A high‐pressure mass spectrometric and density functional theory investigation of the thermochemical properties and structure of protonated dimers and trimers of glycine

Raspopov, Serguei A.; McMahon, T. B.

doi:10.1002/jms.908

Cited by 30 publications

(35 citation statements)

References 27 publications

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“…Recently, the proton-bound dimers of the simplest aliphatic amino acids were reported in the 700-2000 cm À1 region as well as the glycine proton-bound dimer in the O-H/N-H stretching region (Atkins et al, 2008). These spectroscopic studies confirmed previous thermochemical and computational studies (Raspopov & McMahon, 2005) which proposed that the structures of these species are ion-dipole complexes between a N-protonated amino acid and the carboxyl end of the other amino acid rather than proton-bound dimers bound by the amino groups of both amino acids. The spectrum of the proton-bound glycine dimer in the high-energy region also showed evidence for very strong intramolecular hydrogen bonding in the form of broad bands extending down to 2800 cm À1 as well as an absorption assigned to the shared proton stretching vibration.…”

Section: Infrared Spectroscopy Of Biologically Significant Ionssupporting

confidence: 82%

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Fridgen

2009

Mass Spectrometry Reviews

202

179

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In this article, the new and exciting techniques of infrared consequence spectroscopy (sometimes called action spectroscopy) of gaseous ions are reviewed. These techniques include vibrational predissociation spectroscopy and infrared multiple photon dissociation spectroscopy and they typically complement one another in the systems studied and the information gained. In recent years infrared consequence spectroscopy has provided long-awaited direct evidence into the structures of gaseous ions from organometallic species to strong ionic hydrogen bonded structures to large biomolecules. Much is being learned with respect to the structures of ions without their stabilizing solvent which can be used to better understand the effect of solvent on their structures. This review mainly covers the topics with which the author has been directly involved in research: structures of proton-bound dimers, protonated amino acids and DNA bases, amino acid and DNA bases bound to metal ions and, more recently, solvated ionic complexes. It is hoped that this review reveals the impact that infrared consequence spectroscopy has had on the field of gaseous ion chemistry.

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Section: Infrared Spectroscopy Of Biologically Significant Ionssupporting

confidence: 82%

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Fridgen

2009

Mass Spectrometry Reviews

202

179

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“…By contrast, in aqueous solution, the reverse stability order is observed and the question of as to whether a comparable situation exists inside protonated clusters may be asked. Indeed several recent studies show that the two forms, covalent and zwitterionic, may intervene in clusters (Julian, Hodyss, & Beauchamp, 2001; Raspopov & McMahon, 2005; Wu & McMahon, 2005). The thermochemistry of gas‐phase interaction between protonated glycine and ammonia has been studied both experimentally by high‐pressure mass spectrometry and theoretically (Wu & McMahon, 2005).…”

Section: Structural and Energetic Aspects Of The Protonationmentioning

confidence: 99%

Gas‐phase basicities of polyfunctional molecules. Part 1: Theory and methods

Bouchoux

2007

Mass Spectrometry Reviews

116

197

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The experimental and theoretical methods of determination of gas-phase basicities, proton affinities and protonation entropies are presented in a tutorial form. Particularities and limitations of these methods when applied to polyfunctional molecules are emphasized. Structural effects during the protonation process in the gas-phase and their consequences on the corresponding thermochemistry are reviewed and classified. The role of the nature of the basic site (protonation on non-bonded electron pairs or on p-electron systems) and of substituent effects (electrostatic and resonance) are first examined. Then, linear correlations observed between gas-phase basicities and ionization energies or substituent constants are recalled. Hydrogen bonding plays a special part in proton transfer reactions and in the protonation characteristics of polyfunctional molecules. A survey of the main properties of intermolecular and intramolecular hydrogen bonding in both neutral and protonated species is proposed. Consequences on the protonation thermochemistry, particularly of polyfunctional molecules are discussed. Finally, chemical reactions which may potentially occur inside protonated clusters during the measurement of gas-phase basicities or inside a protonated polyfunctional molecule is examined. Examples of bond dissociations with hydride or alkyl migrations, proton transport catalysis, tautomerization, cyclization, ring opening and nucleophilic substitution are presented to illustrate the potentially complex chemistry that may accompany the protonation of polyfunctional molecules. # 2007 Wiley Periodicals, Inc., Mass Spec Rev 26:775-835, 2007

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“…For instance, a high-pressure mass spectrometric and density functional theory investigation of the thermochemical properties and structure of protonated dimers and trimers of glycine was reported by Raspopov and McMahon. [38] Atkins et al [39] carried out a IR multiple photon dissociation spectra study on proton-and sodium-ion-bound glycine dimers.…”

mentioning

confidence: 99%

Glycine Dimers: Structure, Stability, and Medium Effects

Friant-Michel

Ruiz‐López

2010

ChemPhysChem

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We report a study on different ionization states and conformations of the bimolecular (Gly)(2) system by means of quantum mechanical calculations. Optimized geometries for energy minima of the glycine dimer, as well as relative energies and free energies were computed as a function of the medium: gas phase, nonpolar polarizable solvent, and aqueous solution. The polarizable continuum model was employed to account for solvation effects. Energy calculations were done using the MP2/aug-cc-pVTZ and B3LYP/6-311+G(2df,2p) methods on B3LYP/6-31+G(d,p) optimized structures (some single-point energy calculations were also done using the B3PW91 and PBE1KCIS methods). Ionized forms of the glycine dimer (either zwitterion-zwitterion or neutral-zwitterion) are predicted to exist in all media, in contrast to amino acid monomers. In aqueous solution, dimerization is an exergonic process (-4 kcal mol(-1)). Thus, according to our results, zwitterion-zwitterion Gly dimers might be abundant in supersaturated glycine aqueous solutions, a fact that has been connected with the structure of α-glycine crystals but that remains controversial in the literature. Another noticeable result is that zwitterion-zwitterion interactions are substantially underestimated when computed using methods based on density functional theory. For comparison, some calculations for the dimer of the simplest chiral amino acid alanine were done as well and differences to the glycine dimer are discussed.

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A high‐pressure mass spectrometric and density functional theory investigation of the thermochemical properties and structure of protonated dimers and trimers of glycine

Cited by 30 publications

References 27 publications

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Gas‐phase basicities of polyfunctional molecules. Part 1: Theory and methods

Glycine Dimers: Structure, Stability, and Medium Effects

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