碳六十内嵌复合物中钠及氯与碳六十之间的相互作用

本文用量化学及分子力学方法计算了（Ｎａ＠Ｃ６０）及（Ｃｌ＠Ｃ６０）中Ｎａ及Ｃｌ与Ｃ６０之间的相互作用，总的相互作用是吸引。在静电相互作用、色散相互作用及电子云重排斥相互作用三项中前一项占９０％以上，有着决定性的影响，色散相互作用约占５％。对电子云重叠排斥作用来说，由于Ｃｌ＾－的半径比Ｎａ＾＋的大很多，所以在（Ｃｌ＠Ｃ６０）中这种作用要比在（Ｎａ＠Ｃ６０）中大很多。     

C60与铈卟啉相互作用的密度泛函理论研究

应用Perdew-Burke-Ernzerhof (PBE)密度泛函理论对5种可能存在的富勒烯与铈卟啉复合物进行了几何结构优化, 通过分子间距离及结合能数值, 确认了C₆₀和铈卟啉可以通过非键相互作用形成超分子主-客体复合物, 且最有可能的作用位点为C₆₀的C5:6键(相邻五元环与六元环共用碳-碳键). 应用扩展过渡态方法对结合能进行分解, 分解结果显示, 静电能对总吸引能的贡献约为60%, 说明静电作用是复合物稳定存在的最主要因素. 最后对复合物中的电子流向进行了研究, 结果表明复合物中电子的转移与主-客体间相互作用有一定联系, 且电子是从主体铈卟啉流向客体C₆₀.     

重氮树脂型聚电解质复合物与SDS相互作用研究

由于聚电解质与表面活性剂的相互作用具有很多特别的性质而倍受关注［１～１０］,但具有感光性的重氮树脂作为正离子聚电解质与表面活性剂相互作用尚未见报道．本文研究了重氮树脂（ＤＲ）与聚苯乙烯磺酸钠（ＰＳＳ）形成的聚电解复合物（ＤＲ－ＰＳＳ）与十二烷基硫酸钠...     

粒子-聚合物相互作用与粒子-粒子相互作用对聚合物基纳米复合物力学性能的影响

聚合物基纳米复合物(PNCs)具有比传统高分子材料更加优异的光学、力学、热力学等性能,广泛应用于各个工程领域.而纳米粒子(NPs)对材料性能提高的机理则是当前聚合物纳米复合物领域研究的重要问题,聚合物纳米复合体系相互作用的影响因素众多,至今尚未明确并完整建立复合体系相互作用与性能增强之间的关系.本文总结了近年来关于纳米粒子填充聚合物基体力学性能的研究,从粒子-聚合物相互作用和粒子-粒子相互作用角度阐述了聚合物纳米复合体系力学性能的增强机理,并根据体系中不同的结构关系分别总结了聚合物/未改性纳米粒子复合体系和聚合物/聚合物接枝纳米粒子复合体系中影响力学性能的因素.该部分内容具有重要的理论和实践意义,有助于构建复合体系微观结构与宏观性能之间的关系,进而对微观层面调控PNCs的力学性能提供指导.     

MALDI方法研究蛋白质的非共价复合物

飞行时间质谱仪(TOFMS)在理论上无质量范围的限制,可实现大分子蛋白质与核酸的非共价复合物的直接检测.特别是在近中性溶液条件下通过对芥子酸和6-氮杂-2-硫代胸腺嘧啶基质的使用及双层样品制备方法的改善,获得了稳定复合物的高灵敏度质谱检测.肌红蛋白-血红素复合物能够在芥子酸基质的不同pH条件下(pH2.0或pH5.0)同时观察到.而运用双层样品制备方法,获得了核糖核酸酶复合物(RNaseS)在第一次激光照射下的突出质谱峰,但其丰度均随更多的激光打击而减弱.     

HCCO自由基与水分子氢键复合物的从头算研究

在MP2/aug-cc-pvdz水平下,对二体氢键复合物H2O…HCCO(Ⅰ)和HCCO…H2O(Ⅱ)以及三体氢键复合物(H2O)2…HCCO(Ⅲ),H2O…H2O…HCCO(Ⅳ)和H2O…HCCO…H2O(Ⅴ)的几何和相互作用能进行了计算.轨道分析表明Ⅲ中HCCO中的H(1),C(2)通过2个氢键与2个水分子形成了环...     

不对称C60-聚茚复合物的合成与性质

成功合成并分离出两例不对称C₆₀-三聚茚复合物分子,利用高分辨质谱、元素分析,核磁共振氢谱、碳谱对化合物的结构与纯度进行了表征;利用紫外光谱、循环伏安曲线对化合物的电子结构进行了表征。结果表明: C₆₀-分子与三聚茚结合后表现出较为明显的分子内电子转移,证明扩展共轭体系对分子的共轭性有较为明显的调控作用。     

壳聚糖维生素C复合物的合成及性能

通过离子间静电引力作用合成了壳聚糖维生素C复合物。采用红外光谱和差热分析测试技术表征了复合物的结构。溶解度测定结果表明,该复合物具有水溶性。邻苯三酚自氧化速率测定结果表明,该复合物对.O2-的清除作用优于壳聚糖。     

蛋白质相互作用的研究方法

生物体的生理功能主要由细胞中的蛋白质控制和调节。其中,多数蛋白质是通过与配体结合或是作为蛋白质复合物中的一部分参与细胞的代谢过程。因此,研究蛋白质间的相互作用是理解生命活动的基础。本文对现有蛋白质相互作用的研究方法和技术进行了评述。     

C_（60）分子间相互作用势及其晶体压缩系数的计算

根据Ｃ（６０）晶体升华焓的实验值求得了Ｃ（６０）分子间相互作用势的解析表达式。用该表达式计算了Ｃ（６０）分别为面心立方和六方晶格时晶体的结合能，讨论了不同晶格的稳定性问题，解释了Ｃ（６０）晶体一般是面心立方的原因。本文还根据Ｃ（６０）分子间相互作用势计算了Ｃ（６０）晶体的压缩系数，并与文献的实验值进行了比较，所得结果与实验值相符合。     

He+C60↔(He@C60)的反应势垒研究

The reaction barriers of (He+C60(He＠60)) have been calculated by the quantum-chemical method EHMO/ASED in the following four paths: (1) penetrate through the pentagon on the C60 cage; (2) penetrate through the hexagon on the C60 cage,(3) penetrate through the short bond; (4) penetrate through the long bond. Corresponding to each path, there are two choices: (a) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a planar extension and a concerned window is formed; (b) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a spherical extension and a concerned window is formed. The results are given in Figs. 1-2 and Tables 1-2. It is shown that the reaction through path(4) with choice (a) has the least reaction barrier, being optimum. At that case, a window of 9-membered ring is formed. Because the window extension of C6H6 is more free than that of C60, the barrier of He penetrating through C6H6 will be lower than that of He penetrating through C60.     

C60微电极伏安法研究

The microdisk electrode voltammetric behaviors of C_(60) are reported in this communication. This was accomplished by use of a mixed solvent system as Acetonotrile:Xylene=1:4 and a supporting electrolyte as 0.1 mol·L~(-1) Bu_4NPF_6. Au, Pt and Hg (Pt) were used as working electrode. In this new conditions, the successive six step reduction of C60 were obtained at below 15 ℃. It was found that the former five steps are all the single electron reversible reduction, but behaviors of the sixth steps are like EC' processes. Several electrochemical data were determined.     

C60离子束撞击固体表面的坍塌沉积(I)共焦显微拉曼光谱研究

Raman spectroscopy was applied to characterize the species deposited from the mass-selected C60 ion beam which was accelerated to 900 eV. The substrates for the deposition were (0001) surface of highly oriented pyrolitic graphite and (111) surface of gold crystal. The species do not exhibit the Raman scattering features of buckminsterfullerene, but displays peaks at 1585 and 1332 cm-1 instead. The former peak is the chararteristic Ranan peak of hexagonal graphite, and the latter can be attributed to the amorphous carbon in sp3 hybridization. The result reveals that C60 was collapsed to form a new phase when it collides on the solid surface.     

以C60为媒介的网状金纳米粒子聚集体的构筑

通过全甲基化环糊精和卟啉之间的"Click"反应,合成了一种不对称环糊精修饰的卟啉衍生物,并对其结构进行了表征.该化合物与氯金酸作用可以形成平均粒径为5 nm的水溶性金纳米粒子,该金纳米粒子进一步与C60作用形成网状纳米聚集体,并通过紫外光谱和透射电子显微镜验证了聚集体的结构.     

C60离子束撞击固体表面的坍塌与沉积(II)扫描隧道显微研究

Mass-selected C60 beam produced by laser ablation was accelerated and bombarded the (0001) surface of highly oriented pyrolitic graphite and (111) surface of gold single crystal. The samples were characterized by STM. The STM images showed that, the deposited species collapsed and formed planar structure on the solid surface, but the collapsed species were not dissociated and well oriented on the surface. Both positive and negative C60 ions were observed in the desorption mass spectra, confirming that the species collapsed on the solid surface are still the C60 clusters.     

C60的加成反应

富勒烯化学是以全碳分子球烯为母体的新兴有机化学领域, 在材料、医学及立体化学合成方法等方面具有广泛的应用和发展前景。本文综述了C₆₀的加成反应, 较全面地展示了富勒烯的化学性质。     

C12-s-C12•2Br和C12En混合水溶液的胶团化行为

季铵盐二聚表面活性剂C12 s C12•2Br（s=2、3、4、6）和非离子表面活性剂C12E10或C12E23在水溶液中生成混合胶团.其临界胶团总浓度cmcT值介于二元复配体系中各组分的临界胶团浓度和之间.当添加少量非离子型表面活性剂（在水溶液中的摩尔分数α2=0.1）时,混合胶团中C12E10或C12E23的摩尔分数均已超过0.35;随着溶液中非离子型表面活性剂含量的增大,混合胶团中逐渐以C12E10或C12E23成分为主.     

One-pot three-component reaction of C60, amino acid and fluorinated benzaldehyde to C60-pyrrolidine derivatives

A series of fluorinated 2,5-disubstituted C₆₀-pyrrolidine derivatives were synthesized via one-pot three-component reaction of C₆₀, amino acid and fluorinated benzaldehyde under reflux in toluene or microwave irradiation. The cis- and trans-isomers could be isolated by chromatography and fully confirmed by ¹H NMR.     

双亲性C60衍生物水相聚集行为

富勒烯C₆₀几乎不溶于水中,从而阻碍了对富勒烯的进一步研究和潜在应用。双亲性C₆₀衍生物在水相中自组装形成聚集体,在水相具有一定的溶解度,其特殊的结构及性能引起了科学家的广泛关注。本文对双亲性C₆₀衍生物在水相中聚集行为的研究现状及研究进展进行了详细系统的介绍。本文第一部分主要阐述了双亲性C₆₀衍生物的结构,根据修饰到C₆₀表面的功能基类型对双亲性C₆₀衍生物进行了分类。第二部分主要阐述了双亲性C₆₀衍生物在水相的聚集行为以及pH值、溶剂极性、浓度、温度和抗衡离子等因素对聚集行为的影响。     

Reactions of chlorofullerene C60Cl6 with N-substituted piperazines

It was shown for the first time that reactions of C₆₀ halides with aliphatic amines provide a facile route for the synthesis of aminofullerenes, valuable precursors for water-soluble cationic fullerene derivatives. Particularly, chlorofullerene C₆₀Cl₆ and N-substituted piperazines were investigated in this work. It was shown that substitution of chlorine atoms in C₆₀Cl₆ by amine groups is accompanied by partial elimination of addends from the fullerene cage that yields mixtures of di-, tetra- and, hexaaminofullerenes as the final products. Separation of these mixtures by column chromatography resulted in isolation of pure 1,4-diaminofullerenes; this procedure gives much higher and more reproducible yields of these compounds than direct oxidative photoaddition of secondary amines to C₆₀. ESI mass spectrometry and NMR spectroscopy data showed that hexaaminofullerene isomers are major components in inseparable mixtures of polyaddition products. Polyaminofullerenes were found to be readily soluble in aqueous acids; these solutions are unstable because of a facile substitution of protonated amine groups with hydroxyls. Nevertheless, the use of other amine substrates in the investigated reaction can potentially allow the preparation of more stable water-soluble cationic fullerene derivatives for biological studies.