光谱法及热动力学法研究环糊精与四-N-正丙基吡啶基卟啉的作用

通过紫外吸收,荧光光谱,一维、二维核磁共振技术等光谱方法,确定了环糊精与四－N－正丙基吡啶基卟啉2：1型包合物的形成,分子模拟方法进一步证实了该包合物的形成;采用热动力学法研究了温度对包合反应的影响,计算得出包合过程的熵变、焓变及自由能变化,绘出了卟啉类化合物与环糊精包合物的熵焓补偿曲线,进而确定了包合反应的主 要驱动力是焓。     

用分子光谱法研究两种水溶性卟啉与磺丁醚-β-环糊精的超分子体系

本文以紫外可见光谱法和荧光光谱法研究了水溶性的四-(4-甲基吡啶基)卟啉(TMPyP)和四-(4-羧基苯基)卟啉(TCPP)与磺丁醚-β-环糊精(SBE--βCD)形成的超分子体系。结果表明,两种卟啉与磺丁醚-β-环糊精都形成了1∶1的包结物,它们的包结常数分别为1.34×104L.mol-1和1.15×105L.mol-1。     

4，4’－联吡啶－β－环糊精包合物研究

本文合成了以β－环糊精为主体、４．４＇－联吡啶为客体的晶体包合物，通过元素分析、红外光谱、差热、Ｘ－射线粉末衍射等分析方法确定了包合物的形成，实验结果表明：β－环糊精与４，４’－联吡啶分子形成摩尔比为２∶１的包合物，４，４’－联吡啶的吡啶环嵌入β－环糊精分子的疏水性空腔内．     

包合锰卟啉的环糊精聚合物作为过氧化物朊酶模型物的研究

制备了β－环糊精交联聚合物和四（４－三甲铵基苯基）卟啉锰的超分子包合物，并以此包合物作为过氧化物朊酶的模型物。     

β-环糊精对芳香族氨基酸的包合作用研究

研究了β-环糊精与芳香族氨基酸的超分子包合作用,考察了β-环糊精用量、温度、pH值等因素对包合作用的影响.紫外光谱和荧光光谱测定结果表明,β-环糊精与氨基酸形成了包合物,并从主-客体间的尺寸关系、包合驱动力、分子识别等方面讨论了β-环糊精与氨基酸的分子识别机制.     

超分子体系中的分子识别研究──XXXV.含吡啶基β-环糊精衍生物的合成及其对氨基酸分子的手性识别

通过２-氨基吡啶与β环糊精醛３在甲醇水溶液中反应合成了一种新型含吡啶基β－环糊精衍生物４,并采用荧光光谱滴定法测定了它与几种脂肪氨基酸在磷酸盐缓冲溶液（ｐＨ＝ ７．２, ０． １ｍｏｌ· Ｌ－１）中于 ２５℃时形成超分子配合物的稳定常数．化学计量法结果显示,化合物４与氨基酸形成了１：１的超分子配合物．圆二色谱研究表明,在溶液中化合物４的取代基浅包结进入自身环糊精空腔．修饰环糊精中的吡啶基作为一种光谱探针,不仅可以识别氨基酸分子的尺寸或形状,而且还可以识别Ｌ／Ｄ－型手性对映体之间的差异．与单－［６－（１－吡啶基）－６－脱氧］－β－环糊精５相比,化合物４对氨基酸的对映体选择性发生翻转,其中对Ｄ／Ｌ－丝氨酸给出最高的对映体选择性达５．４．从主－客体间几何互补、诱导楔合以及几种弱相互作用力的协同效应,讨论了环糊精衍生物选择性结合氨基酸形成超分子配合物的稳定性．     

水溶性游离碱阳离子卟啉与核酸作用的光谱研究

研究了ｍｅｓｏ－四（对－三甲基氨基苯基）卟啉（ＴＡＰＰ）和ｍｅｓｏ－四（对－甲基吡啶基）卟啉（ＴＭｐｙＰ－４）与核酸作用的电子吸收光谱、荧光光谱和共振光散射光谱的特性，电子吸收和荧光光谱研究表明，这两个水溶性阳离子卟啉与核酸的摩尔比（Ｒ）大于０．２５时，核酸对卟啉的Ｓｏｒｅｔ带有减色效应和荧光猝灭效应；当Ｒ〈０．２５时，核酸与卟啉作用形成新的荧光复合物，共振光散射光谱研究表明，核酸使ＴＡＰＰ的共振     

3，3′，5，5′—四甲基联苯胺—β—环糊精包合物性质的研究

3,3′,5,5′－四甲基联苯胺（TMB）是一种联苯胺类色原试剂,具有良好的氧化还原性,将TMB包合于β－环糊精腔内,由于超分子化合物的形成而使TMB的反应性有所改变。本文采用紫外－可见吸收光谱和电化学方法研究了TMB和β－环糊精形成的包合物的性质。研究表明形成包合物后,无论在溶液体系还是在电极表面,其氧化还原活性得到明显的加强。     

β-环糊精及羟丙基β-环糊精与香兰素包合作用的谱学研究

用^1H-NMR、紫外吸收及荧光光谱研究了香兰素与β－CD和HPβ－CD的包合作用，发现香兰素与HPβ－CD包合时，HPβ－CD的内腔H－3和H－5质子较与β－CD包合时明显移向高场，表明香兰素分子进入HPβ－CD的内腔较深。用Benesi-Hildebrand关系式求得的包合物的平衡常数也证实香兰素分子进入HPβ－CD的内腔较深，所形成的包合物较稳定。     

羟丙基-β-CD包结荧光法测定大黄素的研究

用荧光光谱研究了羟丙基-β-环糊精(HP-β-CD)与大黄素间的相互作用,发现两者可形成1∶1的超分子包合物,大黄素包合物在λex/λem=467/547 nm处发射荧光,包合常数为85.18 L/mol.据此建立了羟丙基-β-环糊精增敏测定大黄素的荧光分析新方法.在0.32～3.24μ-g/mL浓度范围内,大黄素的荧...     

Structure and photoelectric properties of LB films of porphyrin bearing pyridinium with long-chain alkyl group

Ｉｎｒｅｃｅｎｔｙｅａｒｓ,ｔｈｅｓｔｕｄｙｏｎｔｈｅｃｏｎｖｅｒｓｉｏｎａｎｄａｐｐｌｉｃａｔｉｏｎｏｆｓｏｌａｒｅｎｅｒｇｙｈａｓｂｅｅｎｏｎｅｏｆｔｈｅｍｏｓｔａｃｔｉｖｅａｓｐｅｃｔｓｉｎｔｈｅｆｉｅｌｄｓｏｆｎｅｗｅｎｅｒｇｅｔｉｃｓｏｕｒｃｅｄｅｖｅｌｏｐｍｅｎｔ,ｔｈｅｆａｂｒｉｃａｔｉｏｎｏｆｎｏｖｅｌｓｏｌａｒｅｎｅｒｇｙｃｅｌｌｓｂｅｃｏｍｅｓｔｈｅｇｏａｌｏｆｐｅｏｐｌｅ’ｓｅｆｆｏｒｔｓ.Ｉｎｏｒｇａｎｉｃｓｅｍｉｃｏｎｄｕｃｔｉｖｅｓｏｌａｒｅｎｅｒｇｙｃｅｌｌｓｈａｖｅ…     

Synthesis of Glucoside Bonded Metal Porphyrins

Enzyme catalyzed reaction often has high selectivity and efficiency under mild conditions. However, disadvantage of enzyme catalysts is the difficulty of recovery. Metalloporphyrin plays an important role in biological system such as redox reaction, electron transfer,oxygen transportation and charge separation etc.1,2 Metalloporphyrins as superoxide dismutase (SOD) mimics have showed the ability of catalyzing the redox reaction of some harmful radicals , such as O2·―, ·OH. Grove and co-…     

Dual 2-Hydroxypropyl-β-Cyclodextrin and 5,10,15,20-Tetrakis (4-Hydroxyphenyl) Porphyrin System as a Novel Chiral-Achiral Selector Complex for Enantioseparation of Aminoalkanol Derivatives with Anticancer Activity in Capillary Electrophoresis

In this study, a complex consisting of 2-hydroxypropyl-β-cyclodextrin and 5,10,15,20-tetrakis (4-hydroxyphenyl) porphyrin, (named dual chiral-achiral selector complex) was used for the determination of two novel potential anticancer agents of (I) and (II) aminoalkanol derivatives. This work aimed at developing an effective method that can be utilized for the determination of I (S), I (R), and II (S) and II (R) enantiomers of (I) and (II) compounds through the use of a dual chiral-achiral selector complex consisting of hydroxypropyl-β-cyclodextrin and 5,10,15,20-tetrakis (4-hydroxyphenyl) porphyrin system by applying capillary electrophoresis. This combination proved to be beneficial in achieving high separation selectivity due to the combined effects of different modes of chiral discrimination. The enantiomers of (I) and (II) compounds were separated within a very short time of 3.6–7.2 min, in pH 2.5 phosphate buffer containing 2-hydroxypropyl-β-cyclodextrin and 5,10,15,20-tetrakis (4-hydroxyphenyl) porphyrin system at a concentration of 5 and 10 mM, respectively, at 25 °C and +10 kV. The detection wavelength of the detector was set at 200 nm. The LOD for I (S), I (R), II (S), and II (R) was 65.2, 65.6, 65.1, and 65.7 ng/mL, respectively. LOQ for I (S), I (R), II (S), and II (R) was 216.5, 217.8, 217.1, and 218.1 ng/mL, respectively. Recovery was 94.9–99.9%. The repeatability and reproducibility of the method based on the values of the migration time, and the area under the peak was 0.3–2.9% RSD. The stability of the method was determined at 0.1–4.9% RSD. The developed method was used in the pilot studies for determining the enantiomers I (S), I (R), II (S), and II (R) in the blood serum.     

荧光光谱法研究维生素B_1与β-环糊精及其衍生物的包合作用

采用荧光光谱法研究了β-环糊精(β-CD)、甲基-β-环糊精(M-β-CD)、羟丙基-β-环糊精(HP-β-CD)、磺丁基-β-环糊精(SBE-β-CD)对维生素B_1的包合作用.在固定维生素B_1浓度和改变环糊精及其衍生物浓度的情况下,维生素B_1的荧光发射波长的变化以及荧光强度的增强表明了包合物的形成,用荧光双倒数法计算了环糊精及其衍生物与维生素B_1的包合常数.实验结果表明:在pH=7.4的体系中,β-环糊精对维生素B_1的包合能力最强,且四种环糊精与维生素B_1的包合物的包合比均为1∶1.     

Preparation and characterization of the inclusion complex of baicalein with γ-cyclodextrin: an antioxidant ability study

The formation of the complex of Baicalein with γ-cyclodextrin (γ-CD) was studied by UV–Vis absorption spectroscopy, fluorescence spectra and nuclear magnetic resonance spectroscopy (NMR) in solution. The solid inclusion complex of Baicalein with γ-CD was synthesized by the co-precipitation method. The characterization of the solid inclusion complexes have been proved by infrared spectra. The formation constant (K) of complex was determined by fluorescence method. The results suggested that in different pH solutions, γ-CD has different inclusive capacity to different forms of Baicalein. γ-CD was most suitable for inclusion in neutral media. In addition, the experimental resulted confirmed the existence of 1:1 inclusion complex of Baicalein with γ-CD. Kinetic studies of DPPH? with Baicalein and γ-CD complex were done. The results obtained indicated that the Baicalein/γ-CD complex was the most reactive form. Special configuration of complex has been proposed on NMR technique.     

Interaction between certain porphyrins and CdS colloids: a steady state and time resolved fluorescence quenching study

The interaction between porphyrins namely, meso-tetrakis (4-methoxyphenyl)porphyrin (TMeOPP), protoporphyrin IX (PPIX) and Zinc(II) meso-tetraphenylporphyrin (ZnTPP) with colloidal CdS has been studied by using steady state and time resolved fluorescence quenching measurements. The porphyrins adsorbed on the surface of colloidal CdS due to electrostatic interaction. This adsorption leads to changes in the absorption spectra related to the complex formation. The apparent association constant (Kapp) was in the order of 4.34-5.58 x 10(5) M(-1) from the effect of colloidal CdS on the absorption spectra and 0.64-1.6 x 10(5) M(-1) from fluorescence quenching data. Quenching is attributable mainly to static mechanism through ground state complex formation as confirmed by lifetime measurements.     

Synthesis and spectrophotometric study of the acid-base and complexing properties of 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin in acetonitrile

2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin has been synthesized, and its acid-base and complexing properties in the systems 1,8-diazabicyclo[5.4.0]undec-7-ene-acetonitrile, acetonitrile-Zn(OAc)₂, and 1,8-diazabicyclo[5.4.0]undec-7-ene-acetonitrile-Zn(OAc)₂ have been studied by spectrophotometry. Titration of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin with 1,8-diazabicyclo[5.4.0]undec-7-ene is accompanied by successive deprotonation of the pyrrole nitrogen atoms with formation of the corresponding mono- and dianion. The overall acid dissociation constant of the title compound has been determined. The complexation of neutral and doubly deprotonated 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin with Zn(OAc)₂ has been studied, and kinetic parameters for the formation of the zinc complex according to the molecular and ionic mechanisms have been determined. Extra coordination of 1,8-diazabicyclo[5.4.0]undec-7-ene by the zinc complex of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin.     

β-环糊精与维生素E包合物的制备及其光谱特性

分别用溶液法、超声波法、微波辐射法制备了β-环糊精与维生素E的包合物,研究了温度、包合时间、β-环糊精与维生素E的摩尔比对包合率的影响,并用荧光光谱法测定了包合物的包合常数Kf为2.84×103 L/mol,用紫外光谱、红外光谱及荧光光谱对包合物进行了表征。     

meso-5,10,15,20-四（取代2-噻吩基）卟啉及其配合物的合成与表征

用混合溶剂法合成了中位噻吩基取代的卟啉化合物：meso-四(2-噻吩基)卟啉 ，meso-四(4-溴-2-噻吩基)卟啉和meso-四(3-甲基-2-噻吩基)卟啉，产率达到36． 5％-39．3％，考察了溶剂的配比、反应温度、反应时间等因素对反应的影响，其 最佳反应条件为：溶剂配比：丙酸：乙酸：硝基苯：2：2(or3)：1；反应温度： 130~140t；反应时间：50-60min．研究了利用固相合成法合成上述卟啉化合物与过 渡金属盐形成配合物的配位反应，在40℃利用固相合成法合成了卟啉化合物与 Fe2' Fe~3+，CO~2+，Ni~2+，Mn~2+等过渡金属离子形成的配合物，产率为81．1 ％~87．6％．利用元素分析，UV-vis，m，'HNMR， HRMS对卟啉化合物及其配合物 进行了表征，利用TG-DTA研究了它们的热稳定性，利用EPR研究了它们的顺磁性．     

Methoxy-isoporphyrins of water-soluble porphyrins: synthesis,characterization and electrochemical properties

Abstract

Methoxy-isoporphyrins of zinc [5,10,15,20-tetrakis(4-sulfonatophenyl)]porphyrin, ZnTSPP (1a) and zinc [5,10,15,20-tetrakis(4-carboxyphenyl)]porphyrin, ZnTCPP (1b) have been synthesized and characterized using standard spectroscopic techniques (Uv-visible, ¹H NMR) , ESI-mass spectrometry and powder X-ray diffraction studies. The isoporphyrins [5-(methoxy)-5,10,15,20-tetrakis(4-sulfonatophenyl)-5H,15H-porphinato]zinc(II) (2a) and [5-(methoxy)-5,10,15,20-tetrakis(4-carboxyphenyl)-5H,21H-porphinato]zinc(II) (2b) are formed due to nucleophilic attack of the methanol to the zinc porphyrin dication. Ceric ammonium nitrate (CAN) was used to oxidize zinc porphyrin and to form zinc porphyrin dication. The electronic spectra of the isoporphyrin complexes 2a and 2b exhibit an intense peak at near IR region . Electrochemical measurements of the synthesized isoporphyrins showed a typical irreversible reduction peak at lower potential. S-containing nucleophiles, which work as reducing agents, convert the zinc isoporphyrins to their parent porphyrins, which supports the electrochemical observations. Their structural properties have been studied using powder X-ray diffraction. The luminescence properties of isoporphyrins were compared with the parent zinc porphyrins.