金属卟啉在新型材料领域的应用进展

作为新型材料其中一员,卟啉及金属卟啉在光电器件、医药和功能材料等领域具有重要的研究意义和广泛的应用前景。本文综述了近年来卟啉及金属卟啉化合物在新型材料方面的研究,重点介绍了金属卟啉化合物在电化学、分子自组装及催化等方面的应用新进展,并对其未来在新型材料领域的研究进行了展望。     

金属卟啉在医药中的应用

卟啉及金属卟啉作为潜在的治疗药物具有广泛的应用前景。近年来,人们对金属卟啉在医药方面的应用进行了有益的探索。本文论述了某些金属卟啉用于治疗新生儿黄疸和抑制肿瘤方面的研究进展。     

金属卟啉配合物的性能及应用研究进展

金属卟啉配合物是卟啉衍生物中的主体化合物,因其具有优异性能而被广泛地研究与应用.分别从仿生体系、分子识别、催化、材料、有机合成和医疗等方面简要介绍了金属卟啉配合物的优异性能及其应用,旨在让人们了解并熟悉金属卟啉配合物的性能及用途.     

A3B型卟啉合成方法及在仿生催化中的应用

作为金属卟啉类化合物的一个重要类别,A3B型卟啉化合物具有独特的物理、化学、光电及结构特性。本文综述了国内外有关该类化合物的合成方法及在仿生催化应用领域的最新研究成果,系统地介绍了混醛法(Little法和Lindsey法)、"2+2"合成法、线性四烷基吡咯合成法、卟啉中位修饰法和微波合成法。重点阐述了具有独特结构的A3B型卟啉类仿生催化剂——B-链衍生化催化剂、固载A3B型金属卟啉催化剂、A3B型金属卟啉二聚体催化剂、Pacman型双核金属卟啉催化剂及Hangman型金属卟啉催化剂在仿生催化领域中的应用,希望能为卟啉研究者设计、合成更优良的卟啉类催化剂提供参考。未来卟啉仿生催化的主要目标在于合成性能更加优良的卟啉,并应用于大规模工业生产中,在温和条件下实现较高的转化数和选择性。     

卟啉类化合物荧光光谱的性质

卟啉类化合物在荧光探针技术、光敏材料、染料等领域中有广泛的应用,已引起了人们的极大兴趣。对荧光的产生及卟啉、金属卟啉的荧光光谱性质及应用前景进行了综述,并从几个方面讨论了影响卟啉及其衍生物荧光的因素。     

金属卟啉在催化反应中的应用

金属卟啉化合物从结构和性能上都是细胞色素P-450单加氧酶的有效模拟物,综述了卟啉及金属卟啉类化合物作为催化剂在氧化反应、CO_2环加成反应、胺化反应、烷基化反应等诸多反应中的应用,并对目前金属卟啉在催化反应中存在的主要问题以及未来的发展进行了总结。     

金属卟啉仿生材料合成及应用研究

正一、项目简介卟啉(Porphyrin)是一类与生命科学密切相关的物质,卟啉及金属卟啉类化合物广泛存在于自然界生命体中,例如:叶绿素、血红素、维生素B12等。它们在生命过程中,对氧的传递(血红蛋白)、贮存(肌红蛋白)、活化(细胞色素P-450)和光合作用(叶绿素)等起着十分重要作用。如今,随着卟啉和金属卟啉合成的发展,此类化合物在仿生化学、催化、太阳能利用、特种材料、医学和分析化学等方面的应用已越来越广泛。     

金属卟啉在手性识别中的应用

从结构上分析了金属卟啉作为手性分子识别受体的优点,阐述了判断化合物绝对构型的激子手性方法机理,按照单卟啉体系和多卟啉体系介绍了金属卟啉与手性客体分子的识别机理和相关研究成果。初步系统化地对金属卟啉在手性识别中的应用进行综述,意为在相关领域工作的研究者提供参考。     

卟啉及金属卟啉类化合物的研究进展及展望

系统地介绍了卟啉及金属卟啉类化合物在分子结构设计、合成方法和应用研究方面的最新进展及展望.基于大量文献及本课题组的研究工作,特别指出了这类化合物在合成方法上的改进以及在仿生催化烃类选择氧化方法的研究进展.     

卟啉金属有机框架材料在光催化领域的应用

金属卟啉有机框架材料是一种由卟啉或金属卟啉作为结构单元构筑的新型周期性网状结构材料,既具有卟啉拓宽光谱响应范围、降低光生电子-空穴复合率的独特优势,又具有MOFs(金属有机骨架)材料的多孔道、孔道尺寸可调节、比表面积大的优势,成为目前具有良好光电性质的新型光催化剂。近年来,许多科学家们致力于新型光催化剂的开发与应用。尤其是近几年来,随着材料科学的发展,新型光催化剂金属卟啉MOFs成为光催化剂的研究热点并取得了令人欣慰的成果。该文综述了近十年来卟啉/金属卟啉MOFs在二氧化碳还原、裂解水制氢、光降解有机染料等领域的最新应用,并对未来卟啉金属有机框架在光催化领域的发展进行了展望。     

Porphyrins and metalloporphyrins: potential hypoxic agents

Synthetic water-soluble porphyrins and their metalloporphyrin derivatives with Co(III), Cu(II), Ru(II) and Pt(II), containing various functional groups within the meso-positions of the porphyrin, were synthesised and evaluated as hypoxic agents, especially as cytotoxins and radiosensitisers. Cobalt complexes of the porphyrins containing positively charged methylpyridinium groups showed selective toxicity toward hypoxic Chinese Hamster Ovary (CHO) cells. The Co(III) complexes of the cationic and the anionic porphyrins are all weak radiosensitisers toward hypoxic cells, the highest sensitisation enhancement ratio (SER = 1.22, at 50 muM) being with a porphyrin complex containing a cis-arrangement of two nitro and two methylpyridinium meso-substituents. A copper complex of a tetracationic porphyrin showed slight radiosensitisation activity with an SER value of about 1.1. The other metalloporphyrins showed no hypoxic selectivity or radiosensitisation activity. In total, over 50 porphyrin free bases have been synthesised, of which half are water-soluble and have been metallated; thus, the chemistry is now in place for further development of water-soluble hypoxic agents.     

Catalytic Oxidation of Cyclohexane and Cyclooctene over a New Metalloporphyrin Supported on VOPO4 Catalyst

In this work, we report the use of oxovanadium phosphate as support of the 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin iron (III) chloride (Fe(TDCPP)Cl) and of the 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin manganese (III) chloride (Mn(TDCPP)Cl) catalysts for cyclohexane and cyclooctene oxidations by iodosylbenzene. The catalytic results have shown that oxovanadium phosphate support is suitable for metalloporphyrin catalysts leading to an efficient system for the cyclooctene epoxidation and very selective for cyclohexane hydroxylation.     

Synthesis and characterization of poly(catechol) catalyzed by porphyrin and enzyme

Catalytic polymerization of catechol was performed employing the cationic porphyrin and horseradish peroxidase (HRP) as catalysts. The obtained results demonstrate that the cationic metalloporphyrin is a more-efficient catalyst than the HRP in the catechol polymerization. The oxidative polymerization was carried out in the presence of polystyrene sulfonate (PSS) as a template. According to TGA data, poly(catechol) that is synthesized by porphyrin catalyst exhibits more thermal stability than the enzymatic catalyzed product. The GPC indicate higher molecular weight of polymer synthesized by porphyrin as a catalyst. Cyclic voltammetry measurements show that the synthesized polymers have convenient electroactivity. The poly(catechol) and its methyl and methoxy derivatives that are synthesized by porphyrin catalyst show low electrical conductivity.     

四苯基卟啉和金属卟啉的制备

采用二甲苯为溶剂,对硝基苯甲酸催化,苯甲醛和吡咯反应合成四苯基卟啉（ＴＰＰ）,产率可达５５４％;另外,用ＤＭＦ为溶剂,ＴＰＰ与醋酸锌反应生成金属卟啉锌（ＴＰＰＺｎ）,产率可达９７６％。     

一种新型液晶化合物的合成及表征

以CH2C12为溶剂,通过5-（4-氨基）苯基-10,15,20-三苯基卟啉（MATPP）与十二酸直接反应得到一种新型不对称酰胺基卟啉配体5-（4-十二酸酰亚胺基）苯基．10,15,20．三苯基卟啉配体（PDTPPH2）,利用紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等测试方法对化合物的结构加以确认。     

Fabrication of discontinuous fibers of poly (N‐vinylpyrrolidone) containing metalloporphyrin molecules

This study described the preparation of discontinuous fibers of poly (N‐vinylpyrrolidone) (PVP) containing metalloporphyrin (Manganese (III) tetrakis (1‐methyl‐4‐pyridyl) porphyrin pentachloride) molecules using electrospinning method. SEM images showed that before adding the metalloporphyrin molecules, the electrospun nanofibers are straight and smooth, while after adding metalloporphyrin molecules into the PVP solutions, the SEM images clearly showed that there were two different types of fibers: the thinner fibrous phase and the thicker discontinuous fibers. The chemical composition of the resulting PVP/metalloporphyrin composite fibers was characterized by Fourier‐transform infrared (FTIR) and energy dispersive X‐ray (EDX) analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6017–6022, 2006     

新型L-苏氨酸尾式卟啉及其锌(II)配合物合成与表征

为了探索手性金属卟啉配合物的结构与功能 ,用 L-苏氨酸和 5 -[邻 -(2 -溴乙氧基 )苯基 ]-1 0 ,1 5 ,2 0 -三苯基卟啉为原料合成了一种新型 L-苏氨酸尾式卟啉及其锌 (II)配合物 ,通过元素分析、红外光谱、化学分析和质谱等对其进行了结构表征。测试并研究了它们在 40 0 0～ 40 0 cm- 1 范围内的傅里叶变换红外光谱 ,对主要谱带进行了经验归属     

Characterization of Several Metalloporphyrins in Unusual Oxidation States. The Effect of Axial and Equatorial Ligands

The effect of axial and equatorial ligands on the generation of unusual oxidation states in metalloporphyrins is discussed. Selected examples have been taken from the literature. These include the generation of Ni(III) and Ru(III) porphyrins from Ni(II) and Ru(II) complexes containing specific axial and equatorial ligands as well as the generatoin of a Cu(I) metalloporphyrin dianion which is produced upon the overall three-electron reduction of Cu(II) tetracyanoporphyrin. Special emphasis is placed on the oxidation and reduction of σ bonded iron phenyl porphyrins. These complexes, which are stable as Fe(III), may be oxidized by a single electron to yield unstable compounds characterized as containing a great deal of Fe(IV) character, or reduced by a single electron to produce stable species which resemble, in part, radical anions of Fe(III). This singly deduced species may be described by a resonance equilibria between an Fe(III) porphyrin anion radical and an Fe(II) porphyrin anion. Likewise, the singly oxidized complex may be described by a resonance equilibria between an Fe(IV) porphyrin cation and an Fe(III) cation radical.