Reaction of the tamoxifen cation and the bis-(4-methoxyphenyl)methyl cation in aqueous solutions containing 2'-deoxyguanosine

2002 ◽  
Vol 80 (3) ◽  
pp. 269-280 ◽  
Author(s):  
Robert A McClelland ◽  
Cristina Sanchez ◽  
Effiette Sauer ◽  
Sinisa Vukovic
Keyword(s):  
Aqueous Solutions ◽  
Rate Constant ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
High Rate ◽  
Group A ◽  
Stable Product ◽  
High Concentrations ◽  
Conjugate Base

The competition between 2'-deoxyguanosine (dG) and water has been quantitatively evaluated for the allylic carbocation derived from tamoxifen and for the stabilized diarylmethyl cation (bis-(4-methoxyphenyl)methyl). Both systems were examined by the competition kinetics method, in which the products were quantitatively analyzed after the SN1 solvolysis of the corresponding acetate esters in aqueous solutions containing the nucleoside. The principal product of the reaction of both cations with dG is the adduct at the NH2 group, a characteristic of delocalized carbocations. The tamoxifen cation was also examined by laser flash photolysis, with absolute rate constants for the reaction with dG and water being obtained and converted into rate constant ratios. The principal result of this study is that there is a three orders of magnitude difference in the reactivity of these cations towards the neutral form of dG and its conjugate base. Under acidic conditions where the reaction occurs with neutral dG, the guanine–water selectivity is low. Even at relatively high concentrations of dG, the majority of the product is alcohol derived from the water reaction. At pH 10 to 11, in contrast, dG is present as the anion and this is highly competitive. Yields of adduct as high as 90% can be attained. A consequence of the large difference in reactivities is that at neutral pH the majority of the reaction of the cation with dG is actually occurring via the small amount of conjugate base present. A further feature of the results is that the NH2 adduct is the predominant stable product from the anion. To explain the high rate constant for the reaction forming this product, a mechanism is proposed whereby one of the protons of the NH2 group is transferred to N1 as the N2-cation bond is forming.Key words: guanine, DNA adduct, carbocation, tamoxifen.

Photochemical reaction kinetics and mechanism of bisphenol A with K2S2O8 in aqueous solution: a laser flash photolysis study

2021 ◽  
Vol 99 (1) ◽  
pp. 43-50
Author(s):  
Yongchao Zhu ◽  
Mengyu Zhu ◽  
Jingjing Xie ◽  
Yadong Hu ◽  
Ying Liu ◽  
...  
Keyword(s):  
Bisphenol A ◽  
Rate Constant ◽  
Photochemical Reaction ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Phenoxyl Radical ◽  
Laser Flash ◽  
Kinetics And Mechanism ◽  
Main Reaction ◽  
Specific Rate

The photochemical reaction kinetics and mechanism of bisphenol A (BPA) with potassium persulfate (K2S2O8) were investigated by using 266 nm laser flash photolysis and gas chromatography mass spectrum (GC-MS) technique. Sulfate radical (SO4•−), generated upon K2S2O8 photolysis, reacted with BPA with the overall rate constant of (1.61 ± 0.15) × 109 L mol−1 s−1, and two main reaction mechanisms were involved. One was addition channel to generate BPA–SO4•− adduct with a specific second-order rate constant of (1.09 ± 0.15) × 109 L mol−1 s−1. Molecular oxygen was involved in the decay of the BPA–SO4•− adduct with a rate constant of (1.28 ± 0.14) × 108 L mol−1 s−1. Another channel was the formation of BPA’s phenoxyl radical, likely derived from a deprotonation of the cation radical (BPA•+) generated from single electron transfer reactions. The specific rate constant of BPA’s phenoxyl radical formation was determined to be (6.16 ± 0.08) × 108 L mol−1 s−1. The overall rate constant was in line with the sum of aforementioned two specific rate constants for two main reaction channels. By comparing these rate constants, it was indicated that SO4•− addition channel accounted for ∼65% (1.09/1.61) to the overall reaction, and phenoxyl radical formation accounted for only ∼35% (0.62/1.61). The transformation products of BPA were identified by using GC-MS including 4-isopropylphenol, 4-isopropenylphenol, and 2,4-di-tert-butylphenol, and the reaction mechanism was proposed. These results may provide microscopic kinetics and mechanism information on BPA degradation using SO4•−-based advanced oxidation processes.

Flash photolysis production of the tetrahedral intermediate of the methanolysis of methyl benzoate. Direct measurement of the rate of breakdown of the conjugate base form

1990 ◽  
Vol 68 (3) ◽  
pp. 375-382 ◽  
Author(s):  
Robert A. McClelland ◽  
V. M. Kanagasabapathy ◽  
Steen Steenken
Keyword(s):  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Carbonyl Oxygen ◽  
Methyl Benzoate ◽  
Ion Concentration ◽  
Hydroxide Ion ◽  
Tetrahedral Intermediate ◽  
Conjugate Base

Laser flash photolysis in aqueous basic solutions of the ortho acid derivatives 1-(phenyldimethoxymethyl)benzimidazole 2 and 4-bromo-1-(phenyldimethoxymethyl)imidazole 3 results in production of the phenyldimethoxymethyl cation, which has λmax at 260 nm. The cation decays in reactions with water (k = 9.9 × 104 s−1) and hydroxide ion (2.5 × 108 M−1 s−1) to finally yield methyl benzoate, whose formation was monitored at 234 nm. In solutions with pH 10–12, rate constants measured at this wavelength are the same as those obtained at 260 nm, but with pH > 13 and pH < 9, rate constants at 234 nm are smaller. With pH 9–10 and pH 12–13, single exponential kinetics are not observed at 234 nm. This behavior is interpreted in terms of a scheme where at each pH there are two consecutive first-order reactions, cation → phenyldimethoxyhydroxymethane (5) → ester, and the pH dependencies of the rate constants are such that they cross twice over the pH range of this study. The intermediate 5 is the tetrahedral intermediate formed in the methanolysis of methyl benzoate, and the 234-nm buildup at pH > 13 and pH < 9 directly measures its breakdown. At pH > 13 the rate constant is independent of pH with k = 9 × 106 s−1. This represents the rapid expulsion of methoxide from the conjugate base of 5. At pH < 9 the rate constants are proportional to hydroxide ion concentration, with [Formula: see text]. In these solutions the neutral intermediate predominates and the dependence on [OH−] of its rate of conversion to ester is interpreted in terms of breakdown of the anion and protonation of this species by water occurring at comparable rates. Thus, [Formula: see text] represents a situation where there is partial rate-limiting deprotonation of the neutral intermediate by hydroxide. The intermediate of this study bears a close resemblance to the tetrahedral intermediate of the hydrolysis of methyl benzoate. The observation that the anionic forms of such intermediates undergo breakdown at rates similar to those associated with the establishment of proton transfer equilibrium explains why the ester undergoes carbonyl oxygen exchange in base at a rate slower than hydrolysis. Keywords: tetrahedral intermediate, flash photolysis, ester hydrolysis.

Intermediates formed by laser flash photolysis of [PtCl6]2– in aqueous solutions

2005 ◽  
Vol 4 (11) ◽  
pp. 897 ◽  
Author(s):  
Irene V. Znakovskaya ◽  
Yulia A. Sosedova ◽  
Evgeni M. Glebov ◽  
Vjacheslav P. Grivin ◽  
Victor F. Plyusnin
Keyword(s):  
Aqueous Solutions ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash

A reinvestigation of the interaction between triplet states of cyclohexenones and amines

1988 ◽  
Vol 66 (10) ◽  
pp. 2595-2600 ◽  
Author(s):  
D. Weir ◽  
J. C. Scaiano ◽  
D. I. Schuster
Keyword(s):  
Triplet State ◽  
Rate Constant ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Radical Cations ◽  
Laser Flash ◽  
Triplet States ◽  
New Evidence

Laser flash photolysis studies lead to the conclusion that the short-lived triplet states of cyclohexenones are readily quenched by amines. For example, in the case of 2-cyclohexen-1-one (1) its triplet state (τT = 40 ns in acetonitrile) is quenched by triethylamine with a rate constant of (9.0 ± 0.8) × 107 M−1 s−1. Cyclohexenone triplets are also quenched efficiently by DABCO and by triphenylamine leading to the formation of the corresponding amine radical cations. The new evidence reported rules out the involvement of long-lived detectable exciplexes.

Formation and Direct Detection of Non-Conjugated Triplet 1,2-Biradical from β,γ-Vinylarylketone

2015 ◽  
Vol 68 (11) ◽  
pp. 1707 ◽  
Author(s):  
H. Dushanee M. Sriyarathne ◽  
Kosala R. S. Thenna-Hewa ◽  
Tianeka Scott ◽  
Anna D. Gudmundsdottir
Keyword(s):  
Rate Constant ◽  
Density Functional ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Direct Detection ◽  
Density Functional Theory Calculations ◽  
Laser Flash ◽  
Triplet Excited State ◽  
Functional Theory

Laser flash photolysis of 2-methyl-1-phenylbut-3-en-1-one (1) conducted at irradiation wavelengths of 266 and 308 nm results in the formation of triplet 1,2-biradical 2 that has λmax at 370 and 480 nm. Biradical 2 is formed with a rate constant of 1.1 × 107 s–1 and decays with a rate constant of 2.3 × 105 s–1. Isoprene-quenching studies support the notion that biradical 2 is formed by energy transfer from the triplet-excited state of the ketone chromophore of 1. Density functional theory calculations were used to verify the characterization of triplet biradical 2 and validate the mechanism for its formation. Thus, it has been demonstrated that intramolecular sensitization of simple alkenes can be used to form triplet 1,2-biradicals with the two radical centres localized on the adjacent carbon atoms.

Photolysis of aqueous solutions of aniline-2,5-disulfonic acid: steady state and laser flash photolysis studies

2002 ◽  
Vol 1 (7) ◽  
pp. 514-519 ◽  
Author(s):  
Jaouad Elgouch ◽  
Carole Catastini ◽  
Bernadette Lavedrine ◽  
Ghislain Guyot ◽  
Mohamed Sarakha
Keyword(s):  
Steady State ◽  
Aqueous Solutions ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Laser Flash ◽  
Disulfonic Acid
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