ESR study of products of transformation of 3,6-tert-butylpyrocatechol on alumina, zinca, silica, and titania

The formation of semiquinone and phenoxazyl radicals and metallocomplexes with semiquinone ligands was observed by ESR during the interaction of di-tert-butylpyrocatechol with Al₂O₃, ZnO, SiO₂, and TiO₂. In the case of different modifications of SiO₂, admixtures of TiO₂ exhibit a higher reactivity in complex formation with the organic substrate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1975–1978, October, 1998.     

竹红菌甲素敏化氧化还原型谷胱甘肽中的类型Ⅰ和类型Ⅱ反应

本文研究了竹红菌甲素和还原型谷胱甘肽(GluSH)间的光诱导氧化还原作用。甲素是3,10-二羟基-4,10-苝醌衍生物。在GluSH作为电子给体时,甲素经受可见光诱导的单电子还原,生成年醌自由基或二氢甲素,取决于pH值,同时GluSH被氧化。甲素的单电子还原量子效率随pH值增加而增加。在充氧溶液中甲素敏化氧化GluSH的反应通过类型Ⅰ和Ⅱ的混合机制进行。用ESR检测到了通过Fenton反应产生的羟基自由基。在脂质体包裹的甲素溶液中用动力学测定方法证明了甲素敏化GluSH的氧化是通过类型Ⅱ机制进行的。     

Anaerobic Reduction of Anthracycline Antibiotics and Their Model Compounds by Fe(II) Complexes

Abstract

Hydroxyanthraquinones, model compounds for anthracycline antibiotics, are reduced by Fe(II)-ADP and Fe(II)-phosphate complexes to produce semiquinone radicals. In case the corresponding hydroquinone is stable, two electron reduction is caused by the Fe(II)-phosphate complex, rather strong reducing agent.     

Synthesis of and structure–property relationships in zinc complexes of bis‐metaphenylene semiquinone biradical species

The design of novel, functionalized bis‐metaphenylene semiquinone (SQ) ligands and their corresponding metal complexes which combine conformational flexibility and electron‐withdrawing, electron‐donating, and conjugating substituents enable investigation of multiple structure–property relationships. Along these lines, we report the synthesis of three new bis(Zn^II(SQ)Tp^Cum,Me) complexes containing the bis‐metaphenylene coupling fragment. Using electron paramagnetic resonance spectroscopy, ab initio computations and superconducting quantum interference device magnetometry, we show how spin‐density is affected by the bis‐metaphenylene system substituents. Copyright © 2011 John Wiley & Sons, Ltd.     

Kinetics of the interaction of ketyl and semiquinone radicals with dioxygen. Concerted electron and proton transfer involving ketyl and semiquinone radicals

Kinetics of the interaction of ketyl and neutral semiquinone radicals with dioxygen was studied by the flash photolysis technique. The reactivity of neutral semiquinone radicals in the transfer of a hydrogen atom to O₂ is lower than that of ketyl radicals and increases as the reduction ability of the radicals increases, which give evidence for the charge transfer from the radicals to O₂ in the transition state of the reaction. The deuterium kinetic isotope effect of the reaction (up to 2.6) suggests considerable weakening of the O−H bond of the seminquinone radical in the transition state. A cyclic structure of the transition state similar to that in the reactions of ketyl radicals with hydrogen atom acceptors is proposed. In aprotic volvents, solvation has essentially no effect on the reactivity of neutral anthrasemiquinone radicals up to solvent nucleophilicityB≈240. In solvents with higher nucleophilicity and in protic solvents, their reactivity drops sharply. Hydrogen atom transfer reactions involving ketyl and neutral semiquinone radicals are shown to involve concerted electron and proton transfers, and to have transition states in which the partial transfer of an electron and a proton from the ketyl or semiquinone radical to an acceptor occurs. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1131–1137, June, 1997.     

Effect of solvation on the kinetic parameters of the reactions of phenoxyl radicals with phenols and semiquinone radicals with hydroquinones

Experimental rate constants of the reactions of semiquinone radicals with hydroquinones in chlorobenzene at ∼300 K are by almost an order of magnitude higher than the rate constants of the reactions of phenoxyl radicals with phenols, which are equivalent to the former ones by heat effects. To reveal differences in the rate constants of these groups of reactions, we performed quantum chemical calculations of the energy profiles of the reactions and dissociation energies by the B3LYP density functional theory using the GAMESS and GAUSSIAN-03 programs in the 6-31+G^* basis set. The solvation energies were calculated in all stationary points on the reaction coordinate by the method of polarized continuum model. In terms of the intersecting parabolas method, the reactions of semiquinone radicals with hydroquinones and phenoxyl radicals with phenols can be attributed to the same class of reactions only in the gas phase. In solvents this class of reactions is divided into two subclasses due to differences in solvation energies of the preliminary complexes and transition states of these reactions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1495–1501, September, 2006.     

Paramagnetic centers in oak and onion extracts

We have used EPR to study oak bark, bulb onion peel, and their aqueous extracts. We have established that their paramagnetic properties are determined by at least four types of paramagnetic centers: semiquinone radicals, Fe³⁺ ions, and two types of Mn²⁺ ions. We have observed that metal ions are extracted by water from the plant raw material without any change in their original coordination environment. The aqueous extracts were subjected to oxidative processes: mild oxidation in the dried state, strong oxidation when stored as solutions. We have shown that when the solutions are stored, the oxidation reaction is catalyzed by the metal ions and is accompanied by formation of semiquinone radicals. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 440–445, May–June, 2009.     

Stimuli-Responsive Resorcin[4]arene Cavitands: Toward Visible-Light-Activated Molecular Grippers

Resorcin[4]arene cavitands, equipped with diverse quinone ( Q ) and [Ru(bpy)₂dppz]²⁺ (bpy=2,2′-bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine) photosensitizing walls in different configurations, were synthesized. Upon visible-light irradiation at 420 nm, electron transfer from the [Ru(bpy)₂dppz]²⁺ to the Q generates the semiquinone ( SQ ) radical anion, triggering a large conformational switching from a flat kite to a vase with a cavity for the encapsulation of small guests, such as cyclohexane and heteroalicyclic derivatives, in CD₃CN. Depending on the molecular design, the SQ radical anion can live for several minutes (≈10 min) and the vase can be generated in a secondary process without need for addition of a sacrificial electron donor to accumulate the SQ state. Switching can also be triggered by other stimuli, such as changes in solvent, host–guest complexation, and chemical and electrochemical processes. This comprehensive investigation benefits the development of stimuli-responsive nanodevices, such as light-activated molecular grippers.