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This result provides further evidence that while the acylation rate is influenced mainly by polarization, consistent with an addition elimination-type mechaddition elimination-typees specific recognition of the prochiral fluoromechanismoup to position the α-carbon for proton abstraction catalyzedeacylation, which prequiresially abspecificthe precognitionn.
Furthermore, the proton abstraction plays an important role in tuning the second-order NLO response.
We investigated the ability of hydrazone derived from 2,4-dinitrophenylhydrazine to detect CN− by UV vis spectroscopy involving the NH proton abstraction by cyanide ions.
The kinetics is mainly determined by the formation of a van der Waals complex in the first channel and the proton abstraction in the second channel of oxidation.
Kinetic data obtained from experimental proton exchange rates are correlated with thermodynamic data for the proton abstraction based on the density functional theory (DFT) calculations.
The tyrosine acts as the base in the initial proton abstraction, and evidence is provided that the reaction proceeds via an enol intermediate.
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In this work, by employing selected aromatic ketones as proton donors (with pKas≈19), it has been possible to accelerate the rate of the α-proton abstraction by O2− to the point that it is observable within the time scale of cyclic voltammetry.
The resulting azaquinone methide 8, which exhibits zwitterionic character (8′), undergoes 1,6-proton abstraction to form azomethine ylide 9.
The proton-abstraction by O2− from weakly acidic compounds, like aliphatic ketones (with pKas≈21), is endothermic and consequently slow.
A 4-fold difference in the rates of deacylation of (S)- and (R -2-fluoropropionyl-CoA suggested that FlK might utilize chiR -2-fluoropropionyl-CoAR -2-fluoropropionyl-CoAoup of fluoR -2-fluoropropionyl-CoAylation suggestedpecifically posithat one proton FlK abstraction.
In this regard, FlK utilizes chiral recognition of fluoroacetyl-CoA's prochiral fluoromethyl group to position the pro- R proton for preferential abstraction by His 76, indicating that specificity is based not only on the unique reactivity of fluorinated compounds but also potentially on fluorine molecular recognition.
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