四磺酸基酞菁锌的合成及其与牛血清白蛋白作用的研究

酞菁化合物及其金属配合物是一类光氧化还原反应的有效光敏剂,对恶性肿瘤具有荧光定位诊断和光动力治疗作用,并对金黄色葡萄球菌、链球菌以及某些寄生虫具有光灭活作用,已引起人们越来越多的兴趣[1].尤其是含不同数目磺酸取代基的酞菁金属配合物被认为是一种较有效的光动力治疗光敏剂.     

烷氧基取代金属酞菁的合成和在有机溶液中聚集性质的研究

酞菁化合物的结构与卟啉类似,对光和热稳定性好,在可见光区有强的吸收,而且它还具有半导体性能和光生伏打效应。因此作为光导材料,信息记录和储存材料,以及在模拟光合作用研究光敏电子转移反应中作为光敏剂。引起人们广泛的兴趣。一般水溶性酞菁在水溶液中容易形成聚集体。     

电照相用苝四羧酸二酰亚胺系有机光导材料

苝四梭酸二酞亚胺系(PTCDI)化合物具有较强的荧光性能和光稳定性.是一类非常适合作为光电转化材料的有机化合物.目前,该化合物的应用已涉及到太阳能转化材料、电子照像用材料、液晶材料等领域^[1,2],象酞菁、方酸类化合物一样^[3,4],目前国际上已有以苝类化合物制备的有机光导鼓(OPC),但对这类化合物的研究,仅局限在少数几个化合物上,搞清结构与性能之间的关系,对苝类化合物作为光导材料的应用,就显得尤为重要.     

有机金属酞菁类化合物及其非线性光限幅特性

随着激光技术的快速发展, 激光武器的性能也越来越优越, 所造成的危害也越来越大, 各国开始加大力度对激光防护材料进行研究. 酞菁化合物具有限幅窗口宽、限幅效果明显、响应迅速等特点, 是一类非常具有应用前景的光限幅材料. 当前, 制备出限幅性能好、稳定性强的酞菁光限幅材料成为激光防护材料领域中的研究热点. 本文评述和总结了近几年在酞菁光限幅材料方面开展的系统研究工作, 首先介绍了酞菁化合物实现光限幅效应的机制, 并在此基础上详细分析了影响光限幅效应的因素以及光限幅器件化过程对酞菁光物理和光限幅性能的影响机理. 根据分析结果提出了在基础和应用研究方面存在的科学问题, 指出了该类型光限幅材料面临的挑战和今后的重要发展方向.     

金属酞菁的合成及其激光解吸质谱研究

通过简便的合成方法,以邻苯二甲酸酐和尿素为起始原料,经过亚胺化、硝化、氨解步骤,经固相熔融法分别合成四硝基酞菁铜和四硝基酞菁镍,最后经还原得四氨基酞菁铜和四氨基酞菁镍.然后分别测定无取代酞菁镍、四氨基酞菁铜和四氨基酞菁镍的激光解析质谱图,理论值与实测值相吻合,并且化合物含量均在96%以上.     

一种可溶性氯铟酞菁化合物的光限幅性能研究

本工作通过无中心金属酞菁合成了可溶性金属酞菁化合物--四-α-(2-乙基丁氧基)氯铟酞菁,用纳秒脉冲激光在532 nm处检测了它在四氢呋喃溶液中的光限幅过程,发现该化合物具有非常明显的光限幅性能.在很低的入射光能量下,输出能量即开始偏离Beer定律,透过率随着入射光能量的增加迅速下降.这一效应归因于酞菁分子的反饱和吸收.通过纳秒激光闪光光解实验测定了上述化合物在四氢呋喃溶液中的瞬态吸收光谱及三线态寿命,实验结果表明在很宽的波长范围内分子具有较强的激发态吸收性能.     

酞菁钯及其对称取代四硝基衍生物的合成

采用改进的综合法合成了酞菁钯及其对称取代四硝基衍生物4,4‘,4‘‘,4‘‘‘-四硝基酞菁钯,经元素分析和红外光谱分析确定了这两种金属酞菁化合物的组成与结构。     

对四-2,3-吡啶并紫菜嗪铬的薄膜电极的光电化学研究

由于叶绿素具有较高的光能转换效率,使许多人对类似于叶绿素结构的酞菁染料产生了兴趣,本文所研究的对四-2,3-吡啶并紫菜嗪铬的薄膜(PcCrPy)就是酞菁类(CrPy)染料的苯环用吡啶环取代的衍生物,从而使染料容易电沉积到各种支持导体上。已有不少人对酞菁的薄膜进行过电化学和光电化学的研究,但几乎没有人对PcCrPy进行过光电化学的研究。我们已对PeCrPy进行了原位吸收光谱研究和原位拉曼光谱研究。本文将对     

四取代羧基酞菁锌与白蛋白共价结合物的制备与光谱性质

通过成酰胺键的方式制备了一系列含羧基酞菁和白蛋白(牛血清白蛋白(BSA),人血清白蛋白(HSA))之间的共价结合物,所涉及到的酞菁分别是α-四(4-羧基苯氧基)酞菁锌(1)和α-四[4-(2-羧基乙基)苯氧基]酞菁锌(3),以及它们相应的β位四取代酞菁锌(化合物2和4).比较了游离酞菁以及它们的白蛋白结合物在磷酸盐缓冲溶液(PBS)中的光谱性质.结果表明,当酞菁被共价固定于白蛋白大分子上之后,展现出比游离酞菁更明显的单体特征吸收,而且结合物中的酞菁光谱特征不受体系pH值变化的影响.羧基在酞菁环上的取代位置,对酞菁与白蛋白结合前后的光谱转变幅度有影响,α位取代比β位取代更有利于光谱的变化.化合物1和3的白蛋白共价结合物在PBS溶液中甚至呈现出单体形式为主的光谱特征,Q带最大吸收波长分别位于697和706nm附近.     

四(5,6-二氯-1,4-二硫杂环已烯)四氮杂卟啉的金属配合物的电化学还原及光谱电化学表征

关于卟啉和酞菁的金属配合物已有广泛的研究，这二类化合物因其具有特殊的结构和功能，在不同领域里得到广泛应用。四氮杂卟啉的分子结构是这两类化合物分子结构的“混种”，兼有两者的基本特性，而含硫四氮杂卟啉的金属配合物具有比金属卟啉和金属酞菁更为优良的物理化学...     

新型水溶性钴酞菁的制备及其催化氧化硫醇的性能

采用丁二酸酐、顺丁烯二酸酐对四氨基钴酞菁进行改性后制得两种新型水溶性钴酞菁衍生物, 测试了这两种改性钴酞菁对巯基乙醇的催化氧化性能, 并考察了溶液pH值、温度和时间对催化氧化活性的影响, 结果表明, 在pH＝11时, 两种改性钴酞菁对巯基乙醇的催化氧化性能最好;随着温度的升高, 催化氧化性能提高.     

Synthesis and photosensitizing properties of fluoroalkoxyl phthalocyanine metal complexes

Nine fluoroalkoxyl phthalocyanine metal complexes (Zn, AlCl, Mg, Co, Cu, FeCl) were synthesized from 4-(polyfluoroalkoxyl) phthalic anhydride. The fat-soluble phthalocyanines were characterized by elemental analysis, IR, ¹H NMR and fast-atom-bombardment mass spectroscopy. Zinc and aluminum chloride complexes show higher photooxidation ability in solution containing 20% perfluorocarbons than in hydrocarbon solvents.     

Novel efficient preparative method for phthalocyanines from phthalimides and phthalic anhydride with HMDS

A convenient synthesis of peripherally substituted or unsubstituted phthalocyanines having a variety of metals is described. Phthalocyanines can be obtained by heating phthalimides or phthalic anhydride with metal salts, hexamethyldisilazane, a catalytic amount of p-TsOH, and DMF at 150 degrees C.     

Improvement in the synthesis of metallophthalocyanines using microwave irradiation

A successful application of microwave irradiation, in which phthalocyanines were synthesized under solventless conditions from 1,2-phthalonitrile or phthalic anhydride and urea in the presence of metal templates is described. It was found that in comparison with conventional heating, the microwave process is a very useful alternative for cyclotetramerization processes because of reduction of the reaction time, better yield, and easy-to-perform procedure.     

Long Directional Interactions (LDIs) in Oligomeric Cofacial Silicon Phthalocyanines and Other Oligomeric and Polymeric Cofacial Phthalocyanines

Crystal structures have been determined for the three-member set of cofacial silicon phthalocyanines, ((n-C(6)H(13))(3)SiO)[SiPcO](1-3)(Si(n-C(6)H(13))(3)). The staggering angles between adjacent rings in the dimer and trimer of this set are ～16°. The interactions leading to these angles have been investigated by the atoms-in-molecules (AIM) and reduced-density-gradient (RDG) methods. The results show that long directional interactions (LDIs) are responsible for these angles. A survey of the staggering angles in various cofacial phthalocyanines described in the literature has revealed the existence of significant LDIs in a number of them. It is apparent that in many cases the ability of LDIs to dominate the forces giving rise to the staggering angles observed in cofacial phthalocyanines depends on their inter-ring separations.     

C64 Nanographene Tetraimide—A Receptor for Phthalocyanines with Subnanomolar Affinity

Phthalocyanines are extensively used by the dye and pigment industry and in photovoltaic and photodynamic therapy research due to their intense absorption of visible light, outstanding stability, and versatility. As pigments, the unsubstituted phthalocyanines are insoluble owing to strong intermolecular π-π-stacking interactions, which causes limitations for the solution chemistry for both free base and metalated phthalocyanines. Here we show a supramolecular host–guest strategy to dissolve phthalocyanines into solution. C₆₄ nanographene tetraimide ( 1 ) binds two free base/zinc/copper phthalocyanines in a 1 : 2 stoichiometry to solubilize phthalocyanines as evidenced by ¹H NMR spectroscopy, UV/Vis absorption and single-crystal X-ray analysis. Binding studies using a tetra-tert-butyl-substituted soluble phthalocyanine revealed binding affinities of up to 10⁹ M⁻¹ in tetrachloromethane, relating to a Gibbs free energy of −52 kJ mol⁻¹. Energy decomposition analysis revealed that complexes between 1 and phthalocyanines are stabilized by dispersion interactions followed by electrostatics as well as significant charge-transfer interactions.     

Effect of axial ligands on the photophysical properties of new silicon(IV) phthalocyanines

A series of axial di-substituted silicon(IV) phthalocyanines with electron-donating and electron-withdrawing properties were synthesized. The compounds were characterized by elemental analysis, ¹H NMR, IR, and ESI-MS. The effect of axial ligands on the photophysical properties of silicon phthalocyanines was studied by UV/Vis, steady-state and time-resolved fluorescence spectroscopic analyses. Compared with silicon phthalocyanines with electron-donating properties, silicon phthalocyanines with electron-withdrawing properties could expand the π-conjugation in the dyes, resulting in a redshift of Q bands, lower fluorescence emission intensity and fluorescence quantum yields, but increasing fluorescence lifetimes. These results strongly suggest that the molecular design of phthalocyanines is essential for construction of photoactive materials.     

Phthalocyanines prepared from 4-chloro-/4-hexylthio-5-(4-phenyloxyacetic acid)phthalonitriles and functionalization of the related phthalocyanines with hydroxymethylferrocene

The phthalonitrile derivative chosen for the synthesis of substituted phthalocyanines [M: 2H, Zn(II), Co(II)] with four chloro and four phenyloxyacetic acid substituents on the periphery is 4-chloro-5-(4-phenyloxyacetic acid)phthalonitrile. The sodium salt of carboxyl substituted zinc phthalocyanine is good soluble in water. Further reactions of zinc and cobalt phthalocyanines bearing phenyloxyacetic acid with thionylchloride gave the corresponding acylchlorides. This functional group reacted with hydroxymethylferrocene in dry DMF to obtain ferrocenyl substituted phthalocyanines. Also chloro substituent in new phthalonitrile was substituted with hexylsulfanyl substituent and its cyclotetramerization in the presence of Zn(AcO)₂·2H₂O and 2-(dimethylamino)ethanol resulted with zinc phthalocyanine. The compounds have been characterized by elemental analysis, MALDI-TOF mass, FT-IR, ¹H NMR, UV-Vis and fluorescence data. Aggregations properties of phthalocyanines were investigated at different concentrations in tetrahydrofuran, dimethylformamide, dimethylsulfoxide, water, and water/ethanol mixture. Also fluorescence spectral properties are reported.     

四取代酞菁金属配合物异构体~1HNMR的表征

概述了近年来用1 HNMR表征一些四取代酞菁金属配合物异构体的研究进展情况。四取代酞菁配合物存在 4种异构体和 8种磁不等价的异吲哚基。这些磁不等价的异吲哚基对苯环上以及取代基的质子的1 HNMR谱均有所影响 ,因此可以通过测定这些质子的1 HNMR谱来确定异构体。     

New amphiphilic silicon(IV) phthalocyanines as efficient photosensitizers for photodynamic therapy: synthesis, photophysical properties, and in vitro photodynamic activities

A novel series of silicon(IV) phthalocyanines substituted axially with one or two 1,3-bis(dimethylamino)-2-propoxy group(s) have been prepared by ligand substitution and alkoxy exchange reactions. Two dicationic and tetracationic phthalocyanines have also been prepared by methylation of two of these compounds. The nonionic phthalocyanines are essentially nonaggregated in common organic solvents and show a weak fluorescence emission, while the methylated derivatives are also nonaggregated, even in aqueous media, and exhibit a strong fluorescence emission. These new phthalocyanines, in particular the unsymmetrical and amphiphilic analogues, are highly potent against HepG2 human hepatocarcinoma cells and J774 mouse macrophage cells with IC50 values down to 0.02 microM. The photodynamic activities are related to the cellular uptake and the efficiency to generate singlet oxygen. A higher positive charge at the phthalocyanine hinders the uptake, reflected by the lower intracellular fluorescence intensity. Fluorescence microscopic studies have also revealed that the unsymmetrical phthalocyanine SiPc[C3H5(NMe2)2O](OMe) (4) has a high and selective affinity to the mitochondria of HepG2 cells.