[60]Fullerene功能材料的制备研究

由于富勒烯在光、电、磁等方面表现出独特的性质,因此以C60为代表的富勒烯的研究成为最近十几年来研究的一个热点.在C60的功能化研究中,大量的C60衍生物被合成出来;不同的C60衍生物具有更加特殊的性能,使得其在物理、化学、材料学、医学、生物学等方面显示出广阔的应用前景.     

水溶性C60-β丙氨酸衍生物清除超氧阴离子自由基O-·2及对小鼠胸腺细胞生长影响的研究

合成具有特殊生物活性的富勒烯衍生物及其生物活性的研究是近年来十分活跃的研究领域.许多实验显示C 60衍生物在抗爱滋病毒、神经保护、抗菌、 DNA切割和光动力学治疗等方面具有良好的应用前景[1]. 其中C 60衍生物对自由基的清除显得十分重要[2].     

苯醚键相联的C_(60)-卟啉二元化合物的合成、电化学和光谱性质研究(英文)

设计合成了一系列苯醚键相连的C60-卟啉二元化合物及其金属锌配合物:H2Por-p-C60、H2Por-m-C60、H2Por-o-C60、ZnPor-p-C60、ZnPor-m-C60和ZnPor-o-C60,通过质谱、元素分析和核磁共振氢谱对它们的结构进行了表征。基态的电子吸收光谱和电化学研究表明在这些二元体系中C60和卟啉之间存在明显的相互作用。荧光光谱研究表明卟啉单元的荧光几乎被C60单元完全淬灭,并且它们之间的连接位置对荧光淬灭的效率具有显著影响。     

水溶性C60衍生物在生物医学领域的研究现状

富勒烯C60具有完美的结构对称性和独特的物理化学性质,在生物医学、超导、光学和催化等领域有着极为广阔的应用前景。C60在水中的溶解度很低,与生物体的相容性差。这些特点限制了C60在生物医学领域的应用。因此人们合成出了多种水溶性的C60衍生物,并研究了它们的应用。本文综述了近年来水溶性C60衍生物在生物医学领域的研究,包括肿瘤治疗、药物或基因运载、抗氧化、与酶的相互作用、细胞毒性和其它应用,并对其未来的发展提出了展望。     

《化学通报》网络版（Chemistry Online）2006年第10期论文摘要

[w089]碳[60]六加成反应的研究进展**Researches on Hexakis-Addition Reactions of C60王海玲魏先文*(安徽师范大学化学与材料科学学院安徽省功能性分子固体重点实验室芜湖241000)从合成方法学角度阐述了C60六加成化合物的合成、表征和性质研究的最新进展,并展望了其应用前景。The synthesis and characterizationof C60hexakis-additioncompounds were reviewedinthe viewof the syntheticmethodology.The properties and applications of some C60hexakis-additon derivatives were also described.[w090]聚合物磷光电致发光材料的研…     

C60腈胺类衍生物的合成及三阶非线性光学性质

C60的三阶非线性光学性质的研究是近年来富勒烯物理化学性质的研究热点之一[1].研究显示,尽管C60具有三维共轭的π电子体系,其本身并不具有大的三阶非线性系数[2,3].但由于C60分子具有较低的三重简并LUMO能级,显示出较强的电负性,能够与适当的给电子体形成相应的电荷转移体系,其三阶非线性系数可提高一至两个量级[3-6].本文通过合成C60的腈胺和双聚腈胺衍生物及其Fe(Ⅲ)配合物,对其三阶非线性光学性质及电荷转移作了初步探讨.     

侧链上带有C60基团的聚苯乙烯的光电导性能

近几年来,可溶性高分子C60衍生物的合成已取得明显的进展.Weis等[1]报道了以C60封端的聚苯乙烯大分子衍生物,Hawker等[2]合成出聚苯乙烯C60的共聚物.这些单取代的C60衍生物很好地保持了C60原有的性质,加工性能和机械性能均较好.唐本忠等[3]用紫外光照射聚碳酸酯和C60溶液或在AIBN存在的条件下加热以上溶液,得到可溶的聚碳酸酯C60衍生物,该法产率很高(可达99%),且简单易行.Patil等[5]也用类似的方法通过自由基聚合将C60接枝到聚烯烃的高分子链上.我们已报道了将C60接枝到聚烯烃上所得到的共聚物的性能[5,6],但C60高分子衍生物的用途尚不清楚.     

AgmC60(OH)n(NO3)m的合成及其热稳定性

自从富勒烯被发现并克量级制备以来,富勒烯独特的结构和性质引起了人们极大兴趣和关注,对富勒烯及其衍生物的研究已迅速发展[1],由于C60具有光诱导剪切DNA、抑制艾滋病毒等特性,因而在生物化学及医学方面具有潜在应用前景,其中水溶性富勒烯衍生物的研究是富勒烯化学较为活跃的研究领域之一[2～5],尤其是羟基化富勒烯(或称富勒醇fullerenols)的合成方向的研究[5]。目前富勒烯羟基衍生物的合成方法已得以深入研究,但其化学反应性能的研究未见报道,本文合成了羟基C60银盐,并对其热稳定性能进行了研究。1　实验部分1 1　主要仪器及试剂C6…     

含C60的苯乙烯和丙烯酰胺共聚物的合成与表征

在高分子领域中,C60的高分子化一直是C60材料化的一个重要途径.迄今为止,制备含C60高分子的方法有以下几种:(1)采用自由基引发剂、阴离子引发剂或阳离子引发剂引发C60与烯类单体共聚[1,2];(2)对C60进行表面修饰,引入可聚合官能团,合成含C60的单体,随后聚合成含C60的高分子[3];(3)制备出带有功能基团的高分子前体,再通过功能化反应将C60引入高分子链[4～9].     

C60Pt(CO)(Pph3)配合物的合成及氧化还原性能研究

采用配体取代法,即在惰性气氛下以C60取代Pt(CO)2(Pph3)2中的CO及Pph3,合成了C60Pt(CO)(Pph3)富勒烯金属配合物,利用元素分析、红外光谱、紫外可见光谱、光电子能谱等手段对产物进行鉴定和表征,结果表明,C60以σ-π配位方式与Pt形成了稳定的η2型C60配合物.由于该分子存在超共轭作用,分子内电子流动性大,因而该配合物可能具有良好的光电转化性能及催化性能.氧化还原性能研究表明,C60在与金属有机基团Pt(CO)(Pph3)形成配合物后,其还原电位向负方向发生了移动.     

C_9H_(10)O_2-0.5ZnCl_2/Al_2O_3的制备及其氧化脱硫性能

通过将C_9H_(10)O_2-0.5ZnCl_2双酸型低共熔溶剂固载到Al_2O_3上制备了C_9H_(10)O_2-0.5ZnCl_2/Al_2O_3催化剂。该催化剂采用XRD、FT-IR、SEM、EDS、N_2吸附-脱附技术进行了分析。以C_9H_(10)O_2-0.5ZnCl_2/Al_2O_3为催化剂,过氧化氢为氧化剂研究模拟油中芳香族硫化物的脱除性能。考察反应参数如温度、催化剂加入量、O/S物质的量比、硫化物类型等对催化剂脱硫活性的影响。实验结果表明,在模拟油为5 mL、催化剂量为0.2 g、O/S比为8、反应温度为60℃、反应时间为180 min的条件下,模拟油中二苯并噻吩(DBT)脱硫率为99.2%。此外,在模拟油氧化脱硫中催化剂循环使用六次,其氧化脱硫活性略有降低。研究了C_9H_(10)O_2-0.5ZnCl_2/Al_2O_3催化氧化脱硫的反应机理。     

Template-directed Synthesis of Three Metal Oxalates via 4-Connected Building Units

Three novel compounds, [Co（en）3]2[Zr2（C2O4）7]·2H20（HNU-2, en=ethylenediamine）, [Co（NH3）6]· [Ce（CzO4）3（H2O）]·H2O（HNU-3） and [Co（dien）2][Gd（C2On）3]·0.75H2O（HNU-4, dien=dethylenetriamine） were hydro- thermal synthesized based on the templates of [Co（en）3]C13, [C0（NH3）6]C13 and [Co（dien）2]C13, respectively. The Zr4＋ Ce3＋ and Gd3＋ cations are all coordinated by four oxalates to form [M（C2O4）n（H2O）n]m （M=Zr, Ce or Gd; n=0 or 1; m=4 or 5）, which are similar to [In（C2O4）4]5- in NKB-1, and can be regarded as 4-connected building units. The [M（C2O4）a（H2O）n]m units are connected via sharing the bis-bidentate bridging oxalate ligands to form binuclears in HNU-2 and 1D ＂zigzag＂ chains in HNU-3 and HNU-4. cular building units to design 3D open frameworks with It is suggested that these compounds could be used as mole- zeolite topologies.     

Synthesis, reaction and structure of a series of chromium(III) complexes containing oxalate ligand

A series of chromium(III) complexes [Cr(bipy)(HC₂O₄)₂]Cl·3H₂O (1), [Cr(phen)(HC₂O₄)₂]Cl·3H₂O (2), [Cr(phen)₂(C₂O₄)]ClO₄ (3), [Cr₂(bipy)₄(C₂O₄)](SO₄)·(bipy)_0.5·H₂O (4) and [Mn(phen)₂(H₂O)₂]₂[Cr(phen)(C₂O₄)₂]₃ClO₄·14H₂O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed.     

Semiempirical molecular dynamics studies of C60/C70 fullerene oxides: C60O, C60O2 and C70O

The spectral analysis indicates that all isomers of C₆₀O, C₇₀O and C₆₀O₂ have an epoxide-like structure (an oxygen atom bridging across a C–C bond). According to the geometrical structure analysis, there are two isomers of fullerene monoxide C₆₀O (the 5,6 bond and the 6,6 bond), eight isomers of fullerene monoxide C₇₀O and eight isomers of fullerene dioxide C₆₀O₂. In order to simulate the real reaction conditions at 300 K, the calculation of the different isomers of C₆₀O, C₆₀O₂ and C₇₀O fullerene oxides was carried out using the semiempirical molecular dynamics method with two different approaches: (a) consideration of the geometries and thermodynamic stabilities, and (b) consideration of the ozonolysis mechanism. According to the semiempirical molecular dynamic calculation analysis, the probable product of this ozonolysis reaction is C₆₀O with oxygen bridging over the 6–6 bond (C_2v). The most probable product in this reaction contains oxygen bridging across in the upper part of C₇₀ (6–6 bond in C₇₀O-2 or C₇₀O-4) an epoxide-like structure. C₆₀O₂-1, C₆₀O₂-3 and C₆₀O₂-5 are the most probable products for the fullerene dioxides. All of these reaction products are consistent with the experimental results. It is confirmed that the calculation results with the semiempirical molecular dynamics method are close to the experimental work. The semiempirical molecular dynamics method can offer both the reaction temperature effect by molecular dynamics and electronic structure, dipole moment by quantum chemistry calculation.     

Crystal Engineering of Multiple-component Organic Compound:Organic co-Crystals of the Functional Groups of Carboxyl and Amino with Persistent Hydrogen Bonding Motifs

Three small organic molecular co-crystal compounds (C₃N₆H₆)·(C₆H₁₀O₄)·H₂O(1), C₃H₈N₂O(3) and (H₄btec)₂·(4,4'-bipy)(4)(H₄btec=1,2,4,5-benzenetetracarboxylic acid, 4,4'-bipy=4,4'-bipyridine) and one coordination supramolecular compound [Mn(C₂O₄)(H₂O)₂]·C₆H₁₁NO₂(2) were synthesized by hydrothermal reaction. They were characterized by elemental analysis, infrared(IR) spectroscopy and single crystal X-ray diffraction(XRD). Structural analyses reveal that these 2D or 3D supramolecular networks of the compounds were formed by C―H···O, N―H···O, N―H···N, O―H···O and O―H···N hydrogen bonds. Therein, the functional groups of ―COOH, ―NH₂ and ―OH play important roles in constructing supramolecular architectures.     

乙二胺三乙酸与锌(Ⅱ)、钴(Ⅱ)相互作用的固体和溶液化学特性

在水热和弱酸性反应条件下,螯合型表面活性剂前驱体乙二胺三乙酸分别与氯化锌、氯化钴反应,形成水合乙二胺三乙酸金属配合物[M(H₂O)₆][M(ED3A)(H₂O)]₂·2H₂O[M=Zn(1),Co(2);H₃ED3A=乙二胺三乙酸,C₈H₁₄N₂O₆]。 产物经元素分析、红外、热重、液体核磁共振和X射线单晶衍射结构表征。 乙二胺三乙酸和锌(Ⅱ)、钴(Ⅱ)五配位,并与水一起形成典型的[MN₂O₄]或[MO₆]八面体结构。 ¹³C核磁共振实验结果表明,溶液中乙二胺三乙酸与锌形成配合物在弱酸性条件下(pH值3~7)稳定存在,在酸性溶液中完全解离,乙二胺三乙酸进一步经分子内成环反应生成3-酮哌嗪二乙酸(H₂kpda=C₈H₁₂N₂O₅)。     

稀土冠醚类络合物的研究(Ⅲ)——硝酸钪与邻苯二酮-17-冠-5及邻苯二酮-14-冠-4固态络合物的合成与性质

制得硝酸钪与两种冠醚的固态络合物,确定其组成为Sc(NO₃)₃·C₁₆H₂₀O₇·H₂O及Sc(NO₃)₃·C₁₄H₁₆O₆·H₂O。研究了冠醚本身及其钪的相应络合物的合成及有关性质。     

Synthesis and Characterization of Zinc Succinate, Zn(C4H4O4)

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｓｕｃｃｉｎａｔｅｉｏｎ (Ｃ4Ｈ4Ｏ4) 2 -(—ＯＯＣＣＨ2 ＣＨ2 ＣＯＯ— )ｉｓａｖｅｒｓａｔｉｌｅｌｉｇａｎｄｓｉｎｃｅｅａｃｈｏｆｔｈｅｆｏｕｒｔｅｒｍｉｎａｌｃａｒｂｏｘｙｌｏｘｙｇｅｎｓｉｓａｂｌｅｔｏｐａｒｔｉｃｉｐａｔｅｉｎｃｏｏｒｄｉｎａｔｉｏｎｔｏｃｅｎｔｒａｌｍｅｔａｌａｔｏｍ(ｓ)ｉｎａｄｄｉｔｉｏｎｔｏｔｈｅｆｌｅｘｉｂｉｌｉｔｙｏｆｔｈｅＣ—Ｃｂｏｎｅ .Ｓｕｃｈｃｏｏｒｄｉｎａｔｉｎｇｖｅｒｓａｔｉｌｉｔｙｈａｓｂｅｅｎｒｅｆｌｅｃｔｅｄｉｎｓｅｖｅ…     

Factors influencing decomposition of H2O2 over supported Pd catalyst in aqueous medium

Since H₂O₂ decomposition can result in selectivity/yield loss in the direct H₂O₂ synthesis process from H₂ and O₂ over supported Pd catalysts, it is important to have an enhanced understanding about the factors affecting the H₂O₂ decomposition reaction. Herein, detailed studies have been undertaken to investigate the influence of different factors, such as (a) nature and concentration of acid in reaction medium, (b) nature and concentration of halide in presence and absence of acid in reaction medium, (c) pretreatment procedures and (d) catalyst modification by incorporation of different halides, on the H₂O₂ decomposition reaction over a 5% Pd/C catalyst in aqueous medium at 25 °C. This study has shown that the H₂O₂ decomposition activity is profoundly influenced by all the above factors. The effectiveness of the acids in suppressing the H₂O₂ decomposition activity decreased in the following order: hydroiodic acid > hydrobromic acid > hydrochloric acid  acetic acid > phosphoric acid > sulfuric acid > perchloric acid. The ability of the acid to decrease the H₂O₂ decomposition activity was found to very strongly depend on the nature of its associated anion. Halides, such as iodide, bromide and chloride were particularly effective in suppressing the H₂O₂ decomposition activity. Oxidation pretreatment of the catalyst was found to strongly suppress its H₂O₂ decomposition activity, while a reduction treatment was found to promote its activity. A gradual decrease in the H₂O₂ decomposition activity of the catalyst was observed with each successive usage due to in situ sub-surface oxidation of Pd by H₂O₂. Halide incorporation either via the reaction medium or prior catalyst modification had a similar qualitative effect on the H₂O₂ decomposition activity.     

Co/Fe/Al2O3/cordierite催化C3H6选择性还原NO的实验研究

采用溶胶凝胶法和浸渍法制备了负载于蜂窝陶瓷上的Co/Fe/Al₂O₃/cordierite催化剂,在陶瓷管流动反应器上对其催化C₃H₆选择性还原NO的性能进行了测试。结果表明,该催化剂表现出最优脱硝性能,在模拟烟气条件下,当反应温度为550 ℃时可实现97%的脱硝效率。Co的引入可显著增强Fe/Al₂O₃/cordierite催化剂抗SO₂和H₂O的能力。在模拟烟气中同时引入0.02% SO₂和3% H₂O后,1.5Co/Fe/Al₂O₃/cordierite的脱硝性能受影响甚微,当反应温度高于500 ℃时1.5Co/Fe/Al₂O₃/cordierite催化C₃H₆还原NO的效率均可达到90%以上;相比之下,未经Co修饰的催化剂Fe/Al₂O₃/cordierite脱硝性能受到了严重的抑制,在整个反应温度区间（200-700 ℃）内,其催化C₃H₆还原NO的效率最高不足50%。XRD和SEM表征结果表明,经过适量的Co修饰后的1.5Co/Fe/Al₂O₃/cordierite表面变得更疏松,且形成了以钴铁和钴铝双金属氧化物为主要成分的球状晶粒。H₂-TPR结果表明,相比于Fe/Al₂O₃/cordierite,1.5Co/Fe/Al₂O₃/cordierite有更好的低温还原性能。Py-FTIR结果表明,Co的引入可使催化剂表面的Lewis酸明显增加,且生成了Brønsted酸。N₂吸附-脱附表征结果表明,Co可增大催化剂的比表面积。