Free Energies of Hydration in the Gas Phase of Some Phosphate Singly and Doubly Charged Anions:  (HO)2PO2-(Orthophosphate), (HO)O2POPO2(OH)2-(Diphosphate), Ribose 5-Phosphate, Adenosine 5‘-Phosphate, and Adenosine 5‘-Diphosphate

1996 ◽  
Vol 100 (6) ◽  
pp. 2443-2446 ◽  
Author(s):  
Arthur T. Blades ◽  
Yeunghaw Ho ◽  
Paul Kebarle
Keyword(s):  
Gas Phase ◽  
Free Energies ◽  
Doubly Charged

2-Deoxyribose Radicals in the Gas Phase and Aqueous Solution. Transient Intermediates of Hydrogen Atom Abstraction from 2-Deoxyribofuranose

2005 ◽  
Vol 70 (11) ◽  
pp. 1769-1786 ◽  
Author(s):  
Luc A. Vannier ◽  
Chunxiang Yao ◽  
František Tureček
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Atom ◽  
Gas Phase ◽  
Computational Study ◽  
Hydrogen Atom Abstraction ◽  
Oh Radical ◽  
Free Energies ◽  
Intramolecular Hydrogen ◽  
Solvation Free Energies ◽  
Transient Intermediates

A computational study at correlated levels of theory is reported to address the structures and energetics of transient radicals produced by hydrogen atom abstraction from C-1, C-2, C-3, C-4, C-5, O-1, O-3, and O-5 positions in 2-deoxyribofuranose in the gas phase and in aqueous solution. In general, the carbon-centered radicals are found to be thermodynamically and kinetically more stable than the oxygen-centered ones. The most stable gas-phase radical, 2-deoxyribofuranos-5-yl (5), is produced by H-atom abstraction from C-5 and stabilized by an intramolecular hydrogen bond between the O-5 hydroxy group and O-1. The order of radical stabilities is altered in aqueous solution due to different solvation free energies. These prefer conformers that lack intramolecular hydrogen bonds and expose O-H bonds to the solvent. Carbon-centered deoxyribose radicals can undergo competitive dissociations by loss of H atoms, OH radical, or by ring cleavages that all require threshold dissociation or transition state energies >100 kJ mol-1. This points to largely non-specific dissociations of 2-deoxyribose radicals when produced by exothermic hydrogen atom abstraction from the saccharide molecule. Oxygen-centered 2-deoxyribose radicals show only marginal thermodynamic and kinetic stability and are expected to readily fragment upon formation.

Dissociation Behavior of Doubly-Charged Tryptic Peptides:  Correlation of Gas-Phase Cleavage Abundance with Ramachandran Plots

2004 ◽  
Vol 126 (10) ◽  
pp. 3034-3035 ◽  
Author(s):  
Yingying Huang ◽  
Joseph M. Triscari ◽  
Ljiljana Pasa-Tolic ◽  
Gordon A. Anderson ◽  
Mary S. Lipton ◽  
...  
Keyword(s):  
Gas Phase ◽  
Tryptic Peptides ◽  
Ramachandran Plots ◽  
Doubly Charged

THEORETICAL CALCULATION OF pKb VALUES FOR ANILINES AND SULFONAMIDE DRUGS IN AQUEOUS SOLUTION

2012 ◽  
Vol 11 (02) ◽  
pp. 283-295 ◽  
Author(s):  
BAHRAM GHALAMI-CHOOBAR ◽  
ALI GHIAMI-SHOMAMI ◽  
PARIA NIKPARSA
Keyword(s):  
Gas Phase ◽  
Continuum Model ◽  
Correlation Equation ◽  
Polarizable Continuum Model ◽  
Free Energies ◽  
Pcm Model ◽  
Solvation Models ◽  
Polarizable Continuum ◽  
Better Than ◽  
Good Agreement

In this work, calculations of p K b values have been performed for aniline and its substituted derivatives and sulfonamide drugs by using Gaussian 98 software package. Gas-phase energies were calculated with HF /6-31 G ** and B3LYP /6-31 G ** levels of theory. Free energies of solvation have been computed using the polarizable continuum model (PCM), conductor-like polarizable continuum model (CPCM) and the integral equation formalism-polarizable continuum model (IEFPCM) at the same levels which have been used for geometry determination in the gas-phase. The results show that the calculated p K b values using the B3LYP /6-31 G ** are better than those using the corresponding HF /6-31 G **. At first, the correlation equation was found to determine the p K b values of the investigated anilines. Then, this correlation equation was used to calculate the p K b values of the sulfonamide drugs. The results obtained indicate that the PCM model is a suitable solvation model for calculating p K b values in comparison to the other solvation models. For the investigated compounds a good agreement between the experimental and the calculated p K b values was also observed.

Serine–Ca2+ versus serine–Cu2+ complexes — A theoretical perspective

2010 ◽  
Vol 88 (8) ◽  
pp. 759-768 ◽  
Author(s):  
Al Mokhtar Lamsabhi ◽  
Otilia Mó ◽  
Manuel Yáñez
Keyword(s):  
Gas Phase ◽  
Electron Density ◽  
Potential Energy Surfaces ◽  
Metal Ion ◽  
Theoretical Perspective ◽  
Binding Energies ◽  
Interacting Systems ◽  
Intramolecular Hydrogen ◽  
Energy Surfaces ◽  
Doubly Charged

The association of Ca2+ and Cu2+ to serine was investigated by means of B3LYP DFT calculations. The [serine–M]2+ (M = Ca, Cu) potential energy surfaces include, as does the neutral serine, a large number of conformers, in which a drastic reorganization of the electron density of the serine moiety is observed. This leads to significant changes in the number and strength of the intramolecular hydrogen bonds existing in the neutral serine tautomers. In some cases, a proton is transferred from the carboxylic OH group to the amino group and accordingly, some of the more stable [serine–M]2+ complexes can be viewed as the result of the interaction of the zwiterionic form of serine with the doubly charged metal ion. Whereas the interaction between Ca2+ and serine is essentially electrostatic, that between Cu2+ and serine has a non-negligible covalent character, reflected in larger electron densities at the bond critical points between the metal and the base, in the negative values of the electron density between the two interacting systems, and in much larger Cu2+ than Ca2+ binding energies. More importantly, the interaction with Cu2+ is followed by a partial oxidation of the base, which is not observed when the metal ion is Ca2+. The main consequence is that in Cu2+ complexes a significant acidity enhancement of the serine moiety takes place, which strongly favors the deprotonation of the [serine–Cu]2+ complexes. This is not the case for Ca2+ complexes. Thus, [serine–Ca]2+ complexes, like those formed by urea, thiourea, selenourea, or glycine, should be detected in the gas phase. Conversely, the complexes with Cu2+ should deprotonate spontaneously and therefore only [(serine–H)–Cu]+ monocations should be experimentally accessible.

Pyrolysis of Methane to Higher Hydrocarbons: A Thermodynamic Study

1989 ◽  
Vol 42 (10) ◽  
pp. 1655 ◽  
Author(s):  
FP Larkins ◽  
AZ Khan
Keyword(s):  
Gas Phase ◽  
Pressure Range ◽  
Solid Carbon ◽  
Free Energies ◽  
Oxidation Of Methane ◽  
Conversion Of Methane ◽  
Equilibrium Conversion ◽  
Benzene Toluene ◽  
Higher Hydrocarbons ◽  
The Individual

Some basic thermodynamic parameters such as Gibbs free energies, enthalpies of reactions and equilibrium compositions of products from the pyrolysis and partial oxidation of methane to higher hydrocarbons in the gas phase have been determined within a consistent framework for the temperature range 800-1500 K and the pressure range 0.1-3 MPa , by using the CSIRO-SGTE THERMODATA system. It has been established that the pyrolysis of methane to higher hydrocarbons, e.g. acetylene, ethylene, ethane, prop-1-ene, propane, benzene, toluene, naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, considered as separate reactions, is a highly endothermic reaction with the Gibbs free energies for the individual reactions being positive until 1300 K. The aromatics are thermodynamically most favoured with the equilibrium yields increasing with temperature. Addition of O2 lowers the heats of synthesis and the free energies for methane conversion but no enhancement in the equilibrium yields of hydrocarbons is observed. When solid carbon is allowed, it is the dominant product in all cases with the equilibrium yields for all hydrocarbons becoming negligible. Increasing the pressure at a particular temperature has more effect on the lowering of the equilibrium conversion of methane than on the suppression of solid carbon. Such data are valuable for understanding the conversion limits for methane into higher hydrocarbons.

Generation and Characterization of Gas-Phase Doubly Charged Biradical Peptide Ions (M2+••)

2017 ◽  
Vol 89 (14) ◽  
pp. 7773-7780 ◽  
Author(s):  
Y. L. Elaine Wong ◽  
Xiangfeng Chen ◽  
Ri Wu ◽  
Y. L. Winnie Hung ◽  
Hoi Sze Yeung ◽  
...  
Keyword(s):  
Gas Phase ◽  
Peptide Ions ◽  
Doubly Charged
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