Arrhenius activation parameters for the loss of neutral nucleobases from deprotonated oligonucleotide anions in the gas phase

The kinetics and mechanism of the reactions of hydroxylamine and aminoxide anion with methyl iodide were studied with ab initio calculations, Monte-Carlo and QM/MM simulations in gas and aqueous phases. Geometrical parameters and charge calculations show that these reactions proceed through the SN2 (bimolecular nucleophilic displacement) mechanism only. The solvent effects on these reactions were studied by inserting water molecules in reaction media, Onsager model, Monte-Carlo and QM/MM simulations. Activation parameters indicate the expected variation in activation energy and rate coefficient in aqueous phase in comparison to the gas phase. The shift of potential energy barrier through the reactants or products for the studied reactions in the gas phase is in the opposite direction in comparison to the aqueous phase.

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Gas-Phase Kinetics and Activation Parameters for Thermal 1,5-Hydrogen Shifts Interconverting Monodeuterium-Labeled 1,3-Cyclohexadienes

The Journal of Organic Chemistry ◽

10.1021/jo048441e ◽

2005 ◽

Vol 70 (1) ◽

pp. 377-380 ◽

Cited By ~ 5

Author(s):

John E. Baldwin ◽

Bonnie R. Chapman

Keyword(s):

Gas Phase ◽

Activation Parameters ◽

Gas Phase Kinetics ◽

Hydrogen Shifts

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Residual Gas Reactions in the Electron Microscope: I. Qualitative Observations on the Water Gas Reaction

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100101207 ◽

1968 ◽

Vol 26 ◽

pp. 292-293

Author(s):

Richard E. Hartman ◽

Roberta S. Hartman ◽

Peter L. Ramos

Keyword(s):

Electron Beam ◽

Electron Microscope ◽

Gas Phase ◽

Absolute Temperature ◽

Residual Gas ◽

Gas Reactions ◽

Image Position ◽

The Right ◽

Water Gas ◽

Thinning Rate

The action of water and the electron beam on organic specimens in the electron microscope results in the removal of oxidizable material (primarily hydrogen and carbon) by reactions similar to the water gas reaction .which has the form:The energy required to force the reaction to the right is supplied by the interaction of the electron beam with the specimen.The mass of water striking the specimen is given by:where u = gH2O/cm2 sec, PH2O = partial pressure of water in Torr, & T = absolute temperature of the gas phase. If it is assumed that mass is removed from the specimen by a reaction approximated by (1) and that the specimen is uniformly thinned by the reaction, then the thinning rate in A/ min iswhere x = thickness of the specimen in A, t = time in minutes, & E = efficiency (the fraction of the water striking the specimen which reacts with it).

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Integration of Core-Edge Spectroscopy Methods for the Study of Polymers

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s042482010016323x ◽

1996 ◽

Vol 54 ◽

pp. 154-155

Author(s):

E. G. Rightor

Keyword(s):

Excited State ◽

Polymer Blends ◽

Gas Phase ◽

Spatial Resolution ◽

High Spatial Resolution ◽

Electronic States ◽

Core Electron ◽

Bulk Solids ◽

Development Application

Core edge spectroscopy methods are versatile tools for investigating a wide variety of materials. They can be used to probe the electronic states of materials in bulk solids, on surfaces, or in the gas phase. This family of methods involves promoting an inner shell (core) electron to an excited state and recording either the primary excitation or secondary decay of the excited state. The techniques are complimentary and have different strengths and limitations for studying challenging aspects of materials. The need to identify components in polymers or polymer blends at high spatial resolution has driven development, application, and integration of results from several of these methods.

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