2-(4-羟基苯基)[60]富勒烯吡咯烷,通过单因素方法,探讨了反应条件对产物产率的影响,并得到了较适宜反应条件:反应物摩尔比(C60:4-羟基苯甲醛:甘氨酸)为1∶4∶6,反应温度为100℃,反应时间为18 h,此时产物的产率可达到53%(以消耗的C60计)。同时用UV-Vis、1H-NMR、FT-IR、MS等测试手段表征了产物的结构,并利用差热分析仪测试了产物的热稳定性,结果表明,产物在一定温度下,具有良好的热稳定性。     

嘧啶环二炔氮桥C60衍生物的合成及非线性光学性质

合成了嘧啶环二炔氮桥C₆₀衍生物C₆₀NPD ,研究了在532nm、脉宽 8ns条件下的非线性光学特性。通过Z-扫描实验发现C₆₀NPD有很强的非线性吸收和非线性折射,并获得了三阶非线性光学系数χ⁽³⁾ 。同时也研究了光限幅特性，实验结果表明C₆₀NPD有较低的光限幅箝位值。     

Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

Ferric perchlorate-promoted reaction of [60]fullerene with β-keto esters

The ferric perchlorate-promoted reaction of [60]fullerene (C60) with ethyl 2-methylacetoacetate generates fullerenyl hemiketal as a mixture of trans and cis isomers,while the reaction with ethyl acetoacetate gives a C 60-fused dihydrofuran derivative.A possible reaction mechanism for the formation of these products is proposed.     

Photoconductivity of [60]fullerene derivatives

Two [60]fullerene derivatives (compounds 1 and 2) have been synthesized. Their redox properties have been measured by cyclic voltammetry. The photoconductivities of poly(N-vinylcarbazole) (PVK) doped with [60] fullerene and with their derivatives have been studied to explore the possible relationship between the reductibility of fullerenes and the photoconductivity of fullerenes-doped PVK. The charge generation efficiencies of PVK doped with [60]fullerene and with its derivatives have changed remarkably: the diversity of charge generation efficiency is obvious in different doping systems. The result indicates that there is charge transfer between fullerenes and PVK.     

Synthesis and Characterization of [60]Fullerene Ferrocenylmethyl Derivatives

Two new [60]fullerene ferrocenylmethyl derivatives have been prepared via different approaches and characterized by UV-Vis、 FT-IR、 NMR、 FAB-MS spectra and VPO. The second approach , i.e reacting fullerene with ferrocenylmethyl azide directly, was never reported as yet.     

Synthesis and characterization of [60]fullerence ferrocenylmethyl derivatives

Two new [60]fullerene ferrocenylmethyl derivatives have been prepared via different approaches and characterized by UV-Vis, FT-IR, NMR, FAB-MS spectra and VPO. The second approach, i.e. reacting fullerene with ferrocenylmethyl azide directly, was never reported as yet. Foundation item: Supported by the Fund for Ph. D Programme from Ministry of Education, P. R. China (98048624) Biography: Li Xin-hong (1973-), female, Ph. D candidate, research direction: fullerene chemistry.     

Construction of Supramolecular Architectures via Self-assembly

1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).