α-蒎烯的光氧化反应研究

α-蒎烯和氧能在基态条件下形成CCT复合物,在与CCT复合物吸收相应波长的光辐照下,有利于促进蒎烯的光氧化反应。在氧化反应中,存在着明显的溶剂极性的影响,极性愈大,反应的速度愈快。这一切都说明电荷转移在反应中起着重要的作用。此外,正由于存在着基态的CCT复合物,因此α-蒎烯的氧化反应也能在暗的条件下进行。根据蒎烯光氧化和暗氧化反应产物的分析,可以肯定蒎烯在本工作实验条件下的氧化反应是通过自由基机理而进行的。     

吨染料与反胶束体系中CdS的光敏电子转移

用ＡＯＴ／异辛烷／水反胶束体系制备出了不同尺寸大小的纳米ＣｄＳ,并以曙红（ＥＯ）和孟加拉玫瑰红（ＲＢ）为探针分子,研究了它们与硫化镉微粒间的光致电荷转移相互作用,用光照实验和ＥＳＲ技术研究了这些染料向ＣｄＳ的导带注入电子的过程并讨论了作用机理     

对-三氰基乙烯基-N,N-二烷基苯胺的分子内光致电荷分离

本文以对-三氰基乙烯基-N,N-二烷基苯胺为模型化合物,开展共轭π电子体系分子内光致电子转移及电荷分离的研究。通过吸收光谱和荧光光谱探讨了这类分子的电荷分离作用以及在DMSO-H_2O中的簇集作用。     

1,5—二—(2—噻唑)甲簪官能基螯合树脂的合成及其特性研究

通过偶合反应将1,5—二—(2—噻唑)甲(?)接到苯乙烯—二乙烯苯的骨架上,得到一种含氮、硫配位原子的螯合树脂(1)。该树脂1对Au~(3+)的吸附容量最高达1.1mmol/g。吸附在树脂上的金络离子可以用5％硫脲——盐酸(0.1mol/L)溶液进行洗脱,回收率为84％。对pd~z+可被5％硫脲——0.1mol/LHCI热溶液定量洗脱。     

不含亲水基团的偶氮苯衍生物L-B膜的制备和性质研究

本文合成了具有一定结构特点的偶氮苯的衍生物, 以元素分析和^1HNMR鉴定了B产物的组成和结构。采用L-B技术制备了其多层L-B膜, 以紫外可见光谱研究了膜中分子的聚集状态和膜的纵向均匀性; 以偏振紫外确定了膜中分子偶氮基的取向; L-B膜的小角度X射线衍射结果表明膜具有层状有序的周期性结构。     

Novel Roles of Metal Ions in Layered Self-assembled Films of Polynuclear Complexes on Their Photoinduced Electron Transfer Properties

Three metal ion bridged self-assembled(SA)films of cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium were fabricated and characterized by contact angle,UV spectra,cyclic voltammetry and XPS.Theirphotoinduced electron transfer properties(PETP)were examined.Among the titled systems,the highest steady an-odic photocurrent of 1773—1843 nA/cm~1 and the highest quantum yield of 3.2% were achieved.The effects of in-cident light intensity,bias voltage,and electron donor were also studied.The possible mechanism of electron trans-fer was proposed.The results reveal that different metal ion in SA films could affect significantly the photoinducedelectron transfer property.Our experimental results clearly show that bridging metal ions can play both functionaland structural roles in these self-assembled systems.This method of forming functional films can provide a new ap-proach to regulate the property of similar systems.     

光敏电子转移异构反应中的盐效应

本文利用四正丁基四氟硼酸铵为探针, 研究了顺式芪和四环烷的9,10-二氰基蒽敏化光异构化的反应机理, 加入四正丁基四氟硼酸铵明显加快顺式芪的异构反应而减慢四环烷的反应。荧光猝灭及激光闪光光解实验证明四正丁基四氟硼酸铵能促进电荷分离过程而生成离子自由基对。从而证实顺式芪的异构化反应是经由离子自由基的历程, 而四环烷则是通过激基复合物机理。     

降冰片二烯衍生物光敏异构化反应的机理研究

利用甲基卡唑为光敏剂，实现了三个降冰片二烯衍生物的光诱导介键异构化反应，荧光猝灭，化学诱导动态核极化（ＣＩＤＮＰ）以及热力学讨论都支持电子转移敏化机理，有关量子效率的计算表明单重态电子转移机制对光异构化反应的贡献远大于三重态能传递机制，此外还探讨了光异构化反应中的溶剂极性效应。     

TiO2纳米颗粒对钌(II)三联吡啶配合物光损伤小牛胸腺DNA能力的影响

由于极短的激发态寿命, 钌(II)三联吡啶配合物对脱氧核糖核酸(DNA)的光损伤能力低下. 设计合成了三个钌(II)三联吡啶配合物[Ru(ttp)(tpy)]^2＋ (1), [Ru(ttp-COOH)(tpy)]^2＋ (2)和[Ru(ttp-COOH)(tpy-pyr)]^2＋ (3), 其中tpy为2,2':6',2"-三联吡啶, ttp为4′-(4-甲苯基)-2,2':6',2"-三联吡啶, ttp-COOH为4′-(4-羧基苯基)-2,2':6',2"-三联吡啶, tpy-pyr为4'-(1-芘基)-2,2':6',2"-三联吡啶. 比较了TiO₂纳米颗粒对它们光损伤小牛胸腺DNA的影响. 发现TiO₂纳米颗粒在空气和氩气条件下均可显著提高配合物3光损伤DNA的能力. TiO₂纳米颗粒和配合物3间的光诱导电子转移作用及其该作用生成的钌(III)物种可能是促进配合物3对DNA光损伤的主要原因.     

Intermolecular interaction between squarylium cyanine and porphyrin

In this paper, the interaction between squarylium cyanine and porphyrin in chloroform is investigated by absorption and fluorescence spectroscopy. Emphasis has been put on the mechanism of intermolecular energy transfer. The overlap integral J between the absorption spectrum of squarylium cyanine and the fluorescence spectrum of porphyrin was calculated, which reveals that the singlet-singlet energy transfer may occur from porphyrin to squarylium cyanine in solution. In comparison of the observed rate constant [kqII=6.1 ×1013 (mol/L)-1·s-1] for fluorescence quenching of porphyrin by squarylium cyanine with the diffusion rate constant in chloroform [kdif=1.1×1010 (mol/L)-1·s-1] and the rate of energy transfer [ket≤6.7×104 (mol/L)-1·s-1 in the experimentally dilute solutions] estimated from Forster formula, the possibility of energy transfer by electron exchange or/and coulombic mechanism could be excluded. So it has been definitely convinced that the intermolecuiar energy transfer between them is