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
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Journal ArticleDOI
Development of new high-performance visible light photoinitiators based on carbazole scaffold and their applications in 3d printing and photocomposite synthesis
Mira Abdallah,Mira Abdallah,Mira Abdallah,Diego Magaldi,Akram Hijazi,Bernadette Graff,Bernadette Graff,Frédéric Dumur,Jean-Pierre Fouassier,Jean-Pierre Fouassier,Thanh-Tuân Bui,Fabrice Goubard,Jacques Lalevée,Jacques Lalevée +13 more
TL;DR: In this article, the carbazole scaffold was used for photoinitiators/photosensitizers for both the free-radical polymerization of methacrylates and the cationic polymerisation of epoxides upon visible light exposure using LED@405 nm.
Journal ArticleDOI
Fluorescence sensor design for transition metal ions: the role of the PIET interaction efficiency.
TL;DR: The present paper describes the feasibility of optimizing the PIET interaction in the multicomponent sensor system in unbound state, and thus transition metal ion signaling capability of the system.
Journal ArticleDOI
Oxidation Mechanism of NAD Dimer Model Compounds
TL;DR: In this article, a dimeric N-benzyldihydronicotinamide with various oxidants such as quinones, triphenyl carbenium ions and a triplet tris(bipyridine) ruthenium(II) complex was investigated.
Journal ArticleDOI
Rational Design of High-Performance Donor-Linker-Acceptor Hybrids Using a Schiff Base for Enabling Photoinduced Electron Transfer.
Hao-Hua Deng,Kai-Yuan Huang,Shao-Bin He,Li-Ping Xue,Hua-Ping Peng,Zha Daijun,Wei-Ming Sun,Xing-Hua Xia,Wei Chen +8 more
TL;DR: To the best of the knowledge, this is the first example of the development of a covalently bound D-L-A system for fluorescent PET sensing of enzyme activity based on AuNC nanoprobes, using a Schiff base.
Journal ArticleDOI
Probing of Nucleic Acid Structures, Dynamics, and Interactions With Environment-Sensitive Fluorescent Labels
Benoît Y. Michel,Dmytro Dziuba,Dmytro Dziuba,Rachid Benhida,Alexander P. Demchenko,Alain Burger +5 more
TL;DR: This review describes the means by which nucleobase replacement or modification with advanced fluorescent dyes that respond by the changing of their fluorescence parameters to their local environment (altered polarity, hydration, flipping dynamics, and formation/breaking of hydrogen bonds).
References
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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.