scholarly journals The role of electrostatic induction in secondary isotope effects on acidity: theory and computational confirmation

2014 ◽  
Vol 38 (8) ◽  
pp. 3840-3852 ◽  
Author(s):  
E. Amitai Halevi
Keyword(s):  
Aqueous Solution ◽  
Gas Phase ◽  
Isotope Effects ◽  
Electrostatic Induction

How well can secondary isotope effects on acidity in aqueous solution be approximated by gas-phase computations on the hydrated components?

scholarly journals Study of the factors that determine the transfer of water and organic compounds into the gas phase from aqueous solutions in a discharge with a liquid cathode

2021 ◽  
Vol 2100 (1) ◽  
pp. 012025
Author(s):  
A V Chistolinov ◽  
M A Khromov ◽  
R V Yakushin ◽  
M Kh Gadzhiev ◽  
A S Tyuftyaev
Keyword(s):  
Aqueous Solution ◽  
Free Surface ◽  
Aqueous Solutions ◽  
Gas Phase ◽  
Organic Compounds ◽  
Direct Current ◽  
Current Discharge ◽  
Liquid Cathode ◽  
Direct Current Discharge

Abstract A study was performed to investigate the transfer of organic compounds and water from an aqueous solution to the gas phase under the action of a direct current discharge, in which an aqueous solution that contains organic compounds plays the role of a cathode. The effect of the area of the free surface of a liquid in various reactors, as well as the effect of the stirring mode of a solution near the surface of a liquid on the rate of transfer of water and organic compounds under the action of a discharge of this type, have been investigated. It is shown that a change in the area of the free surface of a liquid has no significant effect on the rate of transfer of water and organic compounds from solution to the gas phase under the action of a direct current discharge with a liquid cathode. It is shown that the stirring mode and the temperature of the solution, on the contrary, have a very significant effect on the rate of nonequilibrium transfer of both water and organic compounds from solution to the gas phase under the action of a discharge with a liquid cathode.

Role of hydrophobic residues for the gaseous formation of helical motifs

2019 ◽  
Vol 55 (35) ◽  
pp. 5147-5150 ◽  
Author(s):  
Lin Liu ◽  
Xin Dong ◽  
Yichang Liu ◽  
Nicklas Österlund ◽  
Astrid Gräslund ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Aqueous Solution ◽  
Secondary Structure ◽  
Gas Phase ◽  
Hydrophobic Residues ◽  
Secondary Structure Content

The secondary structure content of proteins and their complexes may change significantly on passing from aqueous solution to the gas phase (as in mass spectrometry experiments).

scholarly journals Reply to the ‘Comment on “The role of electrostatic induction in secondary isotope effects on acidity”’ by C. L. Perrin, New J. Chem., 2015, 39, DOI: 10.1039/C4NJ01887G

2015 ◽  
Vol 39 (2) ◽  
pp. 1522-1524 ◽  
Author(s):  
E. Amitai Halevi
Keyword(s):  
Isotope Effects ◽  
Harmonic Frequencies ◽  
Vibrational Anharmonicity ◽  
Electrostatic Induction

Shifts of harmonic frequencies suffice to explain isotope effects, but it does not follow that vibrational anharmonicity can be neglected.

scholarly journals Comment on “The role of electrostatic induction in secondary isotope effects on acidity” by E. A. Halevi, New J. Chem., 2014, 38, 3840

2015 ◽  
Vol 39 (2) ◽  
pp. 1517-1521 ◽  
Author(s):  
Charles L. Perrin
Keyword(s):  
Isotope Effects ◽  
Electrostatic Induction ◽  
Deuterium Isotope Effects

We reject Halevi's interpretation and reaffirm our conclusion that secondary deuterium isotope effects on acidity are due to n–σ* delocalization.

Kinetic deuterium isotope effect in the reaction of methyl iodide with thiosulfate ion in aqueous solution

1970 ◽  
Vol 48 (9) ◽  
pp. 1452-1455
Author(s):  
Alfred V. Willi ◽  
Chong Min Won
Keyword(s):  
Aqueous Solution ◽  
Gas Phase ◽  
Isotope Effect ◽  
Methyl Iodide ◽  
Isotope Effects ◽  
Force Constants ◽  
Deuterium Isotope Effect ◽  
Model Calculations ◽  
Bending Force ◽  
Reaction Vessels

The kinetic deuterium isotope effect in the reaction of methyl iodide with thiosulfate ion in aqueous solution has been determined as follows: kH/kD (per 3D) = 0.966 (+0.02°), 0.968 (+10.00°), 0.970 (+19.98°). Kinetic experiments have been carried out in reaction vessels with no gas phase. The experimental data are compared with results of model calculations of isotope effects from force constants. Excellent agreement between experimental and calculated isotope effects may be obtained with the following values of the transition state bending force constants: fHCI = 0.295 mdyn Å, fHCS = 0.300 to 0.320 mdyn Å. These values are equal to 50–65% of the corresponding bending force constants in stable molecules.

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