光动力治疗药物合成进展

光动力疗法（Photodynamic Therapy,PDT）是利用光敏剂发生光动力反应进行疾病诊断和治疗的一种新技术。光敏剂经历了第一代光敏剂卟啉及其衍生物、第二代光敏剂酞菁类化合物以及第三代光敏剂,已经逐步走向成熟。本文主介绍了这三代光敏剂的性质及合成。     

萘酞菁衍生物在光动力疗法中的研究进展

光动力治疗作为一种非侵入性治疗方式,具有微创、毒副作用小、可重复治疗等优点。光敏剂是光动力治疗的关键因素之一,萘酞菁作为第二代光敏剂,扩展的π-共轭体系使其在750～900 nm具有强吸收,该近红外光有较深的组织穿透性,且能量足够激发光敏剂,也能避免可见光区吸收带来的皮肤光毒性。但萘酞菁具有较强的聚集倾向,影响其光化学性质及光动力疗效。综述了通过合成萘酞菁衍生物和纳米载体包封来改善其光学性质或增强光动力疗效的进展。     

光动力治疗用酞菁类光敏剂的合成研究进展

本介绍了光动力治疗原理、酞菁类光敏剂的合成方法及其近年来得到的研究进展，并介绍了酞菁在光动力治疗中的光化学生物过程和光漂白现象，还对其存在的缺点和今后的研究方向进行了讨论。     

酞菁铜溶解性研究及其电沉积薄膜的制备

通过测定α-酞菁铜(α-CuPc)在4种不同的有机溶剂中的紫外可见光吸收光谱,研究了不同溶剂以及加入不同量的三氟乙酸(TFAA)对酞菁铜溶解性和质子化的影响.以溶解性研究为基础,探讨了在电化学沉积法制备酞菁铜薄膜时不同工艺条件对其形貌的影响.实验结果表明:加入TFAA后,酞菁铜在硝基甲烷和氯仿中溶解良好,而且在氯仿中更容易质子化;使用扫描电镜(SEM)表征,结果表明TFAA及酞菁铜摩尔含量对薄膜制备的影响最为明显.     

氨基酸修饰的酞菁衍生物的合成及其溶液性质和光动态效应

合成各种不同结构的卟啉与酞菁衍生物是筛选优良光敏剂的基础,用新的合成路线合成了甘氨酸修饰的锌酞菁[ZnPc(NHCH2COOH)4]。测定了它在不同溶剂中的吸收光谱,发现其最大吸收波长红移至750nm左右。这种化合物可以溶于水中,也可以溶解在有机溶剂与水的混合溶剂中。ESR光谱证实它可以有效的产生^1O2,O2^-等活性氧,是一种潜在的新型光敏剂。     

粗制铜酞菁生产技术的评述

酞菁颜料具有鲜艳的色光、着色力和优异的牢固性,受到人们的重视。据有关资料报道,酞菁兰、粗制铜酞菁产品在世界多数国家均有生产,美、英、德、日几个国家年产量都在万吨以上,我国年产量约在两千吨左右。但最近盲目上了许多固相法生产的粗制铜酞菁厂。由于产品质量低劣,销售困难。有鉴于此,本文扼要介绍一下粗制铜酞菁生产技术的概况一、酞菁的结构和特点酞菁的结构是由四个氮杂茂结合成为一个大型多环分子,其发色系统为具有十八个π电子的环状轮烯。酞菁结构中心部分的两个氮原子与两个氢原子结合,为无属酞菁,也可与某种金属原子结合形成稳定的络合物。例如,酞菁与铜结合时为酞菁铜。铜与酞菁结构中心的     

染料敏化太阳能电池中酞菁光敏剂的固定基团的研究进展

染料敏化太阳能电池(DSSC)是太阳能电池中非常有潜力的一个研究方向。敏化染料作为DSSC重要的组成部分在很大的程度上影响着DSSC的光电转化效率,酞菁是一种非常重要的光敏剂,近年来受到广泛的关注。酞菁结构的细微变化都会影响到其HOMO、LUMO能级,影响激发电子注入半导体极板的效率,从而影响太阳能电池效率。本文以酞菁与TiO2的固定基团为主介绍了近年来酞菁染料分子的设计研究进展。     

桥连吸附基团对酞菁敏化太阳能电池性能的影响

染料敏化太阳能电池中,光敏剂是影响电池光伏性能的重要因素,其中酞菁类光敏剂在红光区具有优良的光吸收性能,光化学稳定性高。根据染料敏化太阳能电池的工作原理,通过扩大共轭结构和引入吸电子结构,可以有效的调节染料的能级。综述了吸附基团和桥连结构对染料光敏性能的影响,吸附基团通过共轭结构或直接连接在酞菁环上,会有效的增强电子的流动。     

氯化4,4′,4″,4′′′-四磺基酞菁镓的合成及它的生物活性

金属酞菁化合物可望作为光动力疗法中的新光敏剂用于防治肿瘤。本文叙述氯化4,4′,4″,4(?)-四磺基酞菁镓的制备,它的荧光光谱以及它在正常肌内组织和肿瘤组织中的选择性吸收。     

四葡萄糖基锌酞菁的合成及其光驱动~1O_2生成速率常数的测定

糖酞菁是光动力疗法研究中非常受关注的光敏剂之一。该文合成了两种光动力疗法用光敏剂四葡萄糖基锌酞菁,并通过高分辨质谱及1HNMR对其进行了结构表征,发现不同于[2(3),9(10),16(17),23(24)-四(1,2:5,6-二-O-异丙叉基-α-D-葡萄呋喃糖基)酞菁]锌(Ⅱ)〔缩写为Pc-(Glup)4〕,[2(3),9(10),16(17),23(24)-四(α-D-葡萄呋喃糖-3-基)酞菁]锌(Ⅱ)〔缩写为Pc-(Glu)4〕中的糖基以α-,β-构型两种形式同时存在。对Pc-(Glup)4和Pc-(Glu)4进行了UV-vis和光驱动1O2生成速率常数的测定,结果表明,在甲醇中Pc-(Glu)4以单体形式存在,而Pc-(Glup)4则发生了聚集,它们的1O2生成速率常数分别为8.0×10-4和2.2×10-4。     

负载型酞菁钴(Ⅱ)光催化降解孔雀石绿的研究

采用光催化法研究了MCM-41-α-四(2-甲氧基乙氧基)酞菁钴(Ⅱ)催化剂对孔雀石绿降解速率的影响:在室温30℃中性环境下,研究了负载金属酞菁催化剂对4 mg/L孔雀石绿溶液的降解情况,同时研究了催化剂投加量、过氧化氢浓度对孔雀石绿降解的影响并探讨了光催化降解孔雀石绿的动力学规律.实验结果表明:制备的催化剂对孔雀石绿...     

Fabrication of deodorizing fabric by grafting of metal phthalocyanine derivative onto nonwoven polypropylene fabric

Fabrication of deodorizing fabric was tried by grafting metal phthalocyanine derivative, a catalytic deodorant, onto polypropylene (PP) nonwoven fabric. Fe(III)-4,4′,4″,4‴-tetra carboxamide phthalocyanine (Fe-TCMP) was synthesized. The Fe-TCMP showed high-deodorizing performance when tested for the elimination of 2-mercaptoethanol, an index material for bad-smelling compounds. The Fe-TCMP was converted to Fe(III)-4,4′,4″,4‴-tetracarboxylic acid phthalocyanine (Fe-TCAP) by hydrolysis to have carboxyl groups. It was chemically grafted on the surface of PP nonwoven fabric, which was surface modified to have amine groups with diaminocyclohexane (DACH) plasma. Such fabricated deodorizing fabric showed high-deodorizing performance for 2-mercaptoethanol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 839–846, 2001     

Voltammetric, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of phthalocyanines

In this work, electrochemical, and in-situ spectroelectrochemical characterization of the metallophthalocyanines bearing tetra-(1,1-(dicarbethoxy)-2-(2-methylbenzyl))-ethyl 3,10,17,24-tetra chloro groups were performed. Voltammetric and in-situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. The redox processes are generally diffusion-controlled, reversible and one-electron transfer processes. Differently lead phthalocyanine demetallized during second oxidation reaction while it was stable during reduction processes. An in-situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l’Eclairage) system of colorimetry, has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for the first time in this study.     

Novel perfluoroalkyl phthalocyanine metal derivatives: Synthesis and photodynamic activities

Novel perfluoroalkyl phthalocyanine metal derivatives with four perfluorobutyl or four perfluorohexyl groups were synthesized by a two-step procedure starting from 4-iodophthalonitrile; the preparation of the key intermediate 4-(perfluorohexyl)phthalonitrile was optimized. Values of fluorescence quantum yield in ethanol of 0.11 and 0.38 were obtained for zinc(II) tetra (perfluorobutyl)phthalocyanine and zinc(II) tetra (perfluorohexyl) phthalocyanine, respectively. The photodynamic activities of two, zinc (II) phthalocyanine derivatives upon both HL-60 leukemic cells and A375 melanotic cancer cells in vitro were investigated revealed that the cell viability was slightly better in the case of HL-60 than A375.     

Novel meso-substituted porphyrins: Synthesis, characterization and photocatalytic activity of their TiO2-based composites

Two series of novel meso-substituted porphyrins, namely 5,10,15,20-tetra[4-(3-phenoxy)-propoxy]phenyl porphyrin, the structural analogue 5,10,15,20-tetra[2-(3-phenoxy)-propoxy]phenyl porphyrin and their Co(II) Cu(II) and Zn(II) complexes were synthesized. The compounds were characterized using various spectroscopic techniques and their molecular structure was proposed based on density functional theory calculations. The diverse properties of the porphyrin derivatives result from the different stereochemistry of the particular substituents at the meso site on the macrocycle and are controlled also by the coordinated metal. The ¹H NMR spectrum of the free-base porphyrin showed a complicated spin-splitting. The photocatalytic activities in degradation of 4-nitrophenol were investigated using polycrystalline TiO₂ impregnated with the porphyrins and metalloporphyrins. The Cu(II) porphyrin was a more effective sensitizer than other metal containing compounds (M = Co, Zn) as well as the free-base. Photocatalytic activity was also influenced by spatial positions of the substitutions on the porphyrin molecules.     

Catalytic activity of cobalt and iron phthalocyanines or porphyrins supported on different carbon nanotubes towards oxygen reduction reaction

Non-noble metal catalysts for O₂ reduction were prepared by dispersing iron(II) phthalocyanine, cobalt(II) tetra-tert-butylphthalocyanine, cobalt(II) 2,3,7,8,12,13,17,18-octaethyl-porphine, and cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrine on carbon nanotubes (CNTs) used as high surface area support. Different types of CNTs (SWCNTs, DWCNTs and MWCNTs) were investigated as an effective substitute for commonly used carbon black in carbon-supported phthalocyanines and porphyrins. The oxygen reduction reaction (ORR) activity of those CNT-supported catalysts in alkaline and acidic solutions was studied. The results show that: (i) all catalytic systems including MWCNTs are more efficient for O₂ reduction than those with SWCNTs and DWCNTs, (ii) the oxidative chemical treatment of the CNTs increases the electrocatalytic performance of the corresponding CNT-supported catalysts, (iii) similarly to Vulcan-supported catalysts, iron(II) phthalocyanine gives the best electroactivity among the investigated CNT-supported materials and (iv) finally, the MWCNT-supported iron(II) phthalocyanine catalyst chemically treated in oxidative conditions shows an ORR catalytic activity comparable to a commonly used Pt/C catalyst with similar current densities and a very low overpotential (60 mV).     

Novel alpha-7-oxy-4-(4-methoxyphenyl)-8-methylcoumarin substituted metal-free,Co(II) and Zn(II) phthalocyanines: Photochemistry,photophysics, conductance and electrochemistry

Novel alpha-substituted metal-free, Co(II) and Zn(II) phthalocyanines, bearing four 7-oxy-4-(4-methoxyphenyl)-8-methylcoumarin moieties were synthesized. The compounds were characterized by elemental analysis, IR, UV–vis, ¹H NMR, ¹³C NMR and MALDI-TOF mass spectroscopies. The Zn(II) phthalocyanine compound showed J-type aggregation in non-coordinating solvents. The photophysical and photochemical properties of these compounds were described in different solvents. Direct current conductivity measurements of the films of Co(II) and Zn(II) phthalocyanines as a function of temperature showed that these compounds are semiconductors with the activation energies within the range of 0.40–0.84 eV. The variation of alternating current conductivity of the films with frequency was found to be represented by the function σ_AC = Aω^s. The results indicated that charge transport mechanism of the films can be explained by hopping. The redox properties of the compounds were also examined in dimethylsulfoxide and dichloromethane by voltammetry and in situ spectroelectrochemistry. The compounds displayed metal and/or phthalocyanine ring-based reduction and oxidation processes. The electrochemistry of a phthalocyanine compound forming a J-aggregated species has been investigated. It was found that some redox couples of the Zn(II) compound in dichloromethane is split due to the equilibrium between its aggregated and non-aggregated species.     

Synthesis and photophysical properties phthalocyanine-pyrene dyads

Metal-free, zinc (II) and nickel(II) phthalocyanines (3-5) with a 1-pyrenylmethoxy substituent on each benzo group were prepared from 4-(1-pyrenylmethoxy)phthalonitrile (2). The new compounds have been characterized by elemental analyses, IR, UV/vis, mass and ¹H NMR spectroscopy. The electronic spectra exhibit an intense π-π∗ transition of pyrene unit identity together with characteristic Q and B bands of the phthalocyanine core. The energy transfer to phthalocyanine core and radiative decays of the pyrene emission and phthalocyanine core were examined. Energy transfer through methoxy bridges has been confirmed by ultraviolet irradiation of pyrene antenna leading to red light emission in 3 and 4.     

Use of gas-diffusion electrodes for high-rate electrochemical reduction of carbon dioxide. II. Reduction at metal phthalocyanine-impregnated electrodes

The use of polytetrafluoroethylene-bonded, carbon gas-diffusion electrodes, prepared with carbon impregnated with metal phthalocyanines, for the electrochemical reduction of carbon dioxide in aqueous, acidic solution has been investigated. High rates of reduction of carbon dioxide to carbon monoxide were demonstrated at electrodes impregnated with cobalt (II) phthalocyanine. In contrast, formic acid, and not carbon monoxide, was produced at low rates at electrodes impregnated with either manganese, copper or zinc phthalocyanine. This marked variation in reaction product on changing the central metal ion of the organometallic complex is rationalized in terms of a reaction mechanism involving, as the first step, the electrochemical reduction of cobalt (II) to cobalt (I).