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.     

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...     

Fluorescence Studies of gold(III)-Norfloxacin Complexes in Aqueous Solutions

Formation of gold(III) complexes with the synthetic antibiotic norfloxacin (NF) was investigated in aqueous solution at pH 4.0, 7.5 and 10.6, with the ligand in cationic, zwitterionic and anionic forms, respectively. UV-Visible spectroscopy, steady state and time-resolved fluorometry were used to characterize the complexes. Binding sites, association constants and fluorescence lifetimes of the complexes were obtained. Au³⁺ binding to zwitterionic NF produced a fluorescence decrease and a small red shift. Fluorescence changes as a function of Au³⁺ concentration were fitted using a one-site binding model and the association constant was obtained, K_b^zw = 1.7 ×10⁵  \textM¹ K_b^{{zw}} = {1}.{7} \times {1}{0^{{5}}}\;{{\text{M}}^{{1}}} . The association of Au³⁺ with cationic NF was much weaker, the obtained binding constant being K_b^cat = 2.4 ×10³  \textM¹ K_b^{{cat}} = {2}.{4} \times {1}{0^{{3}}}\;{{\text{M}}^{{1}}} . The Au³⁺ binding site for these species involves the carboxyl group, in agreement with a much stronger association of the cation with the carboxylate anion than with the neutral acid. Association of Au³⁺ with nonfluorescent anionic NF presented a clear evidence of two binding sites. The highest affinity site is the unprotonated piperazinyl group with K_b^pip \geqslant 5 ×10⁷  \textM ^{- 1} K_b^{{pip}} \geqslant {5} \times {1}{0^{{7}}}\;{{\text{M}}^{{ - {1}}}} , and the low affinity site includes the carboxylate anion. The results point out to important pH dependent differences in complex formation between transition metal ions and fluoroquinolones, leading to different binding sites and association constants that change by several orders of magnitude.     

Photophysical Properties and Photoreduction of 5,10,15,20-Tetrakis-(4-N-Methylpyridyl)Porphyrin in Formamide

The photophysical characteristics and photochemical conversions of 5,10,15,20-tetrakis-(4-N-methylpyridyl)porphyrin in a highly polar solvent, formamide, are investigated. It has been established that no photochemical reactions occur on excitation in the visible spectral region, while UV excitation ( = 347 nm) causes photoreduction of porphyrin molecules followed by the formation of protonated products. The solvent molecules serve as a reducing agent. Photoreduction occurs in both air-saturated and deoxygenated solutions, but the nature of the products formed is different: chlorin molecules are formed in the air-saturated solutions and the successive photoconversion porphyrinphlorinporphometheneporphyrinogene occurs in the deoxygenated solutions.     

Particle Formation from Single Droplets of Aqueous Solutions of Lead Nitrate

The thermal evolution of droplets of aqueous solution of lead nitrate was studied in a drop-tube furnace, which simulates typical conditions for material synthesis, through spray pyrolysis, and for the thermal destruction of liquid-containing waste. The processes of droplet evaporation, precursor precipitation within the droplet and thermolysis of the precipitated particles were followed by means of the spectral analysis of the ultraviolet light scattered by the aerosol produced during the heating of aqueous droplets (100 μm) of lead nitrate, with different salt concentrations, from ambient temperature up to 1200 K. Dimensions and physico-chemical properties of the droplets/particles were obtained in situ by means of ultraviolet spectra of light scattering (UVSLS) and compared with scanning electron microscopy (SEM) of the sampled material. A plasma generated in the air by an optical breakdown induced by a Nd:YAG laser was employed as the light source in the wavelength range 200–400 nm, thus allowing an exceptionally high photon flux in the ultraviolet region where intense and species-specific interactions with metal species take place. The spray drying process was followed by measuring the light transmitted by the droplets in the backward region. As the drying process progresses, the surface concentration reaches a saturation value and solute is deposited as a solid phase forming a surface crust, which grows steadily. At this point in the process of droplet drying, information was retrieved from the light reflected by the particle interface. Two spectral scattering behaviors were detected at temperatures above the salt precipitation within the droplet. On the basis of Mie calculations and SEM measurements, these behaviors were attributed to lead nitrate particles with typical diameters of the residual droplets (about 50 μm) and to micrometer-sized lead oxide particles. The effect of salt concentration on the drying process and the thermolysis of lead nitrate to oxide was investigated by changing the salt concentration from very dilute conditions up to almost the saturation concentration.     

Optical Properties of Nano 5,10,15,20-Tetraphenyl-21H,23H-Prophyrin Nickel (II) Thin Films

Optical properties of the as-deposited and annealed films of 5, 10, 15, 20-Tetraphenyl-21H, 23H-Porphyrin nickel (II), (NiTPP) were investigated using spectrophotometric measurements of both transmittance and reflectance at normal incidence of light in the wavelength range, 200–1100 nm. The obtained data of refractive index, and absorption index, were used to estimate the type of transition and both optical and fundamental gaps. The normal dispersion (λ > 600 nm) of refractive index is discussed in terms of single oscillator model of Wemple-Didomenico, while the anomalous dispersion (λ < 600 nm) is discussed according to multi oscillator. The dispersion parameters; oscillator energy, dispersion energy, optical dielectric constant at higher frequency, lattice dielectric constant, and the ratio of carrier concentration to the effective mass N/m* were determined. The real part of the dielectric constant, the imaginary part of the dielectric constant, the loss factor, the volume and the surface energy loss functions were estimated and discussed.     

An Investigation of the Digitized Raman Band Profiles of Aqueous Mg(ClO4)2 - NaSCN Solutions

Abstract

Raman spectra, together with factor analysis and band deconvolution procedure, have been used to study formation of magnesium thiocyanate complexes in aqueous solutions at ambient and elevated temperatures. The total salt concentration in solutions, containing different mole ratio of Mg²⁺ to SCN, varied between 3.4 and 7.5 mol dm^?3. Factor analyses indicated that two linearly independent scattering components in the band envelopes, recorded in the V₁ and v₃ stretching regions of SCN, for all solutions with total salt concentration of 3.4 mol dm^?3. The appearance of a pseudo-isosbestic point in the area normalized spectra supported this result, as well as the baud resolution procedure. The latter revealed the third scattering component in the spectra of solutions with total salt concentration above 3.5 mol dm^?3 Resolved components have been assigned to the free thiocyanate, the 1:1 and 1:2 magnesium thiocyanate complexes. The equilibrium constant K_c of the 1:1 complex is of an order of 10^?1 mol dm^?3.     

Concentration Fluorescence Quenching of L(-)-Tyrosine in Aqueous and Nonaqueous Solutions

Abstract

A number of studies have demonstrated the dependence of both the fluorescence lifetimes and quantum yields of tyrosine in solution upon the nature of the solvent as well as upon the absence or the presence of air in the tyrosine solutions employed. Photobleaching of tyrosine in vacuum at pH 6.1 was found to be practically zero, whereas exposure of tyrosine to the full light of a Hglamp for 10 to 20 minutes gave rise to formation of non-fluorescing photoproducts⁽¹⁾. In addition, the phosphorescence lifetimes of tyrosine were determined as 2.7⁺?0.2 sect 2.7⁺0.2 sec. and < 1 sec in 1% ETOH in aqueous solution and at pH 6.1 and pH 13, respectively(l). The very long phosphorescence lifetimes are definitely responsible to a considerable extent as far as photobleaching is concerned. However, the participation of the excited singlet state cannot be ruled out. In a review, the fluorescence lifetimes of tyrosine in queous solutions were found to vary between 2.6 nsec to 3.6 nsec⁽²⁾. On the other hand, the fluorescence quantum yields of tyrosine and various anologous compounds displayed a strong dependence upon the solvent. Such solvents used were water, n-butanol and p-dioxane. The following values of φ_fl were obtained: For p-HO-C₆H₄ -CH₂COOH; φ_fl=0.01, 0.22 and 0.34; for p-HO-C₆H₄-CH₃; φ_fl= 0.23, 0.39 and 0.45 and for p-HO-C₆H₄-CH₂CN; φ_fl =0.16, 0.34 and 0.34, respectively⁽³⁾. Furthermore, the value φ_fl of p-HO-C₆H₄-CH₂CH(NH⁺ ₃)C00^? in aqueous solutions was found to be 0.21, where- as that of p-HO-C₆H₄-CH²CH(NH⁺ ₃)COOH in similar solutions was 0.06. The fluorescence lifetime and quantum yield of phenol in Ethanol were found to be 4.7 nsec and 0.10, respectively⁽⁴⁾.     

Self-aggregates formation of 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes and of their binary mixtures with the liquid crystal 4-octyl-4′-cyanobiphenyl (8CB) have been studied. Absorption and fluorescence studies were carried out. Both absorption and fluorescence spectra have revealed the formation of self-aggregates of dye molecules in monomolecular layers. Moreover, information about the molecular organization at the air-solid substrate interface has been obtained.     

5,10,15,20-四-(4-十六烷基吡啶基)卟啉LB膜结构的研究

研究了两亲性卟啉５,１０,１５,２０－四－（４－十六烷基吡啶基）卟啉溴化物在气－液界面上的成膜性能,制备了其ＬＢ膜。用扫描隧道显微镜和ＵＶ－Ｖｉｓ光谱,荧光光谱,小角Ｘ射线衍射等实验方法研究了ＬＢ膜的形貌和卟啉大环分子在ＬＢ膜中的排列、取向和分子间的相互作用。结果表明,制备的ＬＢ膜结构均匀,性能稳定,在ＬＢ膜内,脂肪链并不是直立的,卟啉分子大环几乎平躺在基片上。     

Aggregation Kinetics of Meso-tetrakis(4-sulfonatophenyl) Porphine in the Presence of Proteins: Temperature and Ionic Strength Effects

The kinetics of J-aggregation was studied through UV/Vis spectroscopy for meso-tetrakis(4-sulfonatophenyl) porphine—TSPP at pH = 2.0 using the protein human serum albumin as template. The effect of protein concentration on the kinetics was monitored by the appearance of the J-aggregate band at 486 nm and the simultaneous decrease of the monomer absorption at 434 nm. A simple equation based on the X ^k Y reaction, where k may be assumed as a pseudo-first-order rate, fits well both the J-aggregation formation and monomer transformation. Temperature dependence of the reaction rate follows an Arrhenius behavior up to T = 38°C, but above this value the dependence is inverted. This temperature seems to reflect the mid-point for the thermal denaturation of HSA. Ionic strength effect clearly exposes the prevalence of the electrostatic nature of this J-aggregation, and using a semi-empirical equation an estimate of the interaction length between TSPP-Na⁺ of 4.5. an was obtained in good agreement with crystallographic data. Absorption band shift and bandwidth were used to estimate the number of monomers in the J-aggregate unit that leads to spectral changes, and a number around 6–7 was found. There is no apparent growth of J-aggregate taking into account the invariance of the bandwidth of J-aggregate band with time at any of the temperatures studied.     

MRI contrast-dose relationship of manganese(III)tetra(4-sulfonatophenyl) porphyrin with human xenograft tumors in nude mice at 2.0 T

Previously we reported that Mn(III)tetra(4-sulfonatophenyl) porphyrin, MnTPPS₄, is a contrast agent which can effectively enhance tumor detection by MRI. By imaging 30 additional athymic nude mice bearing subcutaneous MCF-7 WT human breast carcinoma xenografts, we have extended dose-contrast relationships over a wide range of intraperitoneal (IP) doses ranging from 0.025 to 0.50 mmol/kg. The benefits of IP injection are higher possible doses on a volume basis and a reduction in toxicity versus IV administration. Full coronal cross-section images have been obtained on a 2-T spectrometer. Although individual tumor masses displayed different distribution patterns, reflective of their internal morphology, single doses of 0.10 mmol/kg or greater were necessary to produce a detectable effect. At a dose of 0.50 mmol/kg, marked enhancement was produced. Multiple small dosages administered over the course of several days before imaging did not produce increased enhancement. Preliminary results on the new porphyrin derivative, MnTPPS₃, indicate that the ratio of the toxic dose to the effective dose may be adjustable to render this class of agents clinically useful.     

Possible Wormhole Solutions in (4 + 1) Gravity

We extend previous analyses of soliton solutionsin (4 + 1) gravity to new ranges of their definingparameters. The geometry, as studied using invariants,has the topology of wormholes found in (3 + 1) gravity. In the induced-matter picture, thefluid does not satisfy the strong energy conditions, butits gravitational mass is positive. We infer thepossible existence of (4 + 1) which, compared to their (3 + 1) counterparts, are lessexotic.     

Spin coupling in distorted high-valent Fe(IV)-porphyrin radical complexes

In order to study structural influences on the interaction of Fe(IV) (S=1) and porphyrin cation radical (S=1/2) in high-valent iron porphyrin complexes of the type ¦X-(TMP)Fe=O¦⁺(Cl^–), X=I, Br₂, Br₄ were generated by mCPBA oxidation of corresponding Fe(III) porphyrins. The halogen substitution at the peripheral positions of the porphyrin leads to distortion of the planar porphyrin ring of ¦(TMP)Fe=O¦⁺. The new species have beeen investigated by temperature-dependent EPR and field-dependent Mössbauer spectroscopy; for the evaluation of spectra, we adopted the spin-Hamiltonian formalism including exchange interaction explicitly. As in ¦(TMP)Fe=O¦⁺, strong ferromagnetic spin coupling was observed with|J₀|D=0.9–1 and a zero-field spltting ofD32 cm^–1. For consistent parametrization of EPR and Mössbauer results, anisotropic coupling had to be introduced. Compared to ¦(TMP)Fe=O¦⁺ [1], analysis of the spectroscopic data shows that zero-field splitting and spin coupling is only slightly affected by the halogen distortion of the porphyrin structure.     

Effect of Hydrolysis Conditions on the Direct Formation of Nanoparticles of Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

The effect of the cation concentration, hydrolysis temperature, and composition in the CeO₂–ZrO₂ system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO₂ were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm³ by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm³ at the starting composition of 50 mol% ZrO₂ under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH₄)₂Ce(NO₃)₆. Ceria–zirconia solid solutions containing large amount of ZrO₂ maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h.     

Silicon-29 NMR Study of Alkaline Aqueous and Alcoholic Tri-butylmethyl Ammonium (TBMA) Silicate Solutions

Silicon-29 NMR spectroscopy was used to characterize aqueous and alcoholic alkaline solutions of tri-butylmethyl ammonium (TBMA) silicates. The effect of TBMA cation on the equilibrium of silicate oligomers in aqueous alkaline silicate solutions was investigated using ²⁹Si NMR spectra. It was found that TBMA cation has a structure directing role and directs the silicate species to form minor amounts of silicate anion in the presence of high concentration of silicon. Silicon-29 NMR spectra of TBMA silicate solutions indicate that considerable changes occurred by changing the Si/TBMA ratio. The distribution of silicate species was affected by the presence of the alcohols, specifically methanol.     

LaCl_3溶液中微团簇的光谱研究

对LaCl_3溶液拉曼和荧光光谱及其变化进行了理论计算和实验研究,得到了较为全面的光谱信息。基于密度泛函理论的B3LYP方法,在6-31G(d,p)+Def2-SV(p)基组水平上计算了氯化镧溶液中的微团簇结构,结果表明微团簇分子趋向于形成9配位结构,验证了计算方法的可行性。理论拉曼光谱与实验光谱相比基本一致,随着LaCl_3的加入溶液拉曼光谱在300~600cm~(-1)范围内峰的强度稍微增大,原因可能为La—O振动与水中O—H的面内、面外摇摆峰叠加形成的;在3 000~4 000cm~(-1)范围内,氯化镧溶液与水相比峰形变窄,可能是由于在溶液中原有的水团簇结构破坏后形成的镧水合物中O—H的伸缩振动导致。荧光发射光谱在350nm处出现明显的新峰,且与浓度呈良好的线性关系,从络合物角度实现了对氯化镧溶液的定量分析;同样的基组水平上计算了团簇的荧光发射中心,在误差允许范围内,理论计算与实验值基本吻合,实现了对实验光谱中新峰的指认与归属。