One-electron reduction of thionine studied by pulse radiolysis

One-electron reduction of thionine has been studied by using the technique of nanosecond pulse radiolysis and kinetic spectrophotometry. H,e _aq ⁻ as well as radicals derived from methanol, ethanol, isopropanol, THF, dioxane andt-butanol by H atom abstraction were used as reductants. The rate constants for the transfer of electrons from these radicalts to thionine were directly determined from the pseudo first-order formation rates of the product, semithionine and the one-electron reduction potential of thionine estimated. The absorption spectrum of semithionine in its different conjugate acid-base forms was found to be in agreement with previously reported spectra and the decay of the species was second order. By monitoring transient absorbance changes as a function of pH, twopK _a values were observed and, based on the effect of ionic strength on the second-order decay constants of the species were assigned to the equilibria described.     

Kinetics of the (photo)oxidation of the thionine leuco base with uranyl nitrate

Spectrophotometry and lamp and laser flash photolysis have been used to investigate the kinetics of the formation and decay of thionine and semithionine, obtained in the photooxidation of the thionine leuco base with uranyl nitrate. It has been shown that after the light flash a certain amount of thionine is formed in the cage oxidation of semithionine with uranoyl UO₂ ⁺ (concentration ratio of thionine and semithionine leaving the cage 595). A kinetic scheme of the reaction has been proposed, which describes satisfactorily the experimental data. The equilibrium constant K=1.2±0.3)·10^–4 has been obtained for the dark oxidation of the thionine leuco base with uranyl nitrate in aqueous sulfuric acid (pH 1.0) which is close to the calculated value.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 13–18, January, 1990.     

SENSITIZED PHOTOOXYGENATION ACCORDING TO TYPE I MECHANISM (RADICAL MECHANISM) — PART II. FLASH PHOTOLYSIS EXPERIMENTS

Abstract— In order to gain further insight into the sensitized photooxygenation of the system thionine, allylthiourea, and oxygen, the influence of the leucothionine, which is formed during the photoreaction, was studied by flash photolysis. In the presence of leucothionine, additional thionine (Λ_obs= 598 nm) is reformed; i.e., leucothionine is oxidized to thionine by way of a semithionine intermediate (Λ_bs= 770 nm). This additional semithionine formation due to leucothionine is complete by 30 μsec after the flash. By varying the leucothionine concentration, the flash intensity and the pH it can be shown that the agent which oxidizes leucothionine to semithionine is identical to the agent which transforms semithionine to thionine.     

SENSITIZED PHOTOOXYGENATION ACCORDING TO TYPE I MECHANISM (RADICAL MECHANISM) - PART I. FLASH PHOTOLYSIS EXPERIMENTS

Abstract— The photooxygenation of allylthiourea (ATU) sensitized by thionine does not occur according to the singlet oxygen mechanism but rather proceeds via the formation of radicals. In oxygen-free solution the primary process is a redox reaction between the thionine triplet and ATU where a semithionine- and an ATU-radical are formed. In further reaction steps the leuco form of the dye is finally produced (reductive photobleaching; D
R mechanism after Koizumi). The primary process in an oxygen-containing aqueous solution is the same, since at high concentrations of ATU (0·2 M ) the amount of semithionine formed by a photolytic flash, as well as the time course of disappearance of semithionine, does not depend on the oxygen content of the solution.
The reformation of thionine following flash photolysis has been investigated with regard to oxygen concentration and pH dependence. Two different excitation intensities were used. A quadratic dependence of thionine reformation on excitation intensity at high oxygen concentration was observed, indicating a reaction between two photoproducts.
The dependence of the reaction rate of semithionine on the ionic strength has been investigated. These experiments show that the reaction partner of semithionine carries a charge of + 1 in oxygen-free as well as in oxygen-saturated solution.     

FLASH PHOTOLYSIS OF 3-IODOTYROSINE IN AQUEOUS SOLUTION AT pH 5

Abstract— The 3-tyrosinyl free radicals (3-Tyr) and iodine atom are formed by flash photolysis of 3-iodotyrosine (3-Tyr-I) in aqueous solutions at pH 5. The presence of iodine atoms in the medium is characterized by the absorption spectrum and the decay kinetics of I formed when KI is added to the system. In the absence of radical scavengers, the 3-Tyr adds to or reacts with the parent molecule to produce a transient species, probably a radical dimer, which has an absorption maximum at 405 nm. The decay of this transient follows second order kinetics whose rate constant increases with decreasing 3-iodotyrosine concentration. Measurements of the dependence of the transient yield on the concentration of added ethanol indicate that the 3-Tyr radical reacts with ethanol by hydrogen abstraction. The rate constants of reaction of the 3-Tyr radical with 3-iodotyrosine and ethanol are deduced from results.     

配位体SO2-4对激发态铀(VI)去活化的影响

The dependence of the luminescence decay of electronically excited uranyl ions on the concentrations of uranium and sulphate in aqueous solution has been investigated with a pulsed nitrogen laser as a light source and a programmable transient recorder for lifetime measurements. Single exponential decay of the Luminescence is observed. The deactivation process of the excited uranyl ions should include radiative, nonradiative, water quenching and uranium self quenching and the measured lumine-scenec lifetime inidcates the result of all these processes. The Luminescence lifetime of uranyl ions increases with increasing concentration of sulphate and becomes constant when the equilibrium concentration of sulphate reaches 3.0 mol·L~(-1). The dependence of the Luminesence lifetime is similar to that of the UO_2(SO_4)_3~(4-) formation. This phenomenon can be interpreted in terms of the fact that in aqueous solution uranyl ions exist as aquo-uranyl ions. As the concentration of sulphte increaes the water molecule of hydrated uranyl ions will be replaced by sulphate ions via complex formation, and the quenching of excited uranyl ions by water is reduced. The self quenccing and the water quenching rate constants of UO_2(H_2O)_6~(2+) and UO_2(SO_4)_3~(4-) are estimated. Based on the experimental results a model for the deactivation mechanism of excited uranyl ions in sulphate solution is proposed.     

Kinetics of iridium(III) catalyzed oxidation of benzaldehyde and <Emphasis Type="Italic">p</Emphasis>-nitrobenzaldehyde by cerium(IV) in aqueous acidic medium

Oxidation of benzaldehyde and p-nitro-benzaldehyde by cerium(IV) sulphate in aqueous sulphuric acid is strongly catalyzed by iridium(III) chloride. The complex formed between cerium(IV) and the organic substrate in the first equilibrium step gives another complex in the presence of iridium(III), which ultimately gives the corresponding aromatic acids as the product of oxidation. The order of the reaction follows first-order kinetics at low concentrations to zero order at higher concentrations of both the oxidant and organic substrate. The rate is directly proportional to the concentration of catalyst, but decreases sharply with increasing H⁺ ions and cerium(III) concentrations, while change in ionic strength of the medium or the concentration of acetic acid and Cl⁻ ions has no effect on the rate.     

ANION AND SOLVENT EFFECTS ON THE RATE OF REDUCTION OF TRIPLET EXCITED THIAZINE DYES BY FERROUS IONS

Abstract— The lifetimes of the triplet excited states of thionine and methylene blue were measured in aqueous and 50 v/v% aqueous acetonitrile solutions acidified with 0.01 N sulfuric or trifluoromethyl-sulfonic acid. The rate constants for reaction of the triplet excited dyes with ferrous ions were measured in the same solutions. The triplet lifetimes in the absence of added quenchers were insensitive to a change in acid from trifluoromethylsulfonic to sulfuric or to a change in solvent from water to 50v/v% aqueous acetonitrile (τ for triplet thionine ˜7.5 μs, τ for triplet methylene blue ˜4.5 μs). In contrast, the rate constant for reaction of the triplet dyes with ferrous ions increased by nearly a factor of 10 with a change in acid from trifluoromethylsulfonic to sulfuric. In solutions containing sulfate ions this reaction rate constant increased with increasing sulfate concentration and with a change in solvent from water to 50 v/v% aqueous acetonitrile. The results are discussed in terms of the possibility of association of the positively charged reactive ions with sulfate anions. Quenching of the triplet excited dyes by ferric ions or by ground state dye molecules was shown to be negligible at the concentration used for the ferrous ion quenching study.     

Inorganic particulates in removal of toxic heavy metal ions

Adsorption behavior of zinc, cadmium and mercury ions on hydrous titanium oxide in aqueous solution has been studied as a function of concentration of the metal ion (10⁻²−10⁻⁷M), temperature (303–333 K) and pH 3–10 by applying radiotracer technique. The kinetics of adsorption follows the first order rate law and agrees well with the classical Freundlich isotherm. The removal was found to increase with increasing pH but was suppressed in the presence of EDTA. The overall process is endothermic and irreversible in nature. Part VII. Efficient removal of cadmium ions from aqueous solutions by hydrous manganese oxideS. P. Mishra, D. Tiwary, Radiochim. Acta, 80 (1998) 213.     

Reduction Kinetics of Thionine in Aerobic Condition with D-Galactose

Reduction kinetics of thionine (Th) with D-galactose (RH) was observed on a UV/Visible 1601 Shimadzu spectrophotometer at λmax 599 nm. The results showed that the initially slow reduction kinetics got enhanced and proceeded to completion within a few minutes. A pseudo first order kinetics was observed when influence of different parameters like concentration of dye and reductant, ionic strength and temperature was investigated. A significant shift in wave length from 599 to 517 nm was observed at alkaline pH whereas addition of a small amount of acid caused a shift in equilibrium. This resulted in the generation of oxidized form of thionine which was pragmatic in the presence of atmospheric oxygen. Change in ionic strength at elevated temperature lied to decrease in the rate constant. Thermodynamics activation parameters like Ea reflects a high amount of energy required for reduction of Th with RH whereas entropy of activation (∆S!) and free energy of activation (∆G!) show the highly solvated states of transient complex which was less disorderly arranged than the oxidized form of dye. A mechanism consistent with above findings has been discussed in the relevant section of paper.     

SENSITIZED PHOTOOXYGENATION ACCORDING TO TYPE I MECHANISM (RADICAL MECHANISM) — PART III. EXPERIMENTS WITH CONTINUOUS ILLUMINATION

Abstract— The photochemical reaction in the system thionine (sensitizer), allylthiourea (ATU, acceptor), and oxygen was studied with continuous illumination. In oxygen-free aqueous solution thionine is photoreduced to leucothionine. With oxygen, however, a photooxygenation of the acceptor takes place. At the same time the quantum yield of the bleaching reaction of thionine decreases markedly in comparison with that of the oxygen-free solution. At about 100 sec after the beginning of illumination, the overall quantum yield of the bleaching reaction diminishes further because the leucothionine formed during the reaction now becomes transformed into thionine. The quantum yields do not change significantly over the range of oxygen concentrations studied (initial concentration 1 × 10^-5 to 5 × 10^-5 M ). In addition they are independent of the light intensity. The influence of the pH and the acceptor concentration were also investigated.
The sensitizer is not only bleached reductively, but is also partly destroyed by oxidation. The results are in agreement with the reaction scheme elucidated by flash photolysis measurements.
In accordance with this reaction scheme, the primary reaction (a) of the reductive bleaching of the sensitizer, (b) of the photooxygenation of the acceptor and (c) of the oxidative destruction of the sensitizer, is identical in all cases. This process is the redox reaction between the sensitizer triplet and the acceptor, where a semithionine and an ATU-radical are formed. The reaction represents an example of a Type I photooxygenation according to the notation of Gollnick.     

Removal of Thiram from Aqueous Solutions

In this study activated carbon was used for the removal of thiram from aqueous solutions. Adsorption experiments were carried out as a function of time, initial thiram concentration and temperature. Equilibrium data fitted well to the Freundlich and Langmuir equilibrium models in the studied concentration range. Adsorption kinetics followed a pseudo second‐order kinetic model rather than pseudo first‐order model. The results from kinetic experiments were used to describe the adsorption mechanism. Both boundary layer and intraparticle diffusion played important role in the adsorption mechanism of thiram. Thermodynamic parameters (ΔG₀, ΔH₀, and ΔS₀) were determined and the adsorption process was found to be an endothermic one. The negative values of ΔG⁰ at different temperatures were indicative of the spontaneity of the adsorption process.     

Effect of pH on kinetics of the decay of the radicals formed during photolysis of 2,2,4,6-tetramethyl-1,2-dihydroquinoline in aqueous and micellar solutions

Kinetics of the decay of the transient radicals formed from 2,2,4,6-tetramethyl-1,2-dihydroquinoline (TMQ) in aqueous and micellar solutions of sodium dodecyl sulfate were studied by flash photolysis as a function of pH. In aqueous and micellar solutions of TMQ the mechanism of the decay of the transient species and the reaction products are different from those in homogeneous organic solutions. The decay of the transient radicals follows first-order kinetics in the entire range of pH under consideration in both aqueous and micellar solutions. In aqueous solutions at pH 9–12, the decay rate constant decreases from 25.3 to 3.7 s⁻¹. In micellar solutions at different pH, different types of micellar catalysis were observed. At pH 1, the rate constant in a micellar solution is slightly lower than that in an aqueous solution. At pH 3–11, the decay rate constant increases (positive micellar catalysis). The apparent rate constant depends linearly on the concentration of TMQ in micelles. The rate constant for the reaction of the transient radical cation with TMQ was determined (200 L mol⁻¹ s⁻¹). At pH>13, the decay rate constant in micelar solutions is lower than that in aqueous solutions (negative micellar catalysis). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 703–708, April, 1997.     

CHLOROPHYLL PHOTOCHEMISTRY IN CONDENSED MEDIA—I. TRIPLET STATE QUENCHING AND ELECTRON TRANSFER TO QUINONE IN CELLULOSE ACETATE FILMS*

Chlorophyll-a was incorporated into cellulose acetate films and the triplet state decay kinetics and electron transfer from triplet to p-benzoquinone in aqueous solution was studied using laser flash photolysis and EPR. The triplet was found to decay by first order kinetics with a rate constant which was independent of Chl concentration. The triplet yield, however, was concentration dependent. These properties are due to quenching which occurs only at the singlet state level. In the presence of quinone, the triplet is quenched and, when the quinone is in an aqueous solution in contact with the film, Chl cation radical (C^±) as well as the semiquinone anion radical (Q^±) can be observed. The C decays by second order kinetics with a rate constant of 1.5 × 10⁶M^-1 s^-1. Although triplet conversion to radicals is slightly lower in the films as compared to fluid solutions (? 3 times), the lifetimes of the radicals are greatly increased (? 10³ times).     

Kinetics of the Rapid Base Catalyzed Iodination of Imidazole and 2‐Methylimidazole by Molecular Iodine in Aqueous Medium: pH Effect

The second‐order kinetics of iodination of imidazole and 2‐methylimidazole in aqueous medium at various pH values and temperatures are studied in the presence and absence of a base catalyst. The reactions being electrophilic substitutions, molecular iodine is the sole iodinating agent, as the reactant solutions used are totally devoid of I ^? ions. The specific reaction rates of imidazole ( I ) and 2‐methylimidazole ( II ) for the catalyzed reactions are found to be 87.00 and 62.92 M^?1 s^?1 at 27.0°C, respectively, at 7.0 pH. The base component of the buffer used to maintain the pH catalyzes the reactions. The rapidity of the reactions necessitates the use of a rotating platinum electrode to follow the decay of the unreacted iodine. The study provides a quantitative verification of the reactivities of the substrates.     

The Equilibrium and Kinetic Modelling of the Biosorption of Copper(II) Ions on <Emphasis Type="Italic">Cladophora crispata</Emphasis>

The biosorption of Cu(II) ions on Cladophora crispata was investigated as a function of the initial pH, temperature and initial Cu(II) ion concentration. Algal biomass exhibited the highest Cu(II) uptake capacity at 25C and at the initial pH of 4.5. Equilibrium data fitted very well to both the Langmuir and Freundlich isotherm models. The pseudo second order kinetic model was applied to describe the kinetic data and the rate constants were evaluated in the studied concentration range of Cu(II) ions at all the temperatures studied. The experimental data fitted well to the pseudo second order kinetic model with a high correlation coefficient (R² > 0.99), which indicates that the external mass transfer limitations in the system can be neglected and the chemical sorption is the rate-limiting step. The pseudo second order kinetic constants were also used to calculate the activation energy of Cu(II) biosorption.     

Chloride-catalyzed oxidation of phenol in pulsed-laser irradiation titanium dioxide sols

The kinetics of photolysis of phenol in presence of two kinds of TiO₂ colloid in acid aqueous solution medium was studied by transient absorption spectroscopy. The absorbance and quantum yield of the phenoxyl radicals is strongly influenced by the chloride ions. The process of laser flash photolysis of phenol in the presence of chloride has been discussed.     

Effect of bromide salts on the acid hydrolysis of anti-bacterial hydrophilic Schiff base amino acid iron(II) complexes

Salt effects on the kinetics of acid hydrolysis of some novel hydrophilic iron(II) complexes have been investigated in aqueous medium. The ligands are derived from the condensation of amino acids (glycine, L-alanine, L-leucine, L-isoleucine, DL-methionine, DL-serine or L-phenylalanine) and sodium 2-hydroxybenzaldehyde-5-sulfonate. The reaction was studied under conditions of pseudo first order kinetics. The general rate equation was suggested as follows: rate = k _obs[complex], where k _obs = k ₂[H⁺]. The reaction rate decreases with an increase of the salt concentration.     

Kinetics of Reduction of Thionine with Ribose and the Structural Properties of the Dye at Different pH Using DFT Method

The reaction between the thionine (Th) and the ribose was observed spectrophotometrically and changes in absorbance of Th were recorded at variable concentration of dye, reductant and pH. A pseudo first order rate of reaction was found to establish the reduction kinetics of the dye, studied at a pH range of 0.34 to 12.8. Absorption spectrum of Th at different pH, with ribose showed a pH (12.8) dependent introversion. The reduction most probably took place with enediol intermediate of the sugar at high pH. A full geometry optimization of predominant species of Th namely, mono‐deprotonated, di‐deprotonated Th, and LTh (leuco thionine) respectively, at low and high pH, was performed at B3LYP level of theory. The data obtained from the energy minimization were in excellent agreement with other experimental and theoretical observations. The calculated enthalpies of formation for both reduction reactions (mono‐deprotonated Th+H⁺→leucothionine and di‐deprotonated Th+2H⁺→leucothionine) provided evidences for maximum reduction of the dye at high pH.