ISOSBESTIC DUAL WAVELENGTH SPEOTROPHOTOMETRIC SIMULTANEOUS DETERMINATION OF ZINC AND OADMIUM USING meso-TETRAKIS[4-(TRIMETHYLAMMONIUM) PHENYL] PORPHINE

Iin this paper an isosbestic dual--wavelength spectrophotometric method for the simultaneous determination of zinc and cadmium using meso--tetrakis [4-(trimethylammonium) phenyl] porphine has been developed. The interference from excess of reagent was masked by adding lead ions solution.The molar absorptivities (Ae) for zinc and cadmium were 6. 54 × 105 and 4. 27 × 105 L. mol-1. cm-1,respectively. The method could be used to determine zinc and cadmium in synthetic mixtures, and the satisfied results were obtained.

Ligninolytic Peroxidase-Like Activity of a Synthetic Metalloporphine Immobilized onto Mercapto-Grafted Crosslinked PVA Inspired by the Active Site of Cytochrome P450

A synthetic metalloporphine was immobilized onto a PVA-based and mercapto-grafted solid support, emulating the active site of cytochrome P450. Its ligninolytic peroxidase-like catalytic activity was studied. The coordinated mercapto ligand significantly affected the catalytic features of the catalyst because the oxidation of lignin-model compounds was very slow by comparison with imidazoleand pyridine-coordinated immobilized metalloporphines. Conversely, the catalyst efficiently bleached several industrial dyes and thus demonstrated promising activity for this application. Based on this altered substrate specificity the oxygen-donor catalytic route seems to be more favorable than a single electron oxidation pathway.

Pseudo-Bonding Interaction between Boron-doped Heterofullerene and Zinc Porphine Predicted by DFT Calculation

Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional theory calculation at wB97XD/6-31G（d） level. Strong interaction between porphyrin and heterofullerene moiety was predicted for these complexes based on geometry and electronic structure analysis. Especially, pseudobonding interaction occurring between the B atom of fullerene and the N atom of porphyrin was predicted to occur in C59B-ZnP complex, but be broken in C59B-ZnP complex. Time-dependent density functional theory calculation manifests the redshift of electron absorption for ZnP upon the interaction with heterofullerene.

An ESR Study on Singlet Oxygen Photoproduction of the Meso-Tetrakis-(Substituted Phenyl) Porphine Derivatives

The ability of meso-tetrakis- (substituted phenyl) porphine derivatives for photo-generating singlet oxygen (O2) is studied by ESR spectrometry. The results show that the singlet oxygen yields of most of porphine derivatives are higher than that of HPD. It is also exhibited that the nature and structure of the substituent at the meso position are closely related to the photo-sensitizing ability of meso-tetrakis-(substituted phenyl) porphine.

STUDY AND APPLICATION OF SPECTROPHOTOMETRIC DETERMINATION OF MICRO AMOUNTS OF BISMUTH WITH MESO—TETRAKIS—(4—N—TRIMETHYL AMMONIUMPHENYL)PORPHINE

A new highly sensitive spectrophotometric method has been developed for the determination of micro amounts of bismuth (Ⅲ), based on the formation of Bi (Ⅲ)—meso—tetrakis—(4—N—trimethylammonium phenyl) porphine [T (4TMAP) P] complex. In the presence of Cd (Ⅱ), Bi(Ⅲ) reacts almost instantaneously with T (4TMAP)P in a 0. 6 mol/l NaAc—HAC buffer (PH5.8) at room temperature. The composition of the complex is T(4TMAP)P: Bi=1:1. The absorbance complex obeys Beer's law over the Bi(Ⅲ) concentration range 0.1—1.4 μg/ml. The linear relative coefficient γ is 0.9998. The apparent molar absorptivity was 1.75×10~5 1. mol^(-1). cm^(-1) at 463nm. The relative standard deviation of the method is 1.50％ for Bi(Ⅲ) 7ug/10ml (10 determinations). The interference of foreign ions has been examined. This simple and rapid method can be applied to the assay of Bi(Ⅲ) in some tablets directly.

SYNTHESIS OF MESO-TETRA (4-METHOXYPHENYL-3-SULFONATE) PORPHINE AND SPECTROPHOTOMETRIC STUDY OF COLOUR REACTION WITH COPPER

In this paper meso-tetra (4-methoxyphenyl-3-sulpho) Porphine (TMPPS_4) was synthesized and its colour reaction with copper was studied. It was found to be a highly sensitive and highly selective reagent for the direct spectrophotometric determination of ultramicro amount of copper. The apparent molar absorptivity of the complex is 3.72×10~5L/mol·cm. Beer's law is obeyed for Cu(Ⅱ)of 0～1.4μg/10ml. The interference of 21 different ions and 6 kinds of salts were examined and found to be minimal. The complex formation of Cu(Ⅱ) with TMPPS_4 is generally slow at room temperature<<25℃>, but the reaction can be accelerated in the presence of NH_2OH·>HCl and completed within 5min. At PH 5.2 the Soret band of TMPPS_4 overlaps almost completetely with that of the complex. Therefore, the complex formation is taken to completion at this PH. Then the Soret band of TMPPS_4 shifted away from that of the complex by acidification. This simple and rapid method has been successfully applied to the direct determination of Cu in Al-alloys, industrial water, foods and human hair.

Electrochemical Detection of Superoxide Anion Released by Living Cells by Manganese(Ⅲ) Tetraphenyl Porphine as Superoxide Dismutase Mimic

Superoxide anion,one of the most active reactive oxygen species,is associated with the development of many diseases.So monitoring superoxide anion in living cells is of great significance for the pathological research of many diseases.In this work,a new non-enzymatic sensor tor the detection of superoxide anion(O^·-2)was developed,which was iabricated by the nanocomposites composed of manganese(Ⅲ)tetraphenyl porphine(MnTPP)as superoxide dismutase mimic and electrochemical reduced graphene oxide(ERGO)as electrode support material to modify the glassy carbon electrode(GCE).The electrochemical behavior of the fabricated electrode(MiiTPP/ERGO/GCE)was performed by electrochemical impedance spectroscopy(EIS)and cyclic voltammetry(CV),which revealed that MnTPP/ERGO/GCE possessed good catalytic ability to theelectrochemical reduction of O^·-2.The MnTPP/ERGO/GCE showed excellent electroanalysis perfonnance towards O^·-2 using the technique of diflerential pulse voltanimetry(DPV)with a linear relationship in the range of 0.2—110.0μmol/L,a sensitivity of 445 μA· L·mmol^-1·cm^- 2 and a detection limit of 0.039 μmol/L(S/N=3).The real-time monitoring of O^·-2 from MCF-7 breast cancer cells stimulated by zymosan was realized in this work,which indicates that the MnTPP/ERGO/GCE hold potential application for electrochemical quantification of superoxide anions in biological applications.

Structure and principles of self-assembly of giant“sea urchin”type sulfonatophenyl porphine aggregates

Principles of molecular self-assembly into giant hierarchical structures of hundreds of micrometers in size are studied in aggregates of meso-tetra(4-sulfonatophenyl)porphine(TPPS_(4)).The aggregates form a central tubular core,which is covered with radially protruding filamentous non-branching aggregates.The filaments cluster and orient at varying angles from the core surface and some filaments form bundles.Due to shape resemblance,the structures are termed giant sea urchin(GSU)aggregates.Spectrally resolved fluorescence microscopy reveals J-and H-bands of TPPS_(4)aggregates in both the central core and the filaments.The fluorescence of the core is quenched while filaments exhibit strong fluorescence.Upon drying,the filament fluorescence gets quenched while the core is less affected,showing stronger relative fluorescence.Fluorescencedetected linear dichroism(FDLD)microscopy reveals that absorption dipoles corresponding to J-bands are oriented along the filament axis.The comparison of FDLD with scanning electron microscopy(SEM)reveals the structure of central core comprised of multilayer ribbons,which wind around the core axis forming a tube.Polarimetric second-harmonic generation(SHG)and thirdharmonic generation microscopy exhibits strong signal from the filaments with nonlinear dipoles oriented close to the filament axis,while central core displays very low SHG due to close to centrosymmetric organization.Large chiral nonlinear susceptibility points to helical arrangement of the filaments.The investigation shows that TPPS_(4)molecules form distinct aggregate types,including chiral nanotubes and nanogranular aggregates that associate into the hierarchical GSU structure,prototypical to complex biological structures.The chiral TPPS_(4)aggregates can serve as harmonophores for nonlinear microscopy.

A Simple Determination of Polyethylene Oxide-type Non-ionic Surfactant by Adhesion Method

A simple and rapid method for the determination of polyethylene oxide-type non-ionic surfactants is reported herein. This method is based on the adhesion of calcium/non-ionic surfactant complexes with tetra phenyl porphine sulfonic acid （TPPS） to the wall of reaction vessel upon vigorous shaking. The ion-associate adhering to the inner wall of the vessel was dissolved with water after discarding the solution and spectrophotometrically assayed at 412 nm. From the standard curve for Triton X-100, the order of the sensitivity for different ions was as follows： Ca^2＋〉 K^＋〉 NH4^＋〉 Ba^2＋. The proposed method does not involve extraction of the ion-associated with harmful solvents and can be simply performed by combining a procedure based on hand shaking and the use of a spectrophotometer.

The facile synthesis of 5-formylporphyrin

A facile synthetic route of 5-formylporphyrin（2） has been developed.Using pyrrole and pivaldehyde as the starting materials,2 was obtained through several facile reactions.The synthetic route is easy to perform and can be scaled up,which gives the compound a better application perspective.