溶液自组装法制备卟啉纳米材料研究进展

在溶液中,利用自组装方法制备以卟啉化合物为基础的纳米材料具有优良的光物理和光化学性质,在分子器件和人工模拟光合作用等方面具有巨大的应用前景,是目前的研究热点。本文详细介绍了单卟啉组装方法和多卟啉共组装方法,单卟啉组装包括双溶剂法和表面活性剂辅助法两类方法。简要介绍了卟啉自组装纳米材料在集光天线和光催化方面的应用。目前,自组装方法制备的卟啉化合物纳米材料已经出现了丰富的形态,但仍存在不足,即自组装作用机理有待深入研究,且如何将卟啉纳米材料的制备工艺放大并应用于实际,还有待进一步发展。     

Nitrogen donor-controlled chemoselectivity of reaction in oxidation of sulfides with tetra-n-butylammonium hydrogen monopersulfate catalyzed by a partially β-brominated meso-tetraphenylporphyrinatomanganese(III) acetate: a clue to the nature of active oxidant

Highly efficient and rapid oxidation of different sulfides to the corresponding sulfones with tetra-n- butylammonium hydrogen monopersulfate (TBAO) in the presence of catalytic amounts of Mn(TPPBr₂)OAc at room temperature is reported. Contrary to other nitrogen donors, using 4-cyanopyridine as co-catalyst leads to an increase in the ratio of sulfoxide to sulfone in the products. Comparison of the chemoselectivity of reaction in the presence of different nitrogen donors as co-catalyst shows the involvement of a high-valent Mn-oxo species as well as the six-coordinate Mn(TPPBr₂)(HSO₅)(B) (B = nitrogen donors) complex in sulfide oxidation reactions with TBAO.     

Understanding the Electronic Structures and Absorption Properties of Porphyrin Sensitizers YD2 and YD2-o-C8 for Dye-Sensitized Solar Cells

The electronic structures and excitation properties of dye sensitizers determine the photon-to-current conversion efficiency of dye sensitized solar cells (DSSCs). In order to understand the different performance of porphyrin dye sensitizers YD2 and YD2-o-C8 in DSSC, their geometries and electronic structures have been studied using density functional theory (DFT), and the electronic absorption properties have been investigated via time-dependent DFT (TDDFT) with polarizable continuum model for solvent effects. The geometrical parameters indicate that YD2 and YD2-o-C8 have similar conjugate length and charge transfer (CT) distance. According to the experimental spectra, the HSE06 functional in TDDFT is the most suitable functional for describing the Q and B absorption bands of porphyrins. The transition configurations and molecular orbital analysis suggest that the diarylamino groups are major chromophores for effective CT excitations (ECTE), and therefore act as electron donor in photon-induced electron injection in DSSCs. The analysis of excited states properties and the free energy changes for electron injection support that the better performance of YD2-o-C8 in DSSCs result from the more excited states with ECTE character and the larger absolute value of free energy change for electron injection.     

手性麻黄素-卟啉锰催化剂的合成及催化性能的研究

以一类新型的手性麻黄素 -卟啉作配体 ,制备了金属锰配合物。考察了配合物对烯烃环氧化反应的催化性能 ,发现含麻黄素基团的锰卟啉催化剂在烯烃环氧化的两相溶剂 ( CH2 Cl2 /H2 O)体系中 ,不仅催化活性增强 ,同时具有相转移能力。还探讨了反应条件对环氧化结果的影响规律     

金属离子与卟啉的嵌入反应动力学研究Ⅷ-- 丁二酸缓冲溶液中溴化间四(N-乙腈基-3-吡啶基)卟啉与Cu(Ⅱ)的配位反应

研究了在35士1℃,离子强度0.5 mol/L(KCl)条件下,丁二酸根催化Cu2+离子嵌入溴化间四(N-乙腈基-3-吡啶基)卟啉(H2T-β-ECNPyPBr4)的反应动力学及其机理.结果显示,在丁二酸缓冲体系中反应遵循阴离子催化卟啉变形机理;根据催化剂浓度、溶液的pH与反应速率间的关系,得到其反应动力学方程为d[CuP4+]/dt=5.81{(1.0+1.59×103)[B2]/1.0+1.92×10-5[H+]2}[Cu2+][P]T.     

The interaction of water-soluble iron porphyrins with DNA films and the electrocatalytic properties for inorganic and organic nitro compounds

The electrochemistry of water-soluble iron porphyrins (Fe(n-TMPyP)) (where n=2 and 4) was studied as an electrochemically active film on DNA modified glassy carbon, gold, platinum, and transparent semiconductor tin oxide electrodes in solutions of various pH values. The two layers of the modified electrode containing the iron porphyrin and the DNA film were prepared by depositing the iron porphyrin on a DNA film modified electrode. The Fe(4-TMPyP)/DNA film was electrocatalytic reductive for p-nitrobenzoic acid in a weak acidic, or neutral aqueous solution through an Fe^II species, and the electrocatalytic reduction peak potential became more negative than the cathodic peak of the Fe^III/II redox couple. The electrocatalytic reduction properties by the Fe(2-TMPyP)/DNA film as catalysts for nitrite reduction have also been determined, and shown to be active through an Fe^I species and to be pH-dependent. The electrocatalytic oxidation properties of nitrite by Fe(n-TMPyP)/DNA (for n=2 and 4) film have also been determined and shown to be active through an Fe^IV species with the electrocatalytic oxidation efficiency of NO₂⁻ with Fe^IV(O)(n-TMPyP) being higher than with (HO)Fe^IV(O)(n-TMPyP). The electrocatalytic oxidation efficiency of NO₂⁻ by iron porphyrin is pH-dependent. The electrocatalytic reduction of p-nitrophenol by Fe(2-TMPyP)/DNA film are also discussed.     

卟啉化学研究的新进展

介绍了卟啉化合物的结构特点及应用新进展,重点综述了多种新型卟啉类化合物的合成;新型卟啉类化合物的自组装研究;卟啉类化合物的分子识别及生物活性研究。展望了其广阔的发展和应用前景。期望能在医药学、生命科学、材料科学及环境科学的应用上更有意义。     

5-(4-吡嗪甲酰胺基)苯基-10,15,20-三苯基卟啉和锌配合物的合成及热分析

合成了新型5-(4-吡嗪甲酰胺基)苯基-10,15,20-三苯基卟啉配体(H2P)及其锌配合物(ZnP),通过元素分析、质谱、紫外-可见光谱、核磁共振氢谱、红外光谱对其组成和结构进行分析表征。热分析表明,卟啉配体从410℃开始分解,具有较高的热稳定性。     

Catalytic epoxidation of methyl linoleate

The epoxidation of methyl linoleate was examined using transition metal complexes as catalysts. With a catalytic amount of methyltrioxorhenium (4 mol%) and pyridine, methyl linoleate was completely epoxidized by aqueous H₂O₂ within 4 h. Longer reaction times (6 h) were needed with 1 mol% catalyst loading. Manganese tetraphenylporphyrin chloride was found to catalyze the partial epoxidation of methyl linoleate. A monoepoxidized species was obtained as the major product (63%) after 20 h.     

金属-卟啉框架材料在光催化领域的应用

金属-有机框架(metal-organic frameworks,MOFs)是一种由金属离子或金属簇与多齿有机配体通过配位键连接而形成的有机无机杂化多孔晶态材料,具有较大的比表面积和孔道,同时结构也易于实现剪裁。近十几年MOFs在催化、气体吸附等领域得到了较大发展。卟啉等四吡咯大环结构有很好的光吸收特性,作为连接体应用于MOFs中可有效拓宽其吸收光谱,因此,基于卟啉配体的MOFs被广泛应用于光催化领域。本文综述了近十年来金属-卟啉框架材料在光催化选择性有机合成、析氢、析氧、还原CO₂、降解有机污染物方面的应用,同时对金属-卟啉框架材料未来在光催化领域的发展进行了展望。