Proton transfer ultra-fast

Chattoraj M, King BA, Bublitz GU, Boxer SG (1996) Ultra-fast excited state dynamics in green fluorescent protein multiple states and proton transfer. Proc Natl Acad Sci USA 93 8362-8367... 

The solvated proton is not a point charge it exists in water in two solvated states of H30 aq and H502 aq and the location of the positive charge is smeared over the complex, as determined by quantum mechanical calculations. Any attempt to predict the location of a proton with 1A resolution is an overldir. With the present advances in structural biology, ultra-fast kinetic measurements and computational capabilities, the understanding of the mechanism of proton transfer at the interface should be based on experimental measurements capable of observing molecular events at a real time [2], coupled with an analysis that matches the molecular details of the reaction space. 

The purpose of this review has been to illustrate and document the kinds of information about non-aqueous solvent systems which have been obtained by vibrational spectroscopy. We have seen that these include insight into intermolecular forces and structure of the pure solvents, the nature of the solvation shell around ions and their solvation numbers, the identification of ion pairs and complexes, measurement of mass law constants and their dependence on the polarity of the solvent, the detection and characterisation of the hydrogen bond and measurement of acid and base strengths. Little kinetic data have so far been obtained by Raman spectroscopy but recent progress in the study of ultra-fast proton transfer and the detection of associated ions of type [Br , (Bra)] during the bromination of acetic acid presage considerable advance in this area in the future. ... 

Ultra-Fast Proton-Transfer Reactions (Grunwald). 

Lima JC, Abreu 1, Brouillard R, Maganita AL (1998) Kinetics of ultra-fast excited state proton transfer from 7-hydroxy-4-methylflavylium chloride to water. Chem Phys Lett 298 189-195... 

H-detected triple-resonance H/N/C experiments have been presented that incorporate CO-CA and CA-CB out-and-back scalar-transfer blocks optimized for robust resonance assignment in biosolids under ultra-fast MAS. The first experiment, (H)(CO)CA(CO)NH, pelds H-detected interresidue correlations, in which the chemical shifts of the CA spins are recorded in the first indirect dimension while during the scalar-transfer delays the coherences are present only on the longer-lived CO spins. The second experiment, (H)(CA)CB(CA)NH, correlates the side-chain CB chemical shifts with the NH of the same residue. These high sensitivity experiments are demonstrated on both fully-protonated and 100%-H-N... 

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