We have previously performed empirical valence bond calculations of the kinetic activation barriers, Δ G‡calc, for the deprotonation of complexes between TIM and the whole substrate glyceraldehyde-3-phosphate (GAP, Kulkarni et al. J. Am. Chem. Soc. 2017 , 139 , 10514 - 10525 ). We now extend this work to also study the deprotonation of the substrate pieces glycolaldehyde (GA) and GA·HPi [HPi = ...

A series of 18 alcohols (ROH) has been designed with an enthalpy of deprotonation in the gas phase (H(DP)) in the range 13.8-16.3 eV. The effects of excess electron attachment to the binary alcohol-uracil (ROH...U) complexes have been studied at the density functional level with a B3LYP exchange-correlation functional and at the second-order Møller-Plesset perturbation theory level. The photoel...

A metal ion that attaches to a peptide backbone has the choice of binding to an amide carbonyl oxygen atom or to an amide nitrogen atom by replacement of the amide proton. Coordination to the nitrogen atom is normally accompanied by elimination of the proton, thereby resulting in deprotonation of the ligand. An alternative possibility, not involving deprotonation, is the unusual amide/iminol ta...

We have studied geometries, energies and vibrational spectra of disulfuric acid (H2S2O7) and its anion (HS2O7(-)) hydrated by a few water molecules, using density functional theory (M062X) and ab initio theory (SCS-MP2 and CCSD(T)). The most noteworthy result is found in H2S2O7(H2O)2 in which the lowest energy conformer shows deprotonated H2S2O7. Thus, H2S2O7 requires only two water molecules, ...

A broad range of acyclic primary and secondary 2,4,6-triisopropylbenzoate (TIB) esters have been used in lithiation-borylation reactions, but cyclic TIB not. We studied the use reactions looked at effect ring size (3- → 6-membered rings) on three key steps protocol: deprotonation, borylation 1,2-metalate rearrangement. Although all rings sizes could be deprotonated, cyclohexyl case was impracti...

Catalase peroxidases (KatG's) are bifunctional heme proteins that can disproportionate hydrogen peroxide (catalatic reaction) despite their structural dissimilarity with monofunctional catalases. Using X-ray crystallography and QM/MM calculations, we demonstrate that the catalatic reaction of KatG's involves deprotonation of the active-site Trp, which plays a role similar to that of the distal ...

Different reactivity parameters yield different results for the relative acidity of zeolitic Brønsted sites in thin films and in bulk materials. Whereas the adsorption energies of ammonia and pyridine are about the same, the energy of deprotonation is much lower for two-dimensional systems than for three-dimensional systems. It is shown that this is due to the smaller effective dielectric const...