界面微环境中双亲卟啉的光谱研究

用敏感于微环境变化的UV-Vis光谱,研究了在SDS胶束微环境中,双亲原卟啉P1对体相pH值的依赖关系。体相pH值由弱碱性到强酸性改变的过程中,P1在SDS胶束内存在明显等色点,为一典型的双组分平衡,同时其质子化峰吸收强度逐渐增强,表明P1在胶束内发生了质子化;体相pH值从弱碱到强碱变化时,P1的Soret带红移,吸光度变小,半峰宽加大,这是卟啉从SDS胶束内核转移到胶束表面的结果,由此证明改变pH值可以实现卟啉跨膜转移的控制。     

meso-四(4-磺基苯基)卟啉(TPPS)在水及胶束体系中的二聚行为研究

研究了meso-四（4-磺基苯基）卟啉（TPPS）在胶束（TritonX－100）、KCl水溶液中的电子吸收光谱变化,计算了TPPS的二聚常数KD,用分光光度法研究了TPPS在KCI水溶液中的二聚反应动力学,提出了与实验结果相吻合的二聚机理．根据温度对二聚平衡的影响,计算了二聚平衡的乙和     

单链四苯酚基卟啉在CTAB胶束微环境中的去质子化现象

叶绿素分子的光能转化功能的实现与其聚集状态、所处微环境性质及条件密切相关[1,2]．如何设计控制叶琳类分子在膜介质中的增溶位置，对于研究叶琳在膜体系中的跨膜电子传递、光能转化过程具有重要意义．本文研究了长链双亲卟啉──单链四苯酚基叶琳THPPH2在CTAB胶束中的去质子化，该过程能控制叶琳环在胶束中的增溶位置，使其由内核转移到胶束表面．1实验部分1·1仪器和测试条件岛津UV－240型紫外可见光谱仪（带有恒温夹套），狭缝宽2nm，石英池厚1cm，所用试剂皆为分析纯．UV光谱测试均在恒温条件下进行．1．2溶液的配制含一个十六…     

甲苯胺蓝在SDS胶束中的电化学行为研究

在玻碳电极上研究了甲苯胺蓝(TB)及其在SDS胶束中的电化学行为,并与其直接电化学行为进行了比较。研究结果表明,TB在玻碳电极上的电极反应为2电子可逆氧化还原反应过程。通过介质pH对TB电极反应过程影响的研究,确定在pH<4.2,4.25.9时,参与电极过程的质子数分别为3,2和1,同时给出了TB解离常数K1与K2分别为1.68×10-5和1.93×10-6。在浓度分别为0.05mol.dm-3和0.1mol.dm-3PBS缓冲溶液中,TB在SDS浓度接近其临界胶束浓度(CMC)附近时,其还原峰电流(Ipc)和还原峰电位(Epc)随SDS浓度的增加而降低和负移。在大于CMC浓度时,其还原峰电流(Ipc)和还原峰电位(Epc)随SDS浓度的增加而上升和正移,之后出现了一个平台段。同时还测定了TB及其在胶束体系中的扩散系数D及电极反应速率常数Kf,并对SDS胶束对TB电化学行为的影响因素给出了合理的理论解释。     

5,10,15,20-四(4-羧基苯基)卟啉的微波合成

利用微波加热法,由5,10,15,20-四(4-甲氧羰基苯基)卟啉水解合成了四(4-羧基苯基)卟啉,并对反应条件进行了探讨。结果表明：以吡啶为溶剂,氢氧化钾为催化剂,以65W的微波功率辐射30rnin,可使5,10,15,20-四(4．甲氧羰基苯基)卟啉完全水解。反应时间是传统加热法用时的1/48。     

四(4-硝基苯基)卟啉和四(4-氨基苯基)卟啉的合成

四（４氨基苯基）卟啉（ＴＡＰＰ）是含有４个反应活性基团的卟啉衍生物,可在模拟某些生物过程或氧化还原反应的树枝状或簇状分子中作为富电子中心,也可直接用来制备光电器件或作为光电功能聚合物的功能单体和交联剂,因此,ＴＡＰＰ的合成研究具有重要意义［１］．...     

meso—四（4—磺基苯基）卟啉（TPPS）在水及胶束体系中的二聚行为研究

研究了ｍｅｓｏ－四（４－磺基苯基）卟啉在胶束，ＫＣｌ水溶液中的电子吸收光谱变化，计算了ＴＰＰＳ的二聚常数ＫＤ，用分光光度法研究了ＴＰＰＳ在ＫＣｌ水溶液中的二聚反应动力学，提出了与实验结果相吻合的二聚机理。根据温度对二聚平衡的影响。     

吉非罗齐在胶束体系中的荧光光谱性质研究

研究了吉非罗齐在胶束体系中的荧光性质,发现十二烷基硫酸钠(SDS)对吉非罗齐有较强的荧光增敏作用,据此建立了荧光光谱测定吉非罗齐的方法。结果表明,在0.1~1.2μg.mL-1范围内,吉非罗齐与其荧光强度呈良好的线性关系,其线性方程为F=414.76c-0.265,方法检出限为0.05μg.mL-1,回收率为96.3%~101.5%,相对标准偏差(RSD)为1.7%~2.1%。本法用于实际样品分析,获得满意结果。     

SDS胶束体系中亚甲蓝与血清白蛋白的相互作用

The interaction of methylene blue(MB) and bovine serum albumin(BSA) is investigated in the SDS micelle system which is simulated as one kind of coexisted albumin. The interaction parameters of MB and BSA and simulated albumin such as partition coefficient 辍ormal binding free energy 腉、average binding number n are calculated. The results show that most of MB is in the form of monomer in SDS micelle systems;the main interaction of MB and BSA is of static electric and H bind force,and that of MB and simulated albumin is only of static electric force.     

四苯基卟啉类光敏剂在醇-酸体系中的光谱性质研究

研究了四苯基卟啉类光敏剂在醇-酸体系中的光谱性质,以及在此体系中浓度、酸度、表面活性剂等因素对其光谱性质的影响,首次发现在醇-酸体系中四苯基卟啉类光敏剂的光谱性质发生改变,靠近红外区均有中强度吸收,它们在可见光波长的激发下能产生在近红外区的荧光峰,与硫酸比较而言,盐酸配制的醇-酸体系优于硫酸体系.醇与酸的配比最好选择10:1,酸的最佳浓度选择1mol·L-1.优选出四-(p-甲基苯基)卟啉和四-(p-甲氧基苯基)卟啉这两种光敏活性物质.     

Protonation of 5, 10, 15, 20-Tetra（4-hydroxyphenyl）-porphyrin in SDS Micellar Solution

An arnphiphilic porphyrin, 5, 10, 15, 20-tetra(4-hydroxyphenyl)-porphyrin (P) was solubilized in SDS micellar solutions. By taking advantage of protonation property of pyridine groups of amphiphilic porphyrin and the UV-Vis spectral sensitivity of Soret band and Q bands to the microenvironment of the porphyrin moiety, two-step protonation was studied in detail by means of UV-Vis spectroscopy. The free base, monocation and dication were described in detail in SDS micellar solution. The possibility of microphase transition was proposed to relate to the observation of two isosbestic points.     

卟啉配位剂meso－四（对－羧基苯基）卟啉（H_2TCPP）极谱行为的研究

采用直流极谱和循环伏安等多种手段研究了卟啉配位剂（Ｈ_２ＴＣＰＰ）在汞电极上的极谱性质。在碱性介质中，Ｈ_２ＴＣＰＰ的电极反应具有以下三个特性：（１）第一步为受扩散控制的２ｅ并有２Ｈ~＋参与的可逆还原过程，第二和第三步为不可逆各为２ｅ的还原反应；（２）Ｈ_２ＴＣＰＰ在汞电极上存在强吸附性；（３）第一步电极反应产物可发生随后的化学反应，即前两步还原经由ＥＣＥ机理进行。     

Hydrolysis of Cephanone in SDS/n-C_5H_(11)OH/H_2O System

IntroductionMicellesolutioncomposedofsurfactantscanaffect,adjustandcontrolmanychemicalreactionsaccordingtoitseffectsoflocalconcentration ,polarity ,charge ,microvis cosity,electrostatics ,etc ..1,2 Recently ,ithasarousedmuchattentiontoconductchemicalreactionsusingmi croemulsionasmicroreactor .3 7Theeffectofmicelleonthechemicalreactionstemsfromitsstaticelectricityandhy drophobicity .Usually ,cationicsurfactantcancatalyzethereactionbetweennucleophileandneutralmolecule ,whileanionicsurfactantsusp…     

Self-assembly of iron TCPP (meso-tetra(4-carboxyphenyl)porphyrin) into a chiral 2D coordination polymer

Synthetic metalloporphyrin complexes are often used as analogues of natural systems, and they can be used for the preparation of high-dimensional coordination polymers. In this work, a new chiral Fe-TCPP (TCPP is meso-tetra-(4-carboxyphenyl)porphyrin) coordination compound has been synthesized and structurally characterized. The compound is 2D via coordination bonds, and it exhibits strong hydrogen bonds that connect the planar arrays forming the 3D framework. The oxidation of the original Fe^II ions to Fe^III accounts for the formation of this array, in which the topological analysis reveals a very high connectivity based on a simple extension fashion of the structure. DFT calculations have been also carried out to study the stabilization of the Fe^III-compound. This is the third example of a 2D coordination compound based on TCPP in which the dimensionality refers just to coordination bonds, and no other ligands are present in the structure.     

卵磷脂与CCl4、CHCl3的反胶束中水增溶机制的研究

采用红外光谱、核磁共振谱技术研究了ＰＣ（卵磷脂）－ＣＣｌ４、ＰＣ－ＣＨ（Ｄ）Ｃｌ３反胶束中增溶水的缔合状态以及水与ＰＣ分子中不同功能基团的作用随水量的变化。实验结果表明,随反胶束捕集水量的增加,胶束中存在３种不同的缔合水：结合水,界面束缚水,类体相水,其中结合水以配位方式与ＰＣ极性端基的胆碱基团［—Ｎ＋（ＣＨ３）３］作用,以氢键与磷酸脂基ＯＰ（ＯＲ）２Ｏ－１基团结合。另外,用吸收光谱法测定饱和增溶点并根据球型反胶束模型计算了增溶后反胶束的聚集数及水核半径     

Lanthanide Complexes with Acetylacetone and 5-(4-Nitrophenyl)-10,15,20-Triphcnylporphyrin Ligands

Sincethefirstlanthanideporphyrinwassynthesizedin1974',anumberofthisclassofporphyrinshavebeensynthesized'.Becauselanthanideionhasspecialelectronstructure,peopleareinterestedinpropertiesoflanthanideporphyrincomplexessuchascatalyticfunction,opticalstorage,etc3.Ingeneral,moresymmetricallyfunctionallanthanideporphyrinshavebeenstudied,butfewerunsymmetricallanthanideporphyrinsarereported.Nowlanthanidecomplexesofunsymmetricallymeso-substitutedphenylporphyrinacetylacetonate5-(4-nitrophenyl)-10,15,20-tr…     

Electrochemical Behavior of meso-Tetra (4-Sulfonatophenyl) Porphyrin and Its Copper Complex

The complex of Cu-TPPS was formed directly by mixing equal-molar concentrations of Cu~(2+) and meso-tetra(4-sulfonatophenyl) porphyrin(TPPS)in an acetate buffer solution at pH 4-6, and its electrochemical behavior was studied by the techniques of polarography, cyclic voltammetry and spectroelectrochemistry. Three different methods were applied to accelerating the formation of Cu-TPPS in aqueous solution, i.e. heating of solution,using vitamin C as a catalyst and preadsorbing TPPS on a hanging mercury electrode. The voltammetric reductions have shown 2e~- for the first step of TPPS and 4e~- for Cu-TPPS with a peak potential at -1.04V. By applying the method of spectroelectrochemistry using a selfdesigned long-optical-path cell with Hg working electrode, the amount of saturated adsorption of TPPS and Cu-TPPS on mercury surface is found to be the same. Hence, the area of the adsorbed molecule calculated by measuring the area (i×t) under the voltammetric peak is also the same as 395 (?)~2.     

meso-四[(4-苯乙烯氨基)苯基]卟啉合成及其波谱特点

以吡咯和对硝基苯甲醛为原料,经过环化、还原和缩合,合成了meso-四[(4-苯乙烯氨基)苯基]卟啉(TBAPP),通过UV-Vis、FT-IR、1H NMR及元素分析等对产物进行了表征,并对其荧光和电子顺磁共振特性进行了研究。 卟啉产物的EPR测定显示出游离基特征,表明卟啉分子的大π共轭结构对周边基团产生的自由基有稳定作用。 取代基对卟啉的紫外 可见吸收、光致发光及电子顺磁共振特性均有影响。 四席夫碱苯基卟啉TBAPP的Q带比前体四氨基卟啉（TAPP）和母体四硝苯基卟啉（TNPP）红移,而Soret谱带变化较小;TBAPP的440 nm光激发的最大荧光峰658 nm分别比TAPP蓝移5 nm和比TNPP红移9 nm;TBAPP的EPR精细结构比TAPP弱,而比TNPP强。     

Porphyrin Clathrates. Crystal Structures of Two Unexpected Products Obtained by Solvothermal Reactions of Pt-tetra(4-carboxyphenyl)porphyrin with Copper Acetate

The X-ray crystal structure of IX, perchlorate salt of R-(–-2-ethyl-N-benzyl-4,7,19,13-tetraoxa-8,9-benzo-1-azacyclopentadec-8-ene has been determined. In the molecule, the protonated nitrogen atom participates in two N-HO hydrogen bonds. The unusually high proton affinity of aza crown ether leads to the formation of diastreomer instead of complex formation with chiral R-(+)-1-phenyl ethyl ammonium perchlorate and S-(–)-1-phenyl ethyl ammonium perchlorate. The complex ability of host ethers was evaluated in terms of structural modification.