Electrochemical studies of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS) with albumin

An electrochemical investigation of the interaction of TPPS with BSA on a Hg electrode is reported for the first time. The addition of BSA to TPPS solution results in a decrease of both the reduction and the oxidation current with no change of the peak potentials. In presence of BSA, no new peaks appear, and the standard rate constant k _s is not significantly changed. The reaction of TPPS with BSA yields a kind of supramolecular complex TPPS-BSA, which is electrochemically non-active. The equilibrium constant for the complex has been calculated. The decrease of the peak current can be used to determine BSA concentrations. Received: 2 August 1998 / Revised: 21 September 1998 / Accepted: 24 September 1998     

Electrochemical studies of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS) with albumin

An electrochemical investigation of the interaction of TPPS with BSA on a Hg electrode is reported for the first time. The addition of BSA to TPPS solution results in a decrease of both the reduction and the oxidation current with no change of the peak potentials. In presence of BSA, no new peaks appear, and the standard rate constant k _s is not significantly changed. The reaction of TPPS with BSA yields a kind of supramolecular complex TPPS-BSA, which is electrochemically non-active. The equilibrium constant for the complex has been calculated. The decrease of the peak current can be used to determine BSA concentrations. Received: 2 August 1998 / Revised: 21 September 1998 / Accepted: 24 September 1998     

Electrochemical studies of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS) with an antibody

A voltammetric study of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS) with its polyclonal antibody on Hg electrode in Britton–Robinson buffer solution is described. The addition of antibody to TPPS solution can result in a decrease of both the reduction and the oxidation current with no change of the peak potential. In presence of antibody, no new peaks appear. The standard rate constant k_s and the transfer coefficient α are not significantly changed. The reaction of TPPS with antibody yields kind of supramolecular complexes, which are non-electrochemically active. The binding rate as well as the equilibrium constant for the complex has been calculated.     

A Novel Protein Assay Method Using Tetraphenylporphin tetrasulfonate (TPPS4)

Abstract

A sensitive protein assay method which involves the reaction of TPPS₄ with protein is described. When protein is added to TPPS₄ solution, an absorption band with the maximum at 488 nm appears and the absorbance is proportional to the concentration of protein. Just Like the Soret absorption of the porphyrin, the new band is very narrow and there is no overlap at all between them, which means the free dyes would not give any background for the detection of the protein-TPPS₄ complexes. A new spectrophotometric method for determination of protein has been constructed and applied to the determination of human plasma protein and urinary protein; The assay using microtiter plates has also been studied.     

Molecular interactions of monosulfonate tetraphenylporphyrin (TPPS1) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) with dimethyl methylphosphonate (DMMP)

The molecular interactions of monosulfonate tetraphenylporphyrin (TPPS₁) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) with dimethyl methylphosphonate (DMMP) have been investigated by UV–vis and fluorescence spectroscopies. The association constants and interaction stoichiometries of the bindings were obtained through Benesi–Hildebrand (B–H) method. Particularly, both linear and nonlinear fitting procedures were performed to evaluate the possible 1:2 interactions. Experimental results showed that hydrogen-bonding interactions existed in both of the two systems, resulting in regular changes in the absorbance and fluorescence characteristics of the porphyrins. The association constants and stoichiometries determined from absorbance and fluorescence studies were in excellent agreement. Using a nonlinear fitting method, we demonstrated that the one-step 1:2 interaction took place in the TPPS₁–DMMP system, and the association constants were determined to be 71.4 M⁻¹ by absorbance measurements and 70.92 M⁻¹ by fluorescence measurements. The interaction stoichiometry of the TPPS–DMMP system was 1:1, and the association constants were determined to be 16.06 M⁻¹ by absorbance measurements and 16.03 M⁻¹ by fluorescence measurements. It was concluded that the interaction between TPPS₁ and DMMP was stronger than that between TPPS and DMMP.     

Micellization of copolymers via noncovalent interaction with TPPS and aggregation of TPPS

Aggregation of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) was investigated in complex micelles composed of poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG-b-P4VP) and poly(2-(dimethylamino)ethyl methylacrylate)-b-poly(Nisopropylacrylamide) (PDMAEMA-b-PNIPAM) in aqueous solutions.The resultant complex micelles had a complex P4VP/ PDMAEMA/TPPS core and a mixed PEG/PNIPAM shell.Different noncovalent interaction modes between the porphyrin and each copolymer accomplished a co-effect on the ...     

Spectral and photochemical properties of tetraphenylporphyrin tetrasulfonate supported on modified montmorillonite nanoparticles

A photocatalyst that effectively sensitizes the oxidation of 9,10-diphenylanthracene in toluene under irradiation with visible light has been prepared by the treatment of cationic surfactant-modified montmorillonite nanoparticles with a solution of meso-tetrakis(4-sulfonatophenyl)porphyrin. Reaction quantum yields and singlet oxygen generation probability have been determined. The shifts and intensity changes observed for the absorption bands of meso-tetrakis(4-sulfonatophenyl)porphyrin in the catalyst as compared with aqueous solutions are associated with solvation effects. The meso-tetrakis(4-sulfonatophenyl)porphyrin triplet state has been detected using the laser photolysis technique, and the rate constant of its quenching by oxygen on the surface of nanoparticles has been measured.     

Spectrophotometric study of the interaction of some hydroxyanthraquinones (HAQs) with magnesium(II) in a cationic micelle

Six different hydroxyanthraquinones (HAQs) in aqueous micellar (cationic, anionic and non-ionic) media were tested as effective and selective chelators for the MgII ion in alkaline conditions. Of these 1,4 and 1,8-dihydroxyanthraquinones were found to effectively bind to MgII ions and were useful for the ppm level spectral determination of MgII ion. The MgII ion forms 1 : 1 and 1 : 2 chelates with 1,4-and 1,8-dihydroxyanthraquinones, respectively, which have maximum absorption at 610 and 575 nm, respectively. MgII can be determined in the presence of a large excess of foreign ions including the CaII ion. The statistical analysis of the results, apparent pK(a), expected bathchromic shift of the reagent absorption, molar absorptivity change and electronic spectra in various organized media are discussed.     

Fluorometric study of the inclusion interaction of beta-cyclodextrin derivatives with tetraphenylporphyrin and its analytical application

The effects of native beta-cyclodextrin (beta-CD) and four kinds of alkylated beta-cyclodextrin (beta-CDs), i.e. heptakis (2,6-di-O-isobutyl-beta-cyclodextrin) (I), heptakis (2,6-di-O-octyl-beta-cyclodextrin) (II), heptakis (2,6-di-O-dodecyl-beta-cyclodextrin) (III), and heptakis (2,6-di-O-hexadecyl-beta-cyclodextrin) (IV), on the fluorescence behaviors of tetraphenylporphyrin (TPP) are investigated. An obvious fluorescence enhancement is observed from TPP by using alkylated derivatives compared to that obtained in beta-CD aqueous or in water. A 114-N fluorescence emission intensity enhancement is found for the complex with 2,6-di-O-octyl-beta-cyclodextrin relative to the free analyte. The exact stoichiometric ratios and the formation constants of the inclusion complexes have been examined by application of curve fitting method. The linear calibration plots between fluorescence intensity and TPP concentration are determined in the 1.14 x 10(-8)-5.06 x 10(-6) mol l(-1) range.     

Spectrophotometric study of the reaction of the uranyl ion with 4-(2-thiazolylazo) resorcinol

The uranyl ion forms only 1:1 chelates with 4-(2-thiazolylazo) resorcinol (TAR) in solution, UO(2)(TAR)H(+) being formed below pH 3 and UOS(TAR) above pH 3-5. The latter complex may also be precipitated at pH > 3. The quantitative formation of UO(2)(TAR) at pH 7.5-7.8 in solutions containing a small excess of reagent and some triethanolamine as buffer can be used for the sensitive spectrophotometric determination of uranium. Several interfering ions can be masked with a mixture of sodium fluoride, cyclohexanediaminetetraacetic acid and 5-sulphosalicylic acid. TAR is slightly less sensitive than 4-(2-pyridylazo)resorcinol as a reagent for uranium but is more selective.     

四磺基苯基卟啉的表面增强拉曼效应

以三电极电池系统在不同电位下的在位测量测得四磺基苯基卟啉钠水溶液（浓度为５×１０＾－５ｍｏｌ／Ｌ）的表面增强拉曼谱。结果表明，在接近第一还原态电位处对吸附分子活化后，可得到较大倍数的增强信号（１０＾７数量级）。对照简正坐标计量结果，发现与Ｎ原子有关的振动模式有较大的增强，在此基础上提出了增强机理。     

Nitrite catalyzes reductive nitrosylation of the water-soluble Ferri-Heme model FeIII(TPPS) to FeII(TPPS)(NO)

Quantitative investigation of the reaction of the ferri-heme model compound Fe(III)(TPPS)(H(2)O)(2) (1) to give Fe(II)(TPPS)(NO) (2) (TPPS = tetra(4-sulfonato-phenyl)porphinato) in buffered aqueous solution demonstrates a slow pH-independent reductive nitrosylation pathway in the pH range 4-6. The rate of this reaction is subject to modest general base catalysis. In the course of this study, a surprising catalytic pathway whereby nitrite ion (NO(2)(-)) strongly catalyzes the reduction of 1 to 2 under reductive nitrosylation conditions was demonstrated.     

亮绿SF(淡黄)与蛋白质相互作用的光度法研究及其分析应用

在pH 2.0的B-R缓冲介质中,蛋白质与亮绿SF(淡黄)(LGSF)在室温下结合生成复合物,其最大吸收波长为665 nm。本文采用光度法研究了结合反应的最佳条件、结合常数及最大结合位点数,并在此基础上建立了一个测定蛋白质的新方法。该方法测定牛血清蛋白(BSA)、人血清蛋白(HSA)及γ-球蛋白G(IgG)的线性范围至少可达80μg/mL,其表观摩尔吸光系数ε分别为:7.25×105、7.22×105与1.84×106L.mol-1.cm-1。除阴阳离子表面活性剂外,其余大部分物质不干扰蛋白质测定。可见方法具有选择性好、灵敏度高等优点。用于人血清样品中总蛋白的测定,所得结果与考马斯亮蓝G-250法基本一致。     

Spectrophotometric Determination of Manganese with 4(5)-Imidazolealdoxime (Imalox)

Abstract

A method is described for the spectrophotometric determination of manganese by means of its complex with 4(5)-imidazolealdoxime, IMALOX, formed in alkaline medium. The colour system has its absorption maximum at 350 nm and obeys Beer's law over the range 0.8–8.0 μg of Mn per ml. The optimum range is 1–5 μg m^?1. The molar absorptivity is 7850 1 mol^?1 cm^?1. Relatively few ions interfere, and these can be masked with cyanide, tartrate and NTA. The experimental results have been critically analyzed and a comparison with the main spectrophotometric reagents for manganese is presented.     

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     

meso－四（4－溴苯基）卟啉分光光度法测定烟草中的痕量铅的研究

本文研究了在ｐＨ９．０和有Ｔｗｅｅｎ－８０存在下非水溶性试剂ｍｅｓｏ－四（４－溴苯基）卟啉与铅的络合反应条件，络合物的最大吸收波长为４６８ｎｍ，组成摩尔比为１∶１，铅含量在０～２４μｇ／２５ｍＬ范围内有较好的线性关系，表观摩尔吸光系数为２．８７×１０￣５，用于烟草中痕量铅的测定，结果令人满意。     

Absorbance change and static quenching of fluorescence of meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) by trinitrotoluene (TNT)

Meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) interacts with trinitrotoluene (TNT) and forms a 1:1 complex with a new absorbance peak at 422 nm. TNT quenches TPPS emission intensity at 645 and 702 nm when excited at 413 nm. The TPPS-TNT complex is formed in the ground state on the basis of a linear Stern-Volmer plot indicative of static quenching. The association constants determined from absorbance and fluorescence studies are in excellent agreement.     

Spectrophotometric determination of palladium with 4-(2-pyridylazo)-resorcinol (PAR)

Summary A spectrophotometric method for the determination of palladium is described using 4-(2-pyridylazo)-resorcinol as reagent. The method involves the formation of two red coloured chelates of palladium-PAR at p_H 4.0 and 10.5 respectively. The colour reactions have sensitivity of 0.0085g cm^–2 and 0.0071g cm^–2 for logI ₀/I= 0.001. The effects of p_H, time, order of addition of reagents, temperature etc. have been investigated. The composition of the complexes (metalreagent) have been confirmed by two methods as 11 (at p_H 4.0) and 32 (at p_H 10.5).

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Zusammenfassung Eine spektrophotometrische Methode zur Palladiumbestimmung mit PAR [4-(2-Pyridylazo)-resorcin] wurde beschrieben. Zwei rotgefärbte Chelate werden bei p_H 4,0 bzw. 10,5 gebildet. Die Empfindlichkeit der beiden Reaktionen beträgt 0,0085 bzw. 0,0071g · cm^–2. Der Einfluß von p_H, Zeit, Reihenfolge der Reagenzien, Temperatur usw. wurde untersucht. Die Zusammensetzung der Komplexe entspricht dem Molverhältnis Pd: Reagens= =11 bei p_H 4,0 bzw. 32 bei p_H 10,5.