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.     

Spectrophotometric study of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS4) with proteins

The interaction of water-soluble porphyrin TPPS(4) (tetraphenylporphyrin tetrasulfonate) with proteins in acidic solution was studied by spectrophotometry. The absorption spectra of TPPS(4)-protein complexes, the aggregation of TPPS(4) in acidic solution, and comparison of the absorption spectra of TPPS(4)-protein conjugate with that of the TPPS(4)-protein complex was investigated in detail. The effects of denaturants including urea and SDS were also examined. A mechanism was proposed that TPPS(4) would be distributed between microphase of protein and the aqueous solution and then aggregated in the microphase.     

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.     

Electrochemical studies of the interaction of clarithromycin with bovine serum albumin

The interaction of clarithromycin (CAM) with bovine serum albumin (BSA) was investigated in pH 4.5 - 8.0 phosphate buffer solutions in which three irreversible reduction waves P(1), P(2) and P(3) of CAM appeared on linear-sweep voltammetry on a static dropping mercury working electrode. In the acidic media, with the addition of BSA into the CAM solution, a new electrochemically active complex was formed and there was interaction between the carbonyl group C=O in the C-9 position of CAM and BSA. It was found that electrostatic and hydrophobic forces played an important role in the binding reaction. However, new electrochemically non-active complexes were formed at physiological pH condition. The study showed that the formation constant and formation ratio of the interaction between CAM and BSA were 1.51 x 10(12) and 3:1 for P(2) wave, and 4.53 x 10(5) and 1:1 for P(3) wave, respectively. The ion strength enhanced the hydrophobic interaction between CAM and BSA.     

Electrochemical studies of tetraphenylporphyrin and vanadyl porphyrin

The electrochemical reductions and oxidations of tetraphenylporphyrin (TPP) and vanadyl por-phyrin (TPP-VO) were investigated in dimethylformamide at platinum,glass carbon and microdisk electrodes.A new eleetrode reaction mechanism of TPP and TPP-VO is proposed.The kinetic parameters have also been determined.In addition,the theory of molecular hybrid orbitals is used to explain the reduction and oxidation regularity of the transition metal porphyrms     

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 ...     

Electrochemical charactreistics of membranes based on Mn(III) tetraphenylporphyrin

Anion-selective electrodes with polymer membranes based on manganese(III) tetraphenylporphyrin (TPP) complexes with various axial ligands (chloride, perchlorate, nitrate, and rhodanide) were studied. The electrodes showed high (compared with other anions) selectivity toward the salicylate anion in a wide range of concentrations at different pH values. The selectivity coefficients of membrane electrodes $K_{Sal^ - /X^{n - } }^{sel} $ were determined by the bi-ionic potential method. A selectivity series was obtained based on $K_{Sal^ - /X^{n - } }^{sel} $ , which differs from Hofmeister series for classical anion exchangers. The possibility of using these electrodes in clinical practice for determining salicylate ions in human blood was shown.     

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.     

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.     

Spectroscopic studies of zinc(II)tetraphenylporphyrin molecular complex with 1,4-dioxane

The molecular complex of zinc(II)tetraphenylporphyrin with 1,4-dioxane has been obtained. The IR spectra of the [Zn(TPhP)(1,4-dioxane)2] stabile molecular complex between 4000 and 50cm(-1) have been studied. An interpretation is given on the base the "chair" conformation of 1,4-dioxane molecule.     

Electrochemical studies of NiTMpyP and interaction with DNA

In this paper, cyclic voltammetry, linear sweep voltammetry and chronocoulometry in connection with the hang mercury drop electrode were used to study NiTMpyP and its mixture with DNA. The reduction of NiTMpyP in our experimental conditions involves in 4e reduction of TMpyP. NiTMpyP interacting with DNA forms electrochemically non-active complex DNA-2NiTMpyP, which can not be reduced on the Hg electrode. The peak potential of NiTMpyP does not shift and its electrochemical kinetic parameters indicate no significant change in the presence of DNA. However, the reduction current of NiTMpyP decreases obviously due to the formation of DNA-2NiTMpyP, which implies its equilibrium concentration decreases when DNA was mixed. The decrease of peak current is proportional to DNA concentration, which can be applied to estimate DNA concentration.     

吲哚美辛与牛血清白蛋白相互作用的光谱研究

在模拟生理条件下,用荧光光谱法结合圆二色谱法研究了吲哚美辛(IM)与牛血清白蛋白(BSA)的相互作用.实验结果表明,IM对BSA的猝灭机制属于形成复合物的静态猝灭过程,由修正的Stem-Volmer方程求出不同温度下相应的结合常数分别为11.87×104、8.351 ×104、6.110×104L·mol-1.利用范特...     

Electrochemical behavior of Ru(H_2bpp)_2(PF_6)_2 and its interaction with bovine serum albumin(BSA)

In this paper,it was found that Ru（H₂bpp）₂（PF₆）2（H₂bpp = 2,6-bis（pyrazol-3-yl）pyridine） complex had excellent electrochemical activity at the carbon paste electrode in the buffer solution of Tris-HCl（pH 7.0） with a couple reversible redox peaks at 0.296 V and 0.348 V,respectively.Voltammetry was used to investigate the electrochemical behavior of Ru（H₂bpp）₂（PF₆）₂ and the interaction between Ru（H₂bpp）₂（PF₆）₂ and bovine serum albumin（BSA）.In the present of BSA,the oxidation peak current of Ru（H₂bpp）₂（PF₆）₂ complex was decreased linearly and the decrease of oxidation peak current of Ru（H₂bpp）₂（PF₆）₂ is proportional to BSA concentration from 0.1 to 2.5 mg/L with a detection limit 0.02 mg/L.     

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.     

Thermodynamic studies on the interaction of folic acid with bovine serum albumin

Binding of the vitamin folic acid with bovine serum albumin (BSA) has been studied using isothermal titration calorimetry (ITC) in combination with fluorescence and circular dichroism spectroscopies. The thermodynamic parameters of binding have been evaluated as a function of temperature, ionic strength, in the presence of nonionic surfactants triton X-100, tetrabutylammonium bromide, and sucrose. The values of the van’t Hoff enthalpy calculated from the temperature dependence of the binding constant agree with the calorimetric enthalpies indicating that the binding of folic acid to the BSA is a two state process without involving intermediates. These observations are supported by the intrinsic fluorescence and circular dichroism spectroscopic measurements. With increase in the ionic strength, reduction in the binding affinity of folic acid to BSA is observed suggesting predominance of electrostatic interactions in the binding. The contribution of hydrophobic interactions in the binding is also demonstrated by decrease in the binding affinity in the presence of tetrabutylammonium bromide (TBAB). The value of binding affinity in the presence of sucrose indicates that hydrogen bonding also plays a significant contribution in the complexation process. The calorimetric and spectroscopic results provide quantitative information on the binding of folic acid to BSA and suggest that the binding is dominated by electrostatic interactions with contribution from hydrogen bonding.     

ALC-Pr(Ⅲ)-F-三元络合物与蛋白质作用的电化学行为的研究

用电化学方法对ALC-Pr(Ⅲ)-F^-络合物与牛血清白蛋白(BSA)的相互作用进行了研究，发现在pH4．9的六次甲基四胺((CH2)6N4)缓冲液中，ALC-Pr(Ⅲ)-F^-络合物能与BSA生成一种非电活性的超分子复合物，导致ALC-Pr(Ⅲ)-F^-的峰电流降低，峰电流降低值△ip在一定范围内与BSA的质量浓度成线性关系．线性范围为1～17．5mg／L，相关系数为0．998(n=10)，检出限为0．3mg／L，该法可用于血清样品中蛋白质的测定。     

Electrochemical properties of derivatives of tetraphenylporphyrin in dichloromethane

The method of cyclic voltammetry was used to study electrochemical properties of derivatives of tetraphenylporphyrin in dichloromethane. In the case of substituted tetraphenylporphyrin, as dependent on the nature of substituents at the periphery of the porphyrin ring, reduction of porphyrins occurs in the range of negative potentials resulting in formation of a π-anion-radical and dianion, while oxidation of porphyrins with formation of a π-cation-radical and dication occurs in the range of positive potentials. In the case of tetrakis(p-aminophenyl)porphyrin, a poly-porphyrin film is formed on the electrode in the course of electrooxidation. The method of chronoamperometry was used to determine the potential of initiation of electropolymerization of H₂T(p-NH₂Ph)P.     

Electrochemical and spectroscopic studies of the interaction of proflavine with DNA.

The interaction of proflavine with herring sperm DNA has been investigated by cyclic voltammetry and UV-Vis spectroscopy as well as viscosity measurements. Shifts in the peak potentials in cyclic voltammetry, spectral changes in UV absorption titration, an increase in viscosity of DNA and the results of the effect of ionic strength on the binding constant strongly support the intercalation of proflavine into the DNA double helix. The binding constant for the interaction between proflavine and DNA was K = 2.32 (+/- 0.41) x 10(4) M(-1) and the binding site size was 2.07 (+/- 0.1) base pairs, estimated in voltammetric measurements. The value of the binding site size was determined to be closer to that expected for a planar intercalating agent. The standard Gibbs free-energy change is ca. -24.90 kJ/mol at 25 degrees C, indicating the spontaneity of the binding interaction. The binding constant determined by UV absorption measurements was K = 2.20 (+/- 0.48) x 10(4) M(-1), which is very close to the value determined by cyclic voltammetry assuming that the binding equilibrium is static.