Supramolecular Fixation of Three Amines using Cobalt Tetraphenyl- porphyrin for SO2 Removal

In this work, supramolecular fixation of three amines, including aniline, ethylenediamine, and diethylamine, using cobalt tetraphenylporphyrin （CoTPP） for SO2 removal was studied using UV-Vis and fluorescence measurements. The UV-Vis spectra showed that increasing amines concentrations resulted in bathochromic shift for CoTPP Soret absorption band （B band）. Once SO2 was introduced, it competed with CoTPP for aniline, ethylenediamine, and diethylamine, which eventually led to the release of CoTPP and the change of solution colour/absorption band. After that, the CoTPP was regenerated and got back to the first state. The fluorescence spectra offered that CoTPP interacted with aniline, ethylenediamine, and diethylamine to form 1：1 molecular adducts. The interactions of CoTPP with aniline, ethylenediamine, and diethylamine were entropy-driven. The interaction of CoTPP with aniline and diethylamine was endothermic, and that with ethylenediamine was exothermic. Ethylenediamine presented a stronger binding constant value for CoTPP, so it was considered as a potential agent for SO2 removal.

四苯卟啉及其金属配合物对Fe^(3+)离子在水/硝基苯界面迁移的推动作用

关于四苯卟啉（H2TPP）及其第一过渡金属配合物（MTPP,M=Mn,FeCl,Co,Ni,Cu,Zn）对H+通过W/NB界面所产生的推动作用前文已作报道。本文研究上述两者对Fe3+在W/NB界面迁移的影响,并根据实验事实提出可能的微观机理。 实验仪器、电化学测试方法及主要试剂的制备、纯化参照前文。主要结果如下。H2TPP对Fe3+

Synthesis and Photocytotoxicity of Mono-functionalised Porphyrin with Valine Moiety

A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenylring was synthesized for photocytotoxicity examination in four steps, starting from regiospecificmono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Aladenocarcinona cell line was tested.

Topography Structure and Scanning Tunneling Spectrum of Nickel( Ⅱ )-tetraphenylporphyrin Molecules on Au(111)

Scanning tunneling microscopy （STM） and scanning tunneling spectroscopy （STS） were performed on monolayer film of NiTPP supported on Au（111） under ultrahigh vacuum （UHV） conditions. The constant current STM images show remarkable bias dependence. High resolution STM data clearly show the individual NiTPP molecules and allow easy differentiation between NiTPP and CoTPP reported before. Scanning tunneling spectra, as a function of molecule-tip separation, were acquired over a range of tip motion of 0.42 nm. Spectra do not show the variation in band splitting with tip distance. It appears for molecules such as NiTPP that the average potential at the molecule is essentially the same at the same metal substrate. For molecules of the height of NiTPP, the scanning tunneling spectra should give reliable occupied and unoccupied orbital energies over a wide range of tip-molecule distances.

A Simple and Rapid Method for the Detection of Non-Ionic Surfactants

A spectrophotometric approach for the detection of non-ionic surfactant (Triton X-100) has been proposed in this paper. This method does not involve extraction of the ion-associate with harmful solvents, but employs adhesion of the ion-association of potassium/non-ionic surfactants complex and tetraphenylporphyrin tetrasulfonic acid obtained by vigorous shaking. The adhered ion-associate was dissolved with water and its absorbance was measured. The sensitivity for Triton X-100 was determined to be 0.146 (expressed as absorbance of 1 mg/L solution). The adhesion tendency of ion-associate was found to be dependent on the water contact angle, which in turn was influenced by a high adhesion of the ion-associate and by low blank values. In this respect, a tetrafluo-roethylene vessel was found to be the most suitable for the detection of non-ionic surfactants. This spectrophotometrical method is simply and rapidly performed by a procedure based on mechanical shaking and can be employed to detect non-ionic surfactants containing more than 7 polyethylene oxide units.

Synthesis and Spectral Characteristics for Zinc Tetraphenylporphyrin Modified Zinc Oxide Nanowires

A nest-like architectures(ZnO NAs)were prepared onto the conductive glass(ITO)by hydrothermal method.A metal-free porphyrin,tetraphenylporphyrin(H2TPP),was synthesized via Adler method.Zn ions with Zn-unsaturated coordination bonds on the surface of ZnO NAs were used as a template,and also H2TPP was used as"molecular fragments".Zinc tetraphenylporphyrin(ZnTPP)molecules were obtained on the surface of ZnO NAs by in-situ method.ZnO NAs direct provides of zinc source makes ZnTPP stably coated on the surface of ZnO NAs nanosheet,formed a tight composite materials(ZnTPP/ZnO NAs).Due toZnTPP with four phenyls in meso position,the surface of ZnTPP/ZnO NAs was with hydrophobic property.In the photocatalytic experiment,the degradation selectivity for phenol(hydrophobicity)in the mixture of phenol and rhodamine B(hydrophily)was increased under visible irradiation.

Electrochemical and Spectroelectrochemical Studies on Electrooxidation Reactions of (TPP)Co~Ⅱ/NO_3^- System

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Voltammetric Study on the Complexes of the Rare Earths with Tetraphenylporphyrin

Fifteen rare earth-tetraphenylporphyrin(RE-TPP)complexes were directly prepared by mixing equal molar concentrations of RE(ClO_4)_3 and H_2TPP in acetone media.The electrochemical behaviors of these com- plexes and the influence of dissolved oxygen were investigated by voltammetry.Althrough there are some differ- ence between the behaviors of light and heavy rare earth-porphyrins,the central RE ions of the all fifteen com- plexes were reduced from tervalent to divalent state,meanwhile the dissovled oxygen was reduced as superoxide ion O^-.which readily combined with the complex forming peroxide additive complex such as RE-TPP·O^(2-)_2.

Synthesis and Characterization of Cerium Tetraphenylporphyrin Nitrate and Molecular Recognition for NO

Cerium （III） tetraphenylporphyrin nitrate Ce（TPP）NO3 was synthesized by using meso- tetraphenylporphyrin （TPP） and Ce（NO3）.6H20 in mixture solution of CHC13 and C2HsOH （V：V=1：1）. The complex was characterized by UV-Vis, FT-IR, conventional fluorescence, MALDI-TOF-MS, and ^1H NMR spectral techniques. The structure of complex was proposed viaSpectral analyses, in which tetraphenylporphyrin was coordinated to a cerium ion in a tetradentate fashion, while one nitrate was coordinated to the same cerium ion. After bubbling NO to the solution of Ce（TPP）NO3 in CH2Cl2, spectral analyses suggested that Ce（TPP）NO3 could interact with NO to form a novel complex of Ce（TPP）（NO）NO3, and NO was coordinated to the center cerium ion. When nitrogen was poured into the Ce（TPP）（NO）（NO3） solution, the complex could be reduced to Ce（TPP）NO3.

Catalase-Biomimetic Sensor on Base of Electrochemical Electrode TPhPFe（III）IAI2O3/Pb and TPhPFe（III）IAI=O3/Si

It was developed biomimetic electrodes catalase type based on Pb and Si, which for a long time do not lose their activity. Prepared biomimetic sensors compared with their biological counterparts have a number of technological advantages--availability, low cost and ease of process design. With the help of electrode there have been determined low concentrations of H202 in the water solution and pH-changes of the investigated solutions have been shown.

A NEW STAINING METHOD FOR THE MEASUREMENT OF PROTEIN USING TETRAPHENYLPORPHYRIN TETRASULFONATE(TPPS_4)

A new dye-staining method for protein assay is described.The reaction between TPPS_4 and protein molecule causes a shift in the absorption of TPPS_4 from 435 nm to 488nm.The absorbance at 488 nm is proportional to the concentration of protein.The range of Beer's law was 1-5 ug/ml and the Sandell's sensitivity was 0.0087 ug/cm^2.

Theoretical studies on the structural change in the N-protonated tetraphenylporphyrin

The geometries of tetraphenylporphyrin which is a kind of important porphyrin derivatives, and its N-protonated diacid are calculated with AM1 MO method under symmetry restriction. The configurational changes and their effects on molecular aggregation are discussed by means of structure analysis, charge population analysis and frontier orbital analysis.

Photochemical fixation and reduction of sulfur dioxide to sulfide by tetraphenylporphyrin magnesium:Spectroscopic and kinetic studies

The photochemical reaction of sulfur dioxide （802） with tetraphenylporphyrin magnesium （MgTPP） has been investigated in dichloromethane （CH2C12） solution at room temperature with illumination by visible light. Conventional fluorescence, UV-vis, and MS spectral analyses showed that under these conditions, SO2 was initially photochemically fixed by MgTPP to form a 1：1 molecular adduct. On continued irradiation and maintaining the flow of SO2, MS and XRD results showed that MgTPP is re- markably effective in the photochemical reduction of SO2 to sulfide （S2 ）. The kinetics of the photochemical reaction of MgTPP with SO2 was studied in a SO2-saturated solution. Under irradiation, the reaction follows pseudo first order kinetics for MgTPP, having a half-life decreasing from 106 to 57 min as the illumination intensity is increased from 350 to 600 Lm. This investigation of the photochemical fixation and reduction of SO2 by MgTPP is of key interest in elucidating fundamental pho- tochemical reaction mechanisms associated with porphyrins in the presence of SO2; furthermore, the analysis of the photo- chemical reaction may offer new opportunities for the fixation and reduction of SO2 to less harmful species.

Formation of heterocaryotic and homonuclear bridged–dimeric complexes on surface

The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. STM images of molecular adlayers of zinc tetraphenylporphyrin（Zn TPP）, zinc phthalocyanine（Zn Pc）, and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1：1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.

Synthesis and Characterization of a Noncovalently Linked Porphyrin-[1,2-（1 -acridin-10＇-yl-2-aza-2-methylprop-1,3-ylene）- fullerene] Dyad

1,2-（1-Acridin-10＇-yl-2-aza-2-methylprop-1,3-ylene）fullerene was synthesized firstly and characterized by UV-Vis, ^1H NMR, ^13C NMR and electrospray ionization mass spectroscopy, which is capable of forming a stable complex with zinc tetraphenylporphyrin via the axial ligation. The steady state fluorescence studies show efficient quenching of the zinc tetraphenylporphyrin emission upon axial coordination of acridine attached to C60.

Synthesis and properties of tetrathiafulvalene-porphyrin assemblies

Two donor-σ-acceptor molecular systems incorporating tetrathiafulvalene(TTF)and tetraphenylpor-phyrin(TPP)units,TTF-TPP(dyad 1)and TTF-TPP-TTF(triad 2),were synthesized.Both dyad 1 and triad 2 and their synthetic intermediates have been characterized by 1H nuclear magnetic resonance(1H NMR)and mass spectro-graphy(MS).Their ultraviolet and visible spectroscopy(UV-Vis)and cyclic voltammetry(CV)showed negligible intramolecular charge transfer interaction in their ground states.Theirfluorescence intensity was strongly quenched compared with TPP,which implied the photoinduced electron transfer occurred from the TTF unit to the TPP unit in the excited state.On the other hand,theirfluorescence intensity could be modulated by sequential oxidation of the TTF unit using chemical methods,which exhibited their potential application influorescence molecular switch.