Interaction of zinc tetrasulfonated phthalocyanine with cytochrome C in water and Triton-X 100 micelles

The interaction of a zinc tetrasulfonated phthalocyanine with cytochrome c was studied using steady-state spectroscopic techniques and time-correlated single photon counting in water and Triton-X 100 micelles. The dye forms dimers in water with a high equilibrium constant (70 x 10(6) M(-1)). Because of a specific electrostatic interaction, the presence of cytochrome c does not lead to a dissociation of this dimer, but increases its formation, with an equilibrium constant of about 7.9 x 10(9) M(-1). Triton-X 100 micelles dissociate the dimer, creating two populations of dye molecules: one in a hydrophilic media, probably on the surface of the micelles, another on a hydrophobic environment, probably inside the micelles. However, when cytochrome c is added the dye aggregation is again induced leading to a strong fluorescence quenching. This fluorescence quenching may also be caused by a photoinduced electron-transfer due to the formation of a 1:1 complex between the dye and the protein, but the present work does not give direct evidence of such an effect because the fluorescence decays did not show the presence of an extra component. The results presented here are quite different from those reported for aluminum sulfonated phthalocyanines, where aggregation does not occur and the fluorescence quenching is solely due to photoinduced electron-transfer reactions.     

Femtosecond time-resolved transient absorption spectroscopy of xanthophylls

Xanthophylls are a major class of photosynthetic pigments that participate in an adaptation mechanism by which higher plants protect themselves from high light stress. In the present work, an ultrafast time-resolved spectroscopic investigation of all the major xanthophyll pigments from spinach has been performed. The molecules are zeaxanthin, lutein, violaxanthin, and neoxanthin. beta-Carotene was also studied. The experimental data reveal the inherent spectral properties and ultrafast dynamics including the S(1) state lifetimes of each of the pigments. In conjunction with quantum mechanical computations the results address the molecular features of xanthophylls that control the formation and decay of the S* state in solution. The findings provide compelling evidence that S* is an excited state with a conformational geometry twisted relative to the ground state. The data indicate that S* is formed via a branched pathway from higher excited singlet states and that its yield depends critically on the presence of beta-ionylidene rings in the polyene system of pi-electron conjugated double bonds. The data are expected to be beneficial to researchers employing ultrafast time-resolved spectroscopic methods to investigate the mechanisms of both energy transfer and nonphotochemical quenching in higher plant preparations.     

Spectroscopic and electrochemical studies of transition-metal tetrasulfonated phthalocyanines: Part VI. The adsorption of iron tetrasulfonated phthalocyanine on single crystal silver electrodes

The influence of the underpotential deposition of Pb, Tl and Bi on the oxidation of ammonia and on the reduction and oxidation processes of hydroxylamine on platinum has been studied in alkaline solutions. Pronounced inhibition effects caused by underpotential metal adsorbates have been detected for either the oxidation of ammonia or the reduction of hydroxylamine. On the other hand, the same metal adsorbates markedly increase the electrocatalytic activity of the Pt electrode for hydroxylamine oxidation. The observed negative and positive catalytic effects have been interpreted in terms of the electronic and adsorption properties of the Pt substrate, which are strongly modified by the underpotential metal adsorbates.     

Femtosecond transient absorption, nanosecond time-resolved resonance Raman, and density functional theory study of fenofibric acid in acetonitrile and isopropyl alcohol solvents

Hydrogen abstraction reaction of fenofibric acid (FA) in acetonitrile and isopropyl alcohol solvents was studied by femtosecond transient absorption (fs-TA) and nanosecond time-resolved resonance Raman (ns-TR(3)) spectroscopy experiments. The singlet excite state ((1)FA) (nπ*) with a maximum transient absorption at 352 nm observed in the fs-TA experiments undergoes efficient intersystem crossing (ISC) to convert into a nπ* triplet state FA ((3)FA) that exhibits two transient absorption bands at 345 and 542 nm. The nπ* (3)FA species does not decay obviously within 3000 ps. In the ns-TR(3) experiments, the nπ* (3)FA is also observed and completely decays by 120 ns. Compared with the triplet states of benzophenone (BP) and ketoprofen (KP), the nπ* (3)FA species seems to have a much higher hydrogen abstraction reactivity so that (3)FA decays fast and generates a FA ketyl radical like species. In isopropyl alcohol solvent, the nπ* (3)FA exhibits similar reactivity and promptly abstracts a hydrogen from the strong hydrogen donor isopropyl alcohol solvent to generate a ketyl radical intermediate. With the decay of the FA ketyl radical, no light absorption transient (LAT) intermediate is observed in isopropyl alcohol solvent although such a LAT species was observed after similar experiments for BP and KP. Comparison of the ns-TR(3) spectra for the species of interest with results from density functional theory calculations were used to elucidate the identity, structure, properties, and major spectral features of the intermediates observed in the ns-TR(3) spectra. This comparison provides insight into the structure and hydrogen abstraction reactivity of the triplet states of BP derivatives.     

Protonation of tetrasulfonated zinc phthalocyanine in aqueous acetonitrile solution.

The phenomenon of protonation of phthalocyanines (Pc) and its effect upon their photophysical properties has seen considerable neglect in the literature. The work reported here clearly shows that tetrasulfonated zinc Pc, a known photodynamic therapy (PDT) agent, is strongly susceptible to protonation at the azomethine bridges. Absorption and fluorescence spectra demonstrate the absolute dependence of the redshifted peak on the pH of the solution. The fluorescence spectra and lifetimes of the protonated Pc are reported, and the potential application of this phenomenon to the development of a PDT agent with increased selectivity is discussed.     

Vibronic spectra of solutions and sols of copper phthalocyanine

Optical spectra of solutions and sols prepared from finely dispersed crystalline copper phthalocyanine (CuPc) were studied. The CuPc preparation was demonstrated to contain an admixture of an amorphous phase. The amorphous phase proved to be soluble in dioxane and heptane with the formation of a true molecular solution of CuPc. It was found that CuPc molecules are absorbed by polyethylene, polypropylene, polycaproamide, and cellulose triacetate films. The optical spectrum of individual CuPc molecules was demonstrated to differ substantially from those of particles of the pigment. It featured intense vibronic bands belonging to three π → π* transitions typical of aromatic structures and a series of bands characteristics of n → π* transitions involving nitrogen atoms (<29000 cm^?1) but showed no absorption bands characteristic of dispersions of the pigment in the visible spectrum (400–800 cm^?1). It was revealed that the Q-band (λ = 670 nm), assigned in the literature to individual CuPc molecule, in reality belongs to CuPc associates.     

Preparation and characterization of copper(II) tetrasulfonated phthalocyanine nanoparticles formed by laser ablation in poor solvents

Laser irradiation of copper(II) tetrasulfonated phthalocyanine (CuTsPc) microcrystals in poor organic solvents such as methanol, 2-methyl-2-propanol, ethanol, tetrahydrofuran, and acetone has produced CuTsPc nanoparticles with 15–112 nm in diameter. Field emission scanning electron microscopy (FESEM) images have shown the formation of CuTsPc nanoparticles in poor organic solvents used in this work. The mean diameters of CuTsPc nanoparticles obtained from transmission electron microscopy (TEM) images in methanol, 2-methyl-2-propanol, ethanol, tetrahydrofuran, and acetone were determined to be 26, 36, 35, 86, and 78 nm, respectively. A correlation between the size of CuTsPc nanoparticles and a solvent polarity could be found in this work.     

Orientational aspect of transient absorption in solutions

In picosecond spectroscopy transient absorption methods are utilized to measure ground-state repopulation kinetics. Since linearly polarized light pulses from mode-locked lasers are used, the transient absorption characteristics in solutions are governed by the rotational diffusion of the absorbing molecules, too. The theory for isotropic diffusion is given and compared to a measurement on the rhodamine 6G molecule dissolved in solvents of different viscosity using a novel pulse spectrophotometer.     

Spectroscopic and electrochemical studies of transition metal tetrasulfonated phthalocyanines: Part V. Voltammetric studies of adsorbed tetrasulfonated phthalocyanines (MTsPc) in aqueous solutions

Cyclic voltammetric measurements of adsorbed Fe- and Co-tetrasulfonated phthalocyanine (TsPc) and Co-phthalocyanine (Pc) have been carried out on ordinary pyrolytic graphite and silver electrodes at different solution pH ranging from 1 to 13. Many voltammetric peaks were found to be pH dependent with a slope of ?59 mV/ unit pH. In some instances this dependence was observed in alkaline or acid solutions only. The influence of oxygen has been also examined.     

Synthesis,electrochemistry, and electrocatalytic activity of thiazole-substituted phthalocyanine complexes

Journal of Solid State Electrochemistry - We report the synthesis of non-peripheral metallophthalocyanines which carry four 4-(4-methoxyphenyl)-2-thiazole-2-thio units. 1H-NMR, FT-IR, UV–Vis,...     

Effect of pyridine on infrared absorption spectra of copper phthalocyanine

Infrared absorption spectra of copper phthalocyanine in KBr pellet and pyridine solution in 400-1625 and 2900-3200 cm(-1)regions are reported. In the IR spectra of solid sample, presence of weak bands, which are forbidden according to the selection rules of D4h point group, is explained on the basis of distortion in the copper phthalocyanine molecule caused by the crystal packing effects. Observation of a new band at 1511 cm(-1) and change in intensity of some other bands in pyridine are interpreted on the basis of coordination of the solvent molecule with the central copper ion.     

酞菁铜分子的电子态和反饱和吸收

用ROHF-INDO/SDCI方法结合实验研究了酞菁铜分子的电子的电子结构.紫外-可见光谱.激发态分子动态学和反饱和吸收的微观机制.对酞菁铜实现反饱和吸收的必要条件是最低四重态对激光的吸收截面必须大于基态对激光的吸收截面. 在波长为532nm的激光作用下.该条件得到了满足,故Cupc呈现反饱和吸收特征.理论分析与实验结果一致.     

卟啉、酞菁共敏化二氧化钛纳米电极

研究了染料对锌卟啉-氢卟啉(ZnTSPP-H~2TSPP)、锌卟啉-镓酞菁(ZnTSPP-GaTSPc)共敏化二氧化钛纳米电极的光电转换特性和H~2TSPP,GaTSPc在电极表面的聚集态对光电转换的影响,共敏化显著提高了电极的光电转换并产生了混合效应。提出了低占据电荷转移的共敏化机理。     

Absorption spectrophotometric, fluorescence, transient absorption and quantum chemical investigations on fullerene/phthalocyanine supramolecular complexes

The present paper reports the photophysical investigations on supramolecular interaction of a phthalocyanine derivative, namely, 2,9,16,23-tetra-tert-butyl-29H,31H-Pc (1) with C(60) and C(70) in toluene. The binding constants of the C(60) and C(70) complexes of 1 are estimated to be 27,360 and 25,205 dm(3), respectively. Transient absorption measurements in the visible region establishes that energy transfer from C60*T (and C70*T) to 1 occurs predominantly in toluene which is subsequently confirmed by the consecutive appearance of the triplet states of 1. Quantum chemical calculations at DFT level of theory explore the geometry and electronic structure of the supramolecules and testify the significant redistribution of charge between fullerenes and 1.     

Photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine in aqueous and non-aqueous media

The photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine (SiPcS₄ and GePcS₄) in aqueous solution (phosphate-buffered saline (PBS) solution, pH 7.4) (in the presence and absence of cremophore EL (CEL)) and in dimethylsulphoxide (DMSO) were studied. The complexes have intense absorption in the visible/near-IR region though they highly aggregate in aqueous solution with a dimerization constant of 2 × 10⁴ dm³ mol⁻¹. The fluorescence excitation spectra however have only one band suggesting that only the monomer fluoresces. Both the quantum yields of the triplet state (Φ_T) and the triplet lifetimes (τ_T) were found to be higher in DMSO compared to in aqueous solution. Aggregation is hindered by addition of cremophore EL in aqueous solution and this induced disaggregation caused an increased Φ_T and τ_T probably due to the reduced interaction of the phthalocyanines with the aqueous medium in the presence of CEL.     

Spectroscopic studies of electron spin resonance and Raman scattering on novel hybrid poly-p-phenylenebenzobisoxazole (PBO) fibers with copper phthalocyanine

As was shown in the previous study using X-ray analyses, poly-p-phenylene benzobisoxazole fibers can accommodate copper phthalocyanine molecules with a molecularly-dispersed state in the fiber structure. It is necessary for us to investigate the presence/absence of chemical interactions between the two molecules mentioned above for the purpose to make clear the mechanism why such characteristic structures with the well dispersion of copper phthalocyanine molecules in the hybrid fiber were realized. Spectroscopic analyses based on electron spin resonance and Raman scattering were adopted. Because the copper phthalocyanine molecule take a plane form having D_4h symmetry in an ideal state, the spectra from the molecule would express the consequences based on its symmetry as the shape of the spectrum; the presence of characteristic bands in the spectra would be a proof of the existing state of copper phthalocyanine and poly-p-phenylene benzobisoxazole molecules in the hybrid fiber. It is found that both the spectroscopic methods suggested that there were no chemical bond observed between the two molecules of copper-phthalocyanine and poly-p-phenylene benzobisoxazole in the hybrid fiber.