Selective reactivity of glycosyl cation stereoisomers: the role of intramolecular hydrogen bonding.

The impact of the stereochemistry of the glycosyl cation species upon its dynamic properties is examined together with their vibrational spectra in order to gain insight into the effects of configurational isomerism on conformer dynamics and proton mobility. Ab initio molecular dynamics (AIMD) simulations and infrared multiple photon dissociation (IRMPD) spectroscopy explore the conformational and reactive dynamics of two pairs of glycosyl cation isomers: (1) protonated α- and ß- anomers of methyl-D-galactopyranoside and (2) the oxocarbenium ions of the D-aldohexose C2 epimers galactose and talose. Analysis of these simulations together with experimental spectroscopy, interpreted by anharmonic calculations, points to the key role played by the intramolecular hydrogen bonds which are present in a unique pattern and extent in each isomer. We find that the reactivity of galactoside stereoisomers toward acid-catalyzed nucleophilic substitution, as gauged by the ability to form free oxocarbenium ions, differs markedly in a way that agrees with experimental measurements in the condensed phase. Other properties such as conformer stability and vibrational transitions were also found to reflect the characteristic hydrogen bonding interactions present in each isomer. In both systems, the stereochemistry is shown to determine the strength of intramolecular hydrogen bonding as well as between which substituents proton transfer is possible. We expect that the critical impact of non-covalent interactions on stereoisomer selectivity may be a widely found phenomenon whose effects should be further investigated.

Experimental and theoretical study of resonant core-hole spectroscopies of gas-phase free-base phthalocyanine.

We studied N 1s-1 inner-shell processes of the free base Phthalocyanine molecule, H2Pc, in the gas-phase. This complex organic molecule contains three different nitrogen sites defined by their covalent bonds. We identify the contribution of each site in ionized, core-shell excited or relaxed electronic states by the use of different theoretical methods. In particular, we present resonant Auger spectra along with a tentative new theoretical approach based on multiconfiguration self-consistent field calculations to simulate them. These calculations may pave the road towards resonant Auger spectroscopy in complex molecules.

Gas phase dynamics, conformational transitions and spectroscopy of charged saccharides: the oxocarbenium ion, protonated anhydrogalactose and protonated methyl galactopyranoside.

Protonated intermediates are postulated to be involved in the rate determining step of many sugar reactions. This paper presents a study of protonated sugar species, isolated in the gas phase, using a combination of infrared multiple photon dissociation (IRMPD) spectroscopy, classical ab initio molecular dynamics (AIMD) and quantum mechanical vibrational self-consistent field (VSCF) calculations. It provides a likely identification of the reactive intermediate oxocarbenium ion structure in a d-galactosyl system as well as the saccharide pyrolysis product anhydrogalactose (that suggests oxocarbenium ion stabilization), along with the spectrum of the protonated parent species: methyl d-galactopyranoside-H+. Its vibrational fingerprint indicates intramolecular proton sharing. Classical AIMD simulations for galactosyl oxocarbenium ions, conducted in the temperature range ∼300-350 K (using B3LYP potentials on-the-fly) reveal efficient transitions on the picosecond timescale. Multiple conformers are likely to exist under the experimental conditions and along with static VSCF calculations, they have facilitated the identification of the individual structural motifs of the galactosyl oxocarbenium ion and protonated anhydrogalactose ion conformers that contribute to the observed experimental spectra. These results demonstrate the power of experimental IRMPD spectroscopy combined with dynamics simulations and with computational spectroscopy at the anharmonic level to unravel conformer structures of protonated saccharides, and to provide information on their lifetimes.

Biradicalic excited states of zwitterionic phenol-ammonia clusters.

Phenol-ammonia clusters with more than five ammonia molecules are proton transferred species in the ground state. In the present work, the excited states of these zwitterionic clusters have been studied experimentally with two-color pump probe methods on the nanosecond time scale and by ab initio electronic-structure calculations. The experiments reveal the existence of a long-lived excited electronic state with a lifetime in the 50-100 ns range, much longer than the excited state lifetime of bare phenol and small clusters of phenol with ammonia. The ab initio calculations indicate that this long-lived excited state corresponds to a biradicalic system, consisting of a phenoxy radical that is hydrogen bonded to a hydrogenated ammonia cluster. The biradical is formed from the locally excited state of the phenolate anion via an electron transfer process, which neutralizes the charge separation of the ground state zwitterion.

Characterization of neutral fragments issued from the photodissociation of protonated tryptophane.

New information on the photo-fragmentation of biomolecules is obtained from the detection of neutral and ionic fragments using a time and position resolved coincidence technique that reveals whether an ionic photofragment is associated with one or more neutral fragments. In the case of a sequential dissociation, both fragmentation channels are identified as well as their time ordering.

Comprehensive characterization of the photodissociation pathways of protonated tryptophan.

The photofragmentation of protonated tryptophan has been investigated in a unique experimental setup, in which ion and neutral issued from the photofragmentation are detected in coincidence, in time and in position. From these data are extracted the kinetic energy, the number of neutral fragments associated with an ion, their masses, and the order of the fragmentation steps. Moreover, the fragmentation time scale ranging from tens of nanoseconds to milliseconds is obtained. From all these data, a comprehensive fragmentation mechanism is proposed.