Journal ArticleDOI
Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer
Dieter Rehm,Albert Weller +1 more
TLDR
In this article, the rate constants of 60 typical electron donor-acceptor systems have been measured in de-oxygenated acetonitrile and are shown to be correlated with the free enthalpy change, ΔG23, involved in the actual electron transfer process.Abstract:
Fluorescence quenching rate constants, kq, ranging from 106 to 2 × 1010 M−1 sec−1, of more than 60 typical electron donor-acceptor systems have been measured in de-oxygenated acetonitrile and are shown to be correlated with the free enthalpy change, ΔG23, involved in the actual electron transfer process
in the encounter complex and varying between + 5 and −60 kcal/mole. The correlation which is based on the mechanism of adiabatic outer-sphere electron transfer requires ΔG≠23, the activation free enthalpy of this process to be a monotonous function of ΔG23 and allows the calculation of rate constants of electron transfer quenching from spectroscopic and electrochemical data.
A detailed study of some systems where the calculated quenching constants differ from the experimental ones by several orders of magnitude revealed that the quenching mechanism operative in these cases was hydrogen-atom rather than electron transfer.
The conditions under which these different mechanisms apply and their consequences are discussed.read more
Citations
More filters
Journal ArticleDOI
Silyl Glyoxylates as a New Class of High Performance Photoinitiators: Blue LED Induced Polymerization of Methacrylates in Thin and Thick Films
Mariem Bouzrati-Zerelli,Julie Kirschner,Christoph P. Fik,Maximilian Maier,Céline Dietlin,Fabrice Morlet-Savary,Jean Pierre Fouassier,Jean-Michel Becht,Joachim E. Klee,Jacques Lalevée +9 more
TL;DR: Silyl glyoxylates are proposed in this paper as a new class of high performance type I photoinitiators for free radical polymerization under air or in laminate (e.g., (meth)acrylates) upon exposure to different near-UV (at 395 nm; at 405 nm) and blue (at 477 nm) LEDs.
Journal ArticleDOI
Electroactive Polymeric Networks Created by Oxidation of Oligothiophene‐Functionalized Perylene Bisimides
TL;DR: A series of fourfold oligothienyl-functionalized perylene bisimides, N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra(4-(7-[2,2′]bithien-5-yl)-heptanoyloxyphenoxy)perylene-3,4:9,10tetracarboxylic acid bisimide (7b), have been synthesized as mentioned in this paper.
Journal ArticleDOI
Simultaneous analysis of ultrafast fluorescence decays of FMN binding protein and its mutated proteins by molecular dynamic simulation and electron transfer theory.
Nadtanet Nunthaboot,Fumio Tanaka,Sirirat Kokpol,Haik Chosrowjan,Seiji Taniguchi,Noboru Mataga +5 more
TL;DR: Ultrafast fluorescence decays of FMN binding proteins (FBP) from Desulfovibrio vulgaris were analyzed with an electron transfer (ET) theory by Kakitani and Mataga and fit quite well with the observed ones of all WT, W32Y, and W32A.
Journal ArticleDOI
β-Carotene/Limonene Derivatives/Eugenol: Green Synthesis of Antibacterial Coatings under Visible-Light Exposure
Louise Breloy,Célia Ait Ouarabi,Arnaud Brosseau,Pierre Dubot,Vlasta Brezová,Samir Abbad Andaloussi,Jean-Pierre Malval,Davy-Louis Versace +7 more
TL;DR: In this article, the use of β-carotene as a natural photosensitizer for both the cationic photopolymerization and thiol-ene click reactions under visible-light irradiation was reported.
Journal ArticleDOI
Evidence for generation of electronically excited radical ion in very exothermic electron-transfer fluorescence quenching
Koichi Kikuchi,Tomoharu Katagiri,Taeko Niwa,Yasutake Takahashi,Takanori Suzuki,Hiroshi Ikeda,Tsutomu Miyashi +6 more
TL;DR: In this article, the free radical yield of electron-transfer fluorescence quenching and the effective encounter distance are studied to determine the quench mechanism in very exothermic region.
References
More filters
Journal ArticleDOI
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
TL;DR: In this paper, a mechanism for electron transfer reactions is described, in which there is very little spatial overlap of the electronic orbitals of the two reacting molecules in the activated complex, and a quantitative theory of the rates of oxidation reduction reactions involving electron transfer in solution is presented.
Journal ArticleDOI
Chemical and Electrochemical Electron-Transfer Theory
TL;DR: In this article, a review of electron transfer reactions is presented, focusing on the absence of bond rupture in the reaction step, which is a unique feature of purely electron-transfer reactions.
Journal ArticleDOI
Polarographic Oxidation Potentials of Aromatic Compounds
E. S. Pysh,N. C. Yang +1 more
TL;DR: In this article, the oxidation half-wave potentials of fifty-three organic compounds were determined in acetonitrile at a rotating Pt electrode, and these values were correlated with ionization potentials, with interaction energies of charge transfer complexes with trinitrofluorenone, with Huckel coefficients of the resonance integral in the expression for the highest occupied molecular orbital energy level, and with pabsorption band spectra.
Journal ArticleDOI
Electron-transfer and complex formation in the excited state
TL;DR: In this paper, a broad structureless emission band about 5000 cm1 was observed to increase with increasing electron donor concentration at the expense of the fluorescence intensity of the hydrocarbon, thereby following the same Stern-Volmer-type relation as does the well known excimer fluorescence.