Influence of the solvent on the rate constant of the reaction of the cumylperoxy radical with benzyl alcohol

The rate constants of the reaction of stripping of a hydrogen atom from a benzyl alcohol molecule by the cumylperoxy radical were measured in various solvents. The main factor determining the change in the value of the constant with variation of the solvent is the basicity (nucleophilicity) of the medium, an increase in which promotes the occurrence of the reaction.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 615–620, September–October, 1985.     

Temperature effect on quenching of CH(AΔ)

The quenching rate constants of CH(A²Δ) radicals by alcohol, alkane, O₂, and C₂H₄ molecules over the temperature range 297–653 K have been measured using laser photolysis of CHBr₃ at 266 nm to produce CH(A) radical and time-resolved fluorescence measurements. Under the simultaneous effects of multiple attractive potentials and repulsive barrier, the temperature dependence of the quenching process of CH(A²Δ) is discussed qualitatively based on a modified collision complex model.     

Static luminescence quenching by oxygen and nitric oxide for phenanthrene in glassy matrices

Steady-state and pulsed methods have been applied to static phosphorescence and fluorescence quenching for phenanthrene caused by oxygen and nitric oxide. The characteristic fluorescence quenching distances have been determined for oxygen (8.7±0.5 Å) and nitric oxide (8.9±0,5 Å); the phosphorescence quenching involves an exchange mechanism, and measurements have been made on the characteristic quenching distances R₀ and exchange-interaction attenuation parameters L. Estimates have been made on the rate constants for dynamic quenching of the triplet excited states of phenanthrene in low-viscosity liquids, which agree well with the measured values for hexane.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 667–672, November–December, 1988.     

Transfer of a hydrogen atom to acridine in the triplet state

Conclusions The quenching of triplet acridine by substituted phenols, thiophenols, and anilines is accomplished with high rate constants by hydrogen atom transfer with the quantitative formation of the corresponding neutral radicals.The solvation of the reagents by ethanol molecules or a decrease in the electron donor capacity of the quencher is accompanied by a decrease in the reaction rate constants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 178–181, January, 1989.     

Influence of the solvent on the quenching of the fluorescence of anthracene by aromatic amines

The influence of the solvent on the quenching of the fluorescence of anthracene by diethylaniline (DEA) and aniline has been investigated. Fluorescence quenching in these systems obeys the equation of Stern and Volmer. A transition from kinetics-controlled to diffusion-controlled processes takes place with the increase in viscosity () in nonpolar solvents. In polar solvents the quenching rate is limited by diffusion over the whole viscosity range investigated. These peculiar effects of the solvent can be explained by the traditional three-stage quenching scheme of the singlet-excited anthracene by electron donors. It is also possible that the increase in the quenching constant () in polar as compared to nonpolar solvents with the same is related to an increase in the rate constant of non-emitting deactivation in polar media, induced by the quenching agent. In the case of the quenching of fluorescence of anthracene by aniline the process is diffusion-controlled, regardless of the nature of the solvent.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 3, pp. 370–374, May–June, 1985.     

Quenching of singlet oxygen by phenols

The rate constants for the quenching of singlet oxygen by sterically hindered phenols were determined. It was observed that the rate constant for the quenching increases with a decrease in the ionization potential of phenols.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2132–2134, December, 1993.This work was supported by the Russian Foundation for Basic Research (Grant 93-03-5231).     

Reactions of singlet oxygen with biomolecules

Rate constants of singlet oxygen quenching by glycyrrhetic acid, glycyrrhizic acid, isoliquiritigenin, licurazide,d-glucose, andl-arabinose were determined. An increase in the quenching rate constants by more than an order of magnitude is observed on going from aglycone to the corresponding glycoside.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 57–59, January, 1996.     

Nature of electronic states and mechanism of photocoloration of oxaindanespironaphthopyrans

The nature of the electronic states was studied, and the mechanism of photocoloration is discussed for spironaphthopyrans of the oxaindane series. The life times of the T states, the quantum yields, the quenching rate constants, and the activation energies of the photocoloration are determined.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 4, pp. 495–499, July–August, 1989.The authors express their sincere gratitude to V. A. Lokshin for providing the spiropyrans.     

Influence of the temperature on the fluorescence quenching of pheophytin α by toluquinone

The influence of the temperature on the constant for the fluorescence quenching of pheophytin a by toluquinone in various solvents has been investigated. It has been shown that the quenching occurs in alcohols according to both static and dynamic mechanisms. The static quenching is caused by the formation of complexes of two types: charge-transfer complexes of ordinary structure and more stable complexes, in which the donor and acceptor are bound to one another by the alcohol molecules.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 115–118, January–February, 1985.     

Quenching of excited states of pyrene sulfonate solutions and their metal complexes by molecular oxygen

The results of study of fluorescence quenching, by molecular oxygen, of unsubstituted pyrene solutions within the framework of exchange complex are generalized. The oxygen quenching rate constants of the fluorescence and triplet state of pyrene monosulfonate and pyrene tetrasulfonate solutions and their aggregates and complexes (second and first coordination spheres) with REE ions in H₂O, DMSO, and DMFA are measured. The effect of the number of substituting sulfo groups, aggregates, complex formation, and the nature of the solvent on the efficiency of this quenching is investigated. It is shown that, in contrast to metalloporphyrins with the paramagnetic Cu(II) ion, the formation of pyrenesulfonates complexes with REE paramagnetic ions does not lead to an increase in oxygen quenching efficiency of the triplet state of organic ligands.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 23, No. 3, pp. 302–311, May–June, 1987.The authors express their deep gratitude to Prof. V. L. Ermmolaev for a fruitful discussion of the results.     

Kinetics of adsorption and desorption of sodium alkyl sulfates to and from nylon particles

The desorption rate of surfactant ions from nylon particles was investigated at the concentrations below the critical micelle concentration by applying the stopped-flow method. A mixing cell of stopped-flow spectrophotometer was modified with platinum electrodes for electric conductivity detection. The change in electric conductivity with time in the desorption process was monitored by a memory-recorder system. The surfactants used were sodium decyl, sodium dodecyl, sodium tetradecyl, and sodium hexadecyl sulfates. The desorption rate was independent of the surfactant concentration and the rate constants were obtained by applying the first-order reaction scheme. The adsorption rate constants were estimated from the experimental desorption rate constants and equilibrium constants assuming the second-order kinetics. The desorption rate constants were determined to be 1–6 sec^–1 and the adsorption rate constants to be 2–8×10⁴ mol^–1 dm³ sec^–1; the former decreased and the latter increased with increasing number of carbon atoms in alkyl chain of the surfactants.     

Photoinduced Electron Transfer in Host-Guest Complexes of α- and β-Substituted Naphthalene Derivatives with Mono-6-O-m-Nitrobenzoyl-β-Cyclodextrin

Mono-6-O-m-nitrobenzoyl-β-cyclodextrin (mNBCD) was synthesized as a novel supramolecular electron acceptor. Both the theoretical and experimental analyses suggested that mNBCD should possess a self-inclusion conformation. Fluorescence quenching experiments revealed efficient photoinduced electron transfers (PET) between mNBCD and naphthalene compounds in aqueous solution. This PET process was partitioned into a dynamic quenching component caused by bimolecule collision reactions and a static quenching component due to hydrophobic binding between the donor and acceptor molecules. Both the dynamic Stern–Volmer constants and static binding constants were determined. It was found that the binding constants of mNBCD complexes were higher than those of β-cyclodextrin complexes.This revised version was published online in July 2005 with a corrected issue number.     

Formation of linkage isomers via the substitution of halides by selenocyanate in ruthenium(III) complexes

Summary Substitution of the halide ion of [Ru(NH₃)₅X]²⁺ (X=Cl^– or Br^–) by SeCN^– was monitored spectrophotometrically between 45 and 60° C in aqueous medium. The pseudo-first order rate constants were evaluated by Guggenheim's procedure, which shows linearity for 2–3 half-lives. The rate increases linearly with [SeCN^–] and all the plots have a positive intercept on the rate axis. The SeCN^–-independent path represents aquation and the SeCN^–-dependent path represents anation of the aqua complex with simultaneous formation of two isomeric (the N bonded and the Se bonded) products. The formation of the isomeric products is entropy controlled.     

Kinetics of the alkaline hydrolysis of bis(chloromethyl)phosphinic esters

Conclusions The kinetics of the hydrolysis of bis (chloromethyl)phosphinic esters was investigated in KOH medium at 10 and 25°. The rate constants are correlated with the steric constants of the leaving groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 923–924, April, 1967.     

Mechanism of Exciplex Decay: The Quantum Yields and the Rate Constants of Radical Ion Formation from Exciplexes with Partial Charge Transfer

The dynamics of exciplex and radical ion formation was studied in donor–acceptor systems with G ^* _et > –0.1 eV. It was shown that the quenching of excited singlet states of aromatic molecules by electron donors in polar solvents led to the formation of radical ions via exciplex dissociation resulting to complete charge separation. Intersystem crossing and internal conversion into the ground state (back electron transfer) compete with this process. The quantum yields and the rate constants of the radical ion formation were measured.     

Marcus dependence of the fluorescence quenching constant of zinc tetraphenylporphin in isopropanol on the reduction potential of the oxidant

The quenching of the fluorescence of zinc tetraphenylporphin (ZnTPP) by oxidizing agents (quinones and nitro-compounds) in isopropanol) is based on a dynamic as well as on a static mechanism. Static quenching is caused by the formation of outer-sphere molecular complexes, in which the donor and the acceptor are joined by alcohol molecules. The dependence of the constant of static fluorescence quenching on the reduction potential of the oxidant is represented by a bell-shaped curve according to the classical theory of electron transfer.L. V. Pisarzhevskii Institute of Physical Chemistry, Ukrainian Academy of Sciences, Kiev. Translated from Teoretischeskaya i Éksperimental'naya Khimiya, Vol. 27, No. 6, pp. 689–695, November–December, 1991. Original article submitted February 27, 1989.     

光致噻吨酮与胺类、酚类、醇类的电子转移和氢转移反应

利用激光闪光光解方法研究了一系列胺类、酚类、醇类在脱氧乙腈中猝灭噻吨酮(TX)三重态的反应,得到了相应的瞬态吸收光谱和猝灭速率常数(kq).通过对光谱演变特性的分析,推断出三重态噻吨酮与不含有活泼氢的胺发生了电子转移反应,与含有活泼氢的胺发生了电子-质子转移反应.三重态噻吨酮与酚类、醇类反应中观察到噻吨酮加氢自由基的生成,据此推断出三重态噻吨酮与酚类、醇类发生了氢转移反应.胺类的猝灭速率常数随着反应自由能变(ΔG)的增大而减小,说明电子转移影响了噻吨酮三重态的猝灭.酚类的猝灭速率常数先随ΔG增大而减小,后随酚阳离子的酸性增强逐渐增大,可能是猝灭过程中电子转移影响减弱的同时氢转移影响逐渐增强.醇类的猝灭速率常数随着醇的α-C—H键能的增大而减小,说明α-C—H键能是影响噻吨酮三重态猝灭的关键因素.比较以前研究的胺类、酚类、醇类与三重态呫吨酮(XT)、芴酮(FL)反应的结果可知,由于分子结构差异性的影响,相关的猝灭速率常数按照呫吨酮、噻吨酮、芴酮的顺序逐渐减小.     

Fluorescence quenching of anthracene by indole derivatives in phospholipid bilayers

The quenching of anthracene fluorescence by indole, 1,2-dimethylindole (DMI), tryptophan (Trp) and indole 3-acetic acid (IAA) in palmitoyloleoylphosphatidylcholine (POPC) lipid bilayers was investigated. A very efficient quenching of the anthracene fluorescence in the lipid membrane is observed. Stern-Volmer plots are linear for DMI but present a downward curvature for the other quenchers. This was interpreted as an indication of the presence of an inaccessible fraction of anthracene molecules. By a modified Stern-Volmer analysis the fraction accessible to the quenchers and the quenching constant were determined. The changes in the fluorescence emission spectrum of indole and DMI have been used to calculate the partition constants of these probes into the membranes, and bimolecular quenching rate constants were determined in terms of the local concentration of quencher in the lipid bilayer. The rate constants are lower than those in homogeneous solvents, which may be ascribed to a higher viscosity of the bilayer. No changes in the emission spectra of Trp and IAA are observed in the presence of vesicles, indicating that these probes locate preferentially in the aqueous phase, or in close proximity to the vesicular external interface in a medium resembling pure water. In these cases quenching rate constants were determined in terms of the analytical concentration. In the quenching by DMI a new, red shifted, emission band appears; it is similar to that observed in non-polar solvents and it is ascribable to an exciplex emission. The exciplex band is absent in the quenching by IAA and Trp and only very weakly present when the quencher is indole. From the position of the maximum of the exciplex emission, a relatively high local polarity could be estimated for the region of the bilayer where the quenching reaction takes place.     

Effect of the chemical structure of nitroxyl radicals on their reactivity in the reaction with hydrazobenzene and tetranitromethane

The reaction rate constants of reduction of stable radicals of different classes by hydrazobenzene in hexane at 20C, in the range of 0.4–5·10³ M^–1sec^–1, were determined; a single scale of the oxidative properties of stable nitroxyl radicals was constructed. The rate constants of oxidation of a series of nitroxyl radicals by tetranitromethane in aqueous medium at 20C, in the range of 0.06–10 M^–1·sec^–1, were determined. It was shown that the oxidative properties of the nitroxyl group decrease slightly with an increase in its reducing properties for nitroxyl radicals of the piperidine and imidazoline series in reactions with ascorbic acid and tetra-nitromethane in aqueous medium, respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2575–2582, November, 1990.     

Reactivity of Water and Alcohols toward Carbocations Generated in the Photolysis of 2,2,4,6-Tetramethyl-1,2-dihydroquinoline

The rate constants of the decay of carbocation generated in the photolysis of 2,2,4,6-tetramethyl-1,2-dihydroquinoline and the composition of reaction products were studied as a function of solvent composition in the mixtures H₂O–ROH and MeOH–ROH (R = Et, n-Pr, and i-Pr). The rate constants of carbocation decay in alcohols are more than 20 times higher than the corresponding rate constants in water. As follows from the composition of the products obtained in the photolysis in the alcohol–water mixtures, MeOH is only 1.4 times more reactive than water, and EtOH and n-PrOH are even less active than water. The inconsistency in the product composition in the mixtures and the values of the observed rate constants in these solvents was explained by the two-step mechanism of the reaction: the reversible formation of an adduct of the carbocation with the solvent components and subsequent proton transfer to the solvent to form the final product, with the first step determining the product composition and the second step determining the rate of carbocation decay. The relative rate constants of alcohols and water were determined for the two steps. The preferred solvation of the carbocation with water also contributes significantly to the reaction kinetics and the product composition in the water–alcohol solutions.