Stereoisomeric fragment ions arising from decomposition of enol cation radicals of different internal energy content

The least-squares analysis of collisional activation mass spectra provides evidence that 1,1-dihydroxy-3-methylbutene cation radical (a) and 1-hydroxy-1-methoxy-3-methylbutene cation radical (c) (generated in a McLafferty-type rearrangement from 2-isopropyl-3-methylbutanoic acid and its methyl ester) give rise to product ions b and d, the stereochemistry of which at the double bond is determined by the lifetime (internal energy) of a and c, respectively. Decompositions of a and c in the ion source yield predominantly the less stable cis-configurated stereoisomers of b and d, whereas dissociation of a and c at longer lifetimes (lower internal energy) results in the formation of the thermochemically more stable trans isomers of b and d. A qualitative MNDO analysis is provided which takes into account the special features of stereoelectronic control of radical chemistry in the cleavage of a carbon? carbon bond.     

Kinetics and Mechanism of Oxidation of 1-Phenylsemicarbazide by Peroxydisulphate

Kinetics of oxidation of 1-phenylsemicarbazide (PSC) by peroxydisulphate ion (PDS) have been carried out where by the pseudo first order condition was verified at large excess of PDS concentration. The rate of the reaction was followed spectrophotometrically, The stoichiometry was found to be 1:1 where 1-phenylazoformamide is the oxidation product. The effect of acidity on the rate of oxidation was investigated for different temperatures. The parameters of activation ΔG*, ΔH* and ΔS* were computed for both hydrogen ion depedent and hydrogen ion independent reaction pathes. A free radical mechanism was proposed.     

Operating conditions for lithium recovery from natural brines

Lithium recovery from natural brine incontestably requires the optimization of the parameters which influence such a process. This process consists of trapping lithium ions by a gel of aluminum hydroxide prepared under the action of a strong base. Studied parameters are molar ratio [Al]/[Li], stirring time, reaction temperature and apparent pH. A systematic study was carried out varying only one parameter at a time. This procedure makes it possible to fix the studied parameters in order to recover maximum Li⁺. This work is done first on synthetic brines, and then it was considered convenient to check the obtained result using natural brine and an equivalent synthetic brine. Some differences related to lithium yield are established between the two considered brines. This is due in our opinion to the impurities contained in the natural brine, especially magnesium and boron.     

Stable [C2H7O2]+ isomers: Experimental and theoretical evidence for the existence of protonated peroxides and proton-bound dimers in the gas phase

Evidence is presented for the gas phase generation of at least eight stable isomeric [C₂H₇O₂]⁺ ions. These include energy-rich protonated peroxides (ions \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH}_2 {\rm O}\mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2} $\end{document} (e), \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH}_{\rm 2} \mathop {\rm O}\limits^{\rm + } {\rm (H)OH} $\end{document} (f) and \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm O}\mathop {\rm O}\limits^{\rm + } {\rm (H)CH}_{\rm 3} {\rm (g)),} $\end{document} (g)), proton-bound dimers (ions \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH = O} \cdot \cdot \cdot \mathop {\rm H}\limits^{\rm 3} \cdot \cdot \cdot {\rm OH}_{\rm 2} $\end{document} (h) and \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH2 = O} \cdot \cdot \cdot \mathop {\rm H}\limits^{\rm + } \cdot \cdot \cdot {\rm HOCH}_{\rm 3} $\end{document} (i)) and hydroxy-protonated species (ions \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 2} {\rm (OH)CH}_{\rm 2} \mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2} (a), $\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm CH(OH)}\mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2} $\end{document} (b) and \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} {\rm OCH}_{\rm 2} \mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2} $\end{document} (c)). The important points of the present study are (i) that these ions are prevented by high barriers from facile interconversion and (ii) that both electron-impact- and proton-induced gas phase decompositions seem to proceed via multistep reactions, some of which eventually result in the formation of proton-bound dimers.     

Sur une Resolution Stochastique de l'Equation de Schrödinger à Coefficients Analytiques

Under some hypotheses of analyticity and integrability we show the existence and uniqueness of a strong regular solution of the Schrödinger equation using a natural generalisation to the complex case of the Feynman-Kac formula. This explicit representation allows us to study in certain cases the asymptotic behavior of the solution when the Planck constanth tends to zero. The same method can be used for the solution of more general Schrödinger equations.

---

---

Membre du Laboratoire Associé au C.N.R.S., n° 224 Processus Stochastiques et Applications     

Photocatalytic properties of TiO2/ZnO thin film

ABSTRACT

TiO₂, ZnO and ZnO/TiO₂ thin films have been prepared by radio frequency magnetron sputtering method under different temperatures. Their photo catalytic activities have been investigated. The structural of the thin films were characterized by X-ray diffraction and Raman spectroscopy. The photo catalytic activities of TiO₂ and ZnO/TiO₂ samples were evaluated by the photo decomposition of methylene blue. We note that the structural proprieties of the thin films showed a perfect crystallization along the (002) for ZnO, Rutile (110) for TiO₂ and Anatase (101) for TiO₂. The experimental results show that the bilayer ZnO/TiO₂ were the most efficient photo catalysts compared to the layer of TiO₂. This increased catalytic effect can attributed to the interface between the ZnO layer and the TiO₂ one, which modify significantly the chemical potential of the bilayer.     

213 nm Ultraviolet Photodissociation on Peptide Anions: Radical-Directed Fragmentation Patterns

Characterization of acidic peptides and proteins is greatly hindered due to lack of suitable analytical techniques. Here we present the implementation of 213 nm ultraviolet photodissociation (UVPD) in high-resolution quadrupole-Orbitrap mass spectrometer in negative polarity for peptide anions. Radical-driven backbone fragmentation provides 22 distinctive fragment ion types, achieving the complete sequence coverage for all reported peptides. Hydrogen-deficient radical anion not only promotes the cleavage of C_α–C bond but also stimulates the breaking of N–C_α and C–N bonds. Radical-directed loss of small molecules and specific side chain of amino acids are detected in these experiments. Radical containing side chain of amino acids (Tyr, Ser, Thr, and Asp) may possibly support the N–C_α backbone fragmentation. Proline comprising peptides exhibit the unusual fragment ions similar to reported earlier. Interestingly, basic amino acids such as Arg and Lys also stimulated the formation of abundant b and y ions of the related peptide anions. Loss of hydrogen atom from the charge-reduced radical anion and fragment ions are rationalized by time-dependent density functional theory (TDDFT) calculation, locating the potential energy surface (PES) of ππ* and repulsive πσ* excited states of a model amide system.

Open image in new window

Graphical Abstract ?