Ab-initio and experimental study of pentose sugar dehydration mechanism in the gas phase.

In this work pentose sugar (D-xylose, D-ribose and D-arabinose) gas phase dehydration reaction was investigated by means of mass spectrometric techniques and theoretical calculations. The ionic species derived from the dehydration reaction of protonated D-ribose and D-arabinose were structurally characterized by their fragmentation patterns and the relative dehydration energies measured by energy resolved CAD mass spectra. The results were compared with those recently obtained for D-xylose in the same mass spectrometric experimental conditions. Dehydration of C1-OH protonated sugars was theoretically investigated at the CCSD(T)/cc-pVTZ//M11/6-311++G(2d,2p) level of theory. Protonated pentoses are not stable and promptly lose a water molecule giving rise to the dehydrated ions at m/z 133. D-xylose, D-ribose and D-arabinose dehydration follows a common reaction pathway with ionic intermediates and transition states characterized by similar structures. Slightly different dehydration energies were experimentally measured and the relative trend was theoretically confirmed. The overall dehydration activation energy follows the order arabinose < ribose < xylose. Gas-phase pentose sugar dehydration leads to the formation of protonated 2-furaldehyde as final product. Based on the experimental and theoretical evidence a new mechanistic hypothesis starting from C1-OH protonation was proposed.

Experimental detection of tetranitrogen.

Tetranitrogen (N4), which has been the subject of great theoretical interest, has been prepared from the N4+ cation and positively detected as a gaseous metastable molecule with a lifetime exceeding 1 microsecond in experiments based on neutralization-reionization mass spectrometry. An examination of the geometry of N4+ and the fragmentation pattern of the (14)N2(15)N2 neutral molecule has revealed that the latter is characterized by an open-chain geometry with two distinct, closely bound N2 units joined by a longer weaker bond.

S3O, a new sulfur oxide identified in the gas phase.

S3O, a novel, linear sulfur oxide has been detected in the gas phase by means of neutralization reionization mass spectrometry; the upper limit of stability of acyclic forms of SnO oxides has been set by theoretical calculations.

Ionization of ozone/chlorofluorocarbon mixtures in atmospheric gases: formation and remarkable dissociation of

The reactions occurring upon ionization of mixtures containing ozone and CHX2Y (X = H, Cl, F; Y = Cl, F) halocarbons diluted in atmospheric gases (O2, N2) have been investigated in detail by mass spectrometric and theoretical methods. In all systems investigated the reactivity pattern is characterized by the preliminary formation of [CHXY x O3+] adducts which undergo unimolecular dissociation into HXYO2+ and CO. This remarkable dissociation which requires extensive molecular reorganization is exceptional for hydrogenated halocarbons. The work represents the first systematic study of the ionic chemistry in systems containing both ozone and halocarbons diluted in atmospheric gases.

Gas-phase reactions of nitronium ions with acetylene and ethylene: an experimental and theoretical study

A comparative study of the gas-phase reactions of NO2+ with acetylene and ethylene was performed by using FT-ICR, MIKE, CAD, and NfR/ CA mass spectrometric techniques, in conjunction with ab initio calculations at the MP2/6-31+G* level of theory. Both reactions proceed according to the same mechanism, that is, 1,3-dipolar cycloaddition, but yield products of different stability. The C2H2NO2+ adduct from acetylene has an aromatic character and hence is highly stabilized with respect to the C2H4NO2+ adduct from ethylene. Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetaldehyde, which represent the thermodynamically most stable products from the addition of NO2+ to acetylene and ethylene, respectively. As prototypal examples of the reactivity of free nitronium ions with most simple pi systems, the reactions investigated are useful starting points to model the mechanism of aromatic nitration.

Direct Experimental Evidence for the H(2)O(+)O(2)(-) Charge Transfer Complex: Crucial Support to Atmospheric Photonucleation Theory.

Where does rain come from? The first experimental evidence for the existence of the (H(2)O(+)O(2)(-)) charge transfer complex, predicted to play a key role as a nucleation center for atmospheric vapor photonucleation (see picture), is provided by the powerful neutralization - reionization mass spectrometric technique.

Isomeric Cl(2)O(2)(+) and Cl(2)O(2)(-) ions.

Charged species structurally related to several isomers of Cl(2)O(2), of considerable importance in atmospheric chemistry, were obtained by chemical ionization (CI) and characterized by collisionally activated dissociation (CAD) mass spectrometry. The ClOClO(+) and [Cl(2)-O(2)](+) species were prepared by positive ion Cl(2)/CI of ClO(2) and O(2), respectively, whereas the ClClO(2)(+) isomer proved an elusive species of considerably lower stability. The ClClO(2)(-) anion was obtained from the negative ion Cl(2)/CI of ClO(2). The formation process, structure and stability of the ions are discussed in connection with available theoretical results and related to the recent preparation of (Cl(2)O(2))(+)SbF(6)(-) and (Cl(2)O(2))(+)Sb(2)F(11)(-) salts in the solid phase. Copyright 1999 John Wiley & Sons, Ltd.

Experimental detection of hydrogen trioxide

Hydrogen trioxide (HO3) has long been postulated as a key intermediate in important atmospheric processes but has proved difficult to detect. The molecule was unequivocally detected in experiments based on neutralization-reionization and neutralization-reionization/collisionally activated dissociation mass spectrometry, using protonated ozone (HO3+) as the charged precursor. Hydrogen trioxide is a relatively stable species and has a H-O-O-O connectivity and a lifetime exceeding 10(-6) seconds at ambient temperature.

[Polyunsaturated fatty acids and atherosclerosis]. / Acidi grassi poliinsaturi ed aterosclerosi.

The major aspects of the antithrombogenic and antiatherogenic effects of polyunsaturated fatty acids (PUFA) have been outlined. After briefly relating on the biochemistry, the essentiality concept has been defined. Some of the many evidences of their effects both on men and animals have been reported. Eicosanoid metabolism is discussed and eicosanoid compounds derived from omega-6 and omega-3 fatty acids are compared with regard to their effects concerning atherosclerosis. Considerations about the correct amount of PUFA are reported as tentative strategies for a cardiovascular protective diet.