Stacking Gaussian processes to improve $$pK_a$$ p K a predictions in the SAMPL7 challenge

Journal of Computer-Aided Molecular Design - Accurate predictions of acid dissociation constants are essential to rational molecular design in the pharmaceutical industry and elsewhere. There has...     

The competitive behavior for O2 and CO2 reaction during char oxy-fuel combustion: effects of temperature and inherent minerals

Journal of Thermal Analysis and Calorimetry - Coal O2/CO2 combustion is a promising carbon capture and storage technology for coal-fired power plant. Char consumption rate prediction is essential...     

Molecular design of ambipolar redox-active molecules II: closed-shell systems

This mini-review highlights key structural features that should be taken into account when creating ambipolar redox-active closed-shell metal-free molecules. This type of compound is strongly required for the fabrication of all-organic ‘poleless’ batteries and semiconductors. The suggested strategies aimed at stabilization of both oxidized (cationic) and reduced (anionic) redox-states are based on the comprehensive analysis of the most successful structures taken from the recent publications.     

Holography beyond conformal invariance and AdS isometry?

Journal of Experimental and Theoretical Physics - We suggest that the principle of holographic duality be extended beyond conformal invariance and AdS isometry. Such an extension is based on a...     

Reactions of Aryl Benzoates with Potassium Aryloxides: Solvent Effects on Reaction Pathway and Kinetics

Temperature dependences of the relative reactivity of potassium aryloxides XC₆H₄O^?K⁺ toward 2,4‐dinitrophenyl benzoate in 50 mol% dimethylformamide (DMF)–50 mol% H₂O mixture have been studied using the competitive reactions technique. Correlation analyses of the relative rate constants k_X/k_H and differences in the activation parameters (ΔΔН^≠ and ΔΔS^≠) of the competitive reactions have revealed the existence of two isokinetic series of the reactions of 2,4‐dinitrophenyl benzoate with potassium aryloxides with electron‐donating substituent (EDS) and electron‐withdrawing substituent (EWS), respectively. We have investigated the effect of the substituent X on the activation parameters for each isokinetic series and concluded that the mechanism of the reactions of 2,4‐dinitrophenyl benzoate with potassium aryloxides XC₆H₄O^?K⁺ in 50 mol% DMF–50 mol% H₂O mixture is the same as in DMF. Analysis of the obtained data with using the method of two‐dimensional reaction coordinate diagram leads to the conclusion that the variation of the solvent from DMF to 50 mol% DMF–50 mol% H₂O mixture affects the reaction pathway. The rate constant k_X for the reaction of 3‐nitrophenyl benzoate with potassium 4‐methoxyphenoxide and the relative rate constants k_X/k_H for the reaction of 3‐nitrophenyl benzoate with potassium aryloxides XC₆H₄O^?K⁺ with EDS were measured in 50 mol% DMF–50 mol% H₂O mixtures at 25°C, and it has been shown that the addition of water to DMF does not change the mechanism but slows down these reactions.