金属卟啉仿生催化剂进展

细胞色素P-450是一种生物体内催化分子氧氧化内源底物的单加氧酶,其活性片段的核心结构是金属卟啉络合物。人工合成的金属卟啉络合物可作为细胞色素P-450的有效模拟物,应用于烯烃、直链烷烃、环烷烃、芳烃、芳烃侧链、及各种杂原子等多种底物的催化氧化。人工合成的金属卟啉络合物可分为：对称型金属卟啉、非对称型金属卟啉、μ-氧代双核金属卟啉、负载型金属卟啉4大类。现以金属卟啉络合物的结构为线索,论述了结构与催化活性及稳定性的内在联系,重点介绍了近几年国内外金属卟啉仿生催化剂的氧化应用研究进展,及仿生催化氧化的工业化发展前景。     

新型金属卟啉光敏剂的合成及其抗肿瘤活性

合成了新型β-取代卟啉光敏剂2-氢醌-5，10，15，20-四（4-羟基苯基）卟啉铜（Ⅱ）（Cu（Ⅱ）P）和2-氢醌-5，10，15，20-四（4羟基苯基）卟啉锌（Ⅱ）（Zn（Ⅱ）P），并初步研究其抗肿瘤活性．实验结果表明：2-氢醌5，10，15，20-四（4-羟基苯基）卟啉锌（Ⅱ）对慢性骨髓性白血病肿瘤细胞（K562）具有很好的光敏毒性，Zn（Ⅱ）P的浓度为320nmol／L时，就能抑制90％以上的白血病肿瘤细胞的生长．     

卟啉钴配合物与含氮有机碱的加合反应研究

金属卟啉能与有机碱咪唑、吡啶等配合〔１〕，而单纯的卟啉却无此性质，这是由于过渡金属卟啉具有平面结构和轴向不饱合性，容易与有机碱形成加合物，增强了配体活性，提供了有利于反应的空间条件和结构条件。本文研究了一系列卟啉钴配合物与咪唑、吡啶的加合反应与紫外可见光谱的变化规律，求得了加合分子数与平衡常数。     

金属卟啉催化氧气选择氧化对甲基异丙苯绿色合成对甲基苯乙酮

以对甲基异丙苯为原料、无溶剂条件下,选取不同环外取代基和中心金属离子的金属卟啉作为催化剂,氧气为氧源,绿色氧化对甲基异丙苯合成对甲基苯乙酮。探讨了不同种类催化剂的催化活性、不同浓度的催化剂、反应温度和氧气压力对目标化合物的选择性和收率的影响。实验显示,在T(p-OCH_3)PPCo Cl作为催化剂、反应温度为110℃、压力为2.0 MPa时,对甲基异丙苯的转化率为43.4%,对甲基苯乙酮的选择性高达47.4%,收率为20.7%。     

单羟基苯基卟啉及其金属配合物的合成与表征

单羟基苯基卟啉(MHTPP)及其配合物是一类有活性基团,并易于制备其他复杂卟啉化合物的中间体。本文以对羟基苯甲醛,苯甲醛与吡咯为原料,合成了MHTPP,并进一步合成了其6种金属配合物。采用紫外可见光谱、红外光谱及1H NMR谱对产品的结构进行表征,并进行了对比分析。与卟啉单体相比,金属配合物的分子对称性提高,吸收峰的数目相应减少。     

Solid‐phase extraction of phenolic compounds with poly[metalloprotoporphyrin IX]

A highly insoluble metalloporphyrin polymeric material was used as sorbent for the solid‐phase extraction of phenolic compounds. Substantial quantities of phenols (40 to 60 mg/g polymer) were absorbed from aqueous solution comparing satisfactorily with other extraction methods. The polymeric phase presented similar K_SPE values for the hydrophobic compounds tested such as p‐chlorophenol, BPA, p‐nitrophenol, and a significant lower value for the more hydrophilic p‐aminophenol and cresol. Several metallic complexes of protoporphyrin IX (Co²⁺, Cu²⁺, Ni²⁺, Zn²⁺, and Fe³⁺) have been tested. The analytes were extracted with high recoveries at acid and neutral pH values, whereas at pH 10 low recoveries were obtained. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3038–3043, 2001     

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。     

负载金属卟啉用于催化氧化反应的进展

文中记述了近年来固载金属卟啉应用于催化氧化研究反应的现状,包括金属卟啉以及载体的种类,认为固载金属卟啉模拟酶催化剂在催化氧化反应中将有更大的应用前景。     

Metal-Oxo Species in P450 Enzymes and Biomimetic Models. Oxo-Hydroxo Tautomerism with Water-Soluble Metalloporphyrins

Oxygenation reactions (hydroxylation, epoxidation, N- or S-oxide formation, etc.) catalyzed by cytochrome P450 enzymes and related biomimetic models involve an electrophilic oxidative species as the active species, namely a high-valent metal-oxo intermediate. Among the different methods to study the oxygenation reactions mediated by high-valent metal-oxo porphyrin complexes, the recent discovery of oxo-hydroxo tautomerism provides a useful tool to investigate the mechanism of O-atom transfer reactions in aqueous media.     

CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O2 and CO2

The direct synthesis cyclic carbonate from styrene, O₂ and CO₂ is of great academic attraction and industrial value in modern chemistry. The metalloporphyrin/tetrabutylammonium bromide was employed as binary catalyst for this reaction in the presence of O₂ and CO₂ by using methyl 2-cyclopentanone-carboxylate as co-catalysts. The effects of reaction parameters on catalytic performance were investigated systematically. Under the optimal reaction conditions, conversion of styrene (99%) and selectivity to cyclic carbonate (35%) were obtained. The possible mechanism of cascade reaction was proposed by using in-situ ultraviolet and infrared spectroscopy. The results show that the cobalt center is coordinated with the ring oxygen atom of methyl 2-oxocyclopentanecarboxylate to activate oxygen to form a peroxy active species, thereby forming a high-valent cobalt-oxygen intermediate, which passes oxygen atoms to styrene and generate epoxy styrene. Then, styrene oxide opened ring under the catalysis of tetrabutylammonium bromide, and finally formed cyclic carbonate through CO₂ insertion reaction and intramolecular ring-closing reaction.