Resonance Raman Scattering Spectra of Co(II)- and Cu-5,10,15,20-Tetrakis[4-(N-methylpyridyl)]porphyrin in the dd Excited State and Mechanisms of Its Deactivation in a Solution and in Complexes with DNA

Optics and Spectroscopy - Resonance Raman scattering (RRS) spectra of the complexes of 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin with Co(II) and Cu(II) (CoIITMpyP4 and CuTMpyP4) in various...     

SER(R)S of porphyrins on Ag nanoparticles immobilized by silane: a unique way to obtain free‐base porphyrin spectra

We measured the surface‐enhanced resonance Raman scattering (SER(R)S) spectra of 5,10,15,20‐tetrakis (1‐methyl‐4‐pyridyl)porphyrin (TMPyP) by using solid SERS‐active substrates: Ag nanoparticles immobilized by aminosilane on glass plates. We report the surprising result that by using such substrates it is possible to obtain SER(R)S spectra of porphyrins in the unperturbed free‐base form, although by using silver nanoparticles directly in solution, the porphyrin molecules are completely metalated. We suggest that silane used for nanoparticle immobilization modifies the surface properties and, therefore, makes porphyrin metalation impossible. Copyright © 2007 John Wiley & Sons, Ltd.     

Spectroscopic Study of Porphyrin-Caffeine Interactions

The association between water-soluble porphyrins: 4,4′,4″,4?-(21?H,23?H-porphine-5,10,15,20-tetrayl)tetrakis-(benzoic acid) (H₂TCPP), 5,10,15,20-tetrakis(4-sulfonatophenyl)-21?H,23?H-porphine (H₂TPPS₄), 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21?H,23?H-porphine tetra-p-tosylate (H₂TTMePP), 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21?H,23?H-porphine tetra-p-tosylate (H₂TMePyP), the Cu(II) complexes of H₂TTMePP and H₂TMePyP, as well as chlorophyll a with caffeine (1,3,7-trimethylxanthine) has been studied analysing their absorption and emission spectra in aqueous (or acetone in case of chlorophyll a) solution. During the titration by caffeine the porphyrins absorption spectra undergo the evolution – the bathochromic effect can be observed as well as the hypochromicity of the Soret maximum. The association constants were calculated using curve-fitting procedure (K_AC of the order of magnitude of 10³?mol^-1). Whereas the emission spectra point at the presence of the fluorescence quenching effect testifying for the partial inactivation of the porphyrin molecule. The fluorescence quenching constants were calculated from Stern-Volmer plots. The results obtained show that caffeine can interact with water-soluble porphyrins and through formation of stacking complexes is able to quench their ability to emission.     

Effect of the layer charge on the interaction of porphyrin dyes in layered silicates dispersions

Interaction between tetracationic porphyrin, 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP), and layered silicates in aqueous dispersions was studied using absorption, steady-state and time-resolved fluorescence spectroscopies. The charge density of silicates increases in order synthetic laponite (LAP)<Kunipia F montmorillonite (KF)<synthetic fluorohectorite (FHT). Interpretations of the spectra of layered silicate-porphyrin (LSP) systems considered models of dye adsorption on clay mineral colloid particles, analyzing phenomena occurring in similar systems such as structural changes of TMPyP and the formation of dye molecular assemblies. Structural changes of TMPyP, including flattening of the porphyrin molecule, do not fully explain all the spectral observations. One should mention variations of the Q-bands and fluorescence spectra in dependence on the layer charge. The molecular association of the TMPyP molecules is expected to occur to a certain extent in dependence on the layer charge of a clay mineral template. H-aggregates were not observed in any system. Only FHT colloids induced the formation of at least two components with significantly different spectral properties.     

CTAB对四-(4-N-甲基吡啶)卟啉SERS谱的影响

研究了阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB)对四 ( 4 N 甲基吡啶 )卟啉 (H2 TMPyP)及其银配合物 (AgTMPyP)在Ag胶中的表面增强拉曼散射 (SERS)谱的影响 .SERS光谱表明 ,吸附于Ag胶粒的H2 TMPyP与衬底银原子结合形成AgTMPyP ,加入CTAB后 ,部分AgTMPyP表面络合物还原为H2 TMPyP .相似的去金属化反应也出现在AgTMPyP/Ag胶 /CTAB体系中 .CTAB的加入使SERS谱带强度明显增加 .AgTMPyP的去金属化被认为是由于CTAB的存在使Ag胶颗粒表面附近微环境发生改变     

Features of the Quenching of the Triplet States of Water-Soluble Porphyrins by Molecular Oxygen

Using the methods of time-resolved absorption spectroscopy, we have investigated the features of quenching, by molecular oxygen, of the excited triplet states of water-soluble 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin (H₂TMPyP) and 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (H₂TSPP) in water–ethanol solutions. It has been revealed that for both compounds the rate constant of quenching of the triplet states increases with increasing viscosity of the medium. Quenching of the excited triplet states of the dissociated (in water) and undissociated (in ethanol) forms of water-soluble porphyrins occurs with a different efficiency, and the rate constant of quenching the triplet states by molecular oxygen k _T thereby is higher for the dissociated form. It has been shown by means of mathematical modeling that the experimental results obtained can be described in terms of the change in the rate constants of intracomplex transitions in the porphyrin–oxygen collisional complex at varied solution viscosity and their difference for the dissociated and undissociated forms of water-soluble porphyrin.     

Fluorescence quenching of water-soluble porphyrins by molecular oxygen

Quenching by molecular oxygen of excited states of water-soluble anionic 5,10,15,20-tetarkis-(4-sulfonatophenyl)-porphyrin (H₂TSPP) and cationic 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin (H₂TMPyP) in aqueous ethanol was investigated. It was found that fluorescence quenching of dissociated (in water) and undissociated (in ethanol) forms of H₂TSPP was diffusion-controlled and occurred at distances close to contact ones (0.5–0.8 nm). Fluorescence of the dissociated form of H₂TSPP was quenched with rate constant k_S that was 1.7 times greater than that of the undissociated form. It was proposed that this was due to a decrease in the porphyrin molecule oxidation potential on going from the undissociated to the dissociated form. It was shown that the most probable reason for the dramatic increase in the rate constant of the fluorescence quenching of H₂TMPyP in water compared with that of H₂TSPP was the low-lying intramolecular charge-transfer state typical of H₂TMPyP. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 170–176, March–April, 2008.     

Formation of QD-porphyrin molecule complexes in aqueous solutions

The spectral and luminescent manifestations of the electrostatic formation of quantum dot (QD)-porphyrin complexes are studied. The QD luminescence in these complexes is found to be efficiently quenched. The luminescence of molecules complexed with QDs is also partially quenched. The luminescence excitation spectra of porphyrin molecules associated with QDs exhibit a contribution of the QD absorption spectrum, which indicates that energy is transferred from QDs to porphyrin. The efficiency of the nonradiative resonant energy transfer from a QD to a porphyrin molecule is estimated. The observed experimental data agree well with a proposed model of formation of complexes of the QD-organic molecule type.     

Water-soluble porphyrin detection in a pure-silica photonic crystal fiber

Aqueous solutions of the water-soluble porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinatomanganese(III) acetate were inserted into the holes of a photonic crystal fiber, and the porphyrin absorption bands were identified. Results were obtained for three concentrations. The porphyrins in water show no surface interactions with the silica walls of the capillary channels. We discuss the implications for future hybrid electronic and photonic fiber devices.     

Quantification of ultrasonic intensity based on the decomposition reaction of porphyrin

A simple method is proposed for quantification of the effective ultrasonic intensity in the reaction vessel based on the decomposition reaction of 5,10,15,20-tetrakis(4-sulfotophenyl) porphyrin (H₂TPPS⁴⁻). The change of concentration of porphyrin in solution irradiated by the ultrasound wave depends on the irradiation time and the output power of ultrasound generator. The decomposition ratio of porphyrin is defined as the ratio of the concentration of porphyrin after ultrasonic irradiation to that before ultrasonic irradiation. A linear relationship between the decomposition ratio of porphyrin and the concentration Fe³⁺ in the Fricke solution under sonication was obtained. The decomposition ratio was related to the absorption dose in radiation chemistry.     

Fluorescent properties and symmetry of the monodeprotonated form of 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin

The spectral and kinetic properties of the monodeprotonated form of the cationic 5,10,15,20-tetrakis(4-Nmethylpyridyl) porphyrin (H₂TMPyP) in solution are studied. The experimental results obtained are interpreted based on the four-orbital Gouterman model. It is established that the monodeprotonated form HTMPyP⁻ can be assigned to the D4h symmetry point group, and has spectral and photophysical characteristics similar to the characteristics of the fluorescent metal complexes of H₂TMPyP with relatively low electronegativity of the chelated metal ion. It is hypothesized that formation of the monodeprotonated form HTMPyP⁻ is accompanied by a decrease in the oxidation potential of the porphyrin molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 613–619, September–October, 2006.     

Inhibition and Promotion of the Oxidation Processes of Water-Soluble Cationic Co(II)-Porphyrin Under Its Interaction with Nucleic Acids

Using the methods of absorption spectroscopy and resonance Raman scattering, we have made a comparative study of water-soluble cationic Co(II)- and Co(III)-5,10,15,20-tetrakis(4-N-methyl-pyridiniumyl)porphyrins(Co^II(TMpy-P4) and Co^III(TMpy-P4) with DNA and synthetic single- and double-stranded polynucleotides. It has been found that Co^II(TMpy-P4), which in aqueous solutions containing no nucleic acids is readily oxidized to Co^III(TMpy-P4) by the molecular oxygen dissolved there, markedly changes its oxidation ability when bound to nucleic acid. Under interaction with guanine-containing polynucleotides, the rate of change in the oxidation state of cobalt from Co(II) to Co(III) increases as compared to such for the solution of porphyrin in a buffer. But in complexes with DNA and adenine- and thymine-containing polynucleotides, CoII(TMpy-P4), on the contrary, becomes stable. The observed effects of inhibition/promotion of Co^II(TMpy-P4) oxidation when it is bound to nucleic acids are assumed to be due to the weakening/strengthening of the electron-donor properties of the extraligand on cobalt, which leads to a change in cobalt affinity to molecular oxygen. The role of immobilized water molecules in the change in the properties of cobalt extraligands has been considered. On the basis of the analysis of the spectral data obtained, modes for incorporating Co^II(TMpy-P4) into DNA and model polynucleotides are proposed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 538–545, July–August 2005.     

Spectral Manifestations of Anion-Cation Interactions of Water-Soluble Porphyrins

The influence of anion-cation interactions on the structure and electronic absorption spectra of cationic 5,10,15,20-tetrakis-(4-N-methylpyridyl)porphyrin and anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin has been investigated by absorption spectroscopy and molecular modeling. It is shown that the shifts of bands in the electronic absorption spectra appearing when passing from aqueous solutions to solutions in organic solvents are due to the interaction of ionized peripheral substituents of the porphyrin macrocycle with counterions. The bathochromic shift of the Q _x transition is due to the influence of counterions on the energy characteristics of the molecule itself, primarily, as a result of Coulomb interactions changing the relative position of the orbitals and the distribution of electron density on them. The hypsochromic shift of the Q _y transition is a consequence of the increase in the dihedral angle between the plane of the porphyrin macrocycle and the aromatic rings with ionized groups due to the decrease in the -electron interaction between them under the action of counterions.     

Formation of J-Aggregates of 21-thia-5,10,15,20-tetra-(4-sulfonatophenyl)-porphyrin in Acidified Aqueous Solutions

Journal of Applied Spectroscopy - The formation of Jaggregates of 21-thia-5,10,15,20-(tetra-4-sulfonatophenyl)-porphyrin in acidified aqueous solutions is reported for the first time. The...     

Time-Resolved EPR Spectra of Photoexcited Copper Porphyrin

Photoinduced spin-polarized transient electron paramagnetic resonance (EPR) spectra of copper 5,10,15,20-tetrakis(3-pyridyl)porphyrin (3PyNCu) in the frozen solution have been observed in the X-band. The time evolution and the temperature dependence of the spectra have been studied. The effect of molecular oxygen in the frozen solution on the polarization pattern has also been examined. The magnetic resonance parameters of the ground state of 3PyNCu have been obtained by comparing the experimental continuous-wave and echo-detected EPR spectra with the numerical computations. The magnetic resonance parameters of the excited states and the photoinduced polarizations have been investigated by time-resolved EPR (TREPR) spectroscopy and numerical analysis. The experimental spectra have been considered as a sum of the polarized spectra of the ground and excited states. Our analysis confirmed that the TREPR spectra consisted of two main patterns: the enhanced signal from the ground state and the multiplet contribution belonging to the excited quartet state.     

Spectral and Luminescent Properties of 21-Thia-5,10,15,20-Tetra-(4-Sulfonatophenyl)Porphyrin: Role of Heterosubstitution and Halochroism

Journal of Applied Spectroscopy - The spectral and luminescent properties of hydrophilic 21-thia-5,10,15,20-tetra(4-sulfonatophenyl)porphyrin and 5,10,15,20-tetra(4-sulfonatophenyl)porphyrin in...     

2-(2,5-二羟苯基)四苯基卟啉及其金属配合物的合成与表征

对苯二酚与 2 硝基 5 ,10 ,15 ,2 0 四苯基卟啉 1及其铜 (Ⅱ ) 2、镍 (Ⅱ ) 3、锌 (Ⅱ ) 4等金属配合物直接加热反应 ,分别制得 2 (2 ,5 二羟苯基 )四苯基卟啉 1′(81% )及相应金属配合物 2′(71% ) ,3′(6 1% ) ,4′(40 % )。它们的结构由IR ,MS ,UV及1 HNMR ,2D NMR等确定。发现对苯二酚通过碳 碳键与卟啉的吡咯环直接相连 ,氢醌与卟啉环趋于共平面 ,其中一个羟基位于卟啉环的去屏蔽区 ,H原子的核磁位移向低场移动 (δ =7 5 2 ) ,另一个则处于中位苯环的屏蔽区 ,H原子的核磁位移为δ =4 18;氢醌环上的质子也表现出不同的核磁位移 ,其中 6位上H的位移值为δ =4 93,明显向高场位移。     

Excimer laser photofragmentation of metallic nanoparticles

Copper nanoparticles (Cu NPs) were prepared by different chemical methods possessing different sizes. While, silver nanoparticles (Ag NPs) were prepared by borohydride reduction method. The influences the changes in sizes of Ag NPs and Cu NPs were demonstrated by the absorption spectra. When Ag NPs and Cu NPs irradiated with 193 and 308 nm excimer laser, respectively; the maximum absorption decreased as the number of pulses increased up to 10 thousands pulse; due to the size reduction. The TEM photography gives good criteria about the size reduction process. Moreover, the mechanism of photofragmentation was described.     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.      

Laser based fabrication of chitosan mediated silver nanoparticles

We report fabrication of silver nanoparticles (Ag NPs) by laser ablation technique in different concentrations of aqueous chitosan solution. The ablation process of silver plate was carried out by using a nanosecond Q-switched Nd:YAG pulsed laser and the characterization of Ag NPs was done by Transmission electron microscopy, UV-Vis spectroscopy, and X-ray diffraction. UV-visible plasmon absorption spectra revealed that the formation efficiency as well as the stability of nanoparticles was increased by addition of chitosan. On the other hand, the size decrement of nanoparticles was more remarkable in the higher chitosan concentration.