Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 1. Preparation,dissociations, and energetics of 2-hydroxyoxolan-2-yl radical,neutral isomers,and cations

Collisional neutralization of several isomeric C(4)H(7)O(2) cations is used to generate radicals that share some structural features with transient species that are thought to be produced by radiolysis of 2-deoxyribose. The title 2-hydroxyoxolan-2-yl radical (1) undergoes nearly complete dissociation when produced by femtosecond electron transfer from thermal organic electron donors dimethyl disulfide and N,N-dimethylaniline in the gas phase. Product analysis, isotope labeling ((2)H and (18)O), and potential energy surface mapping by ab initio calculations at the G2(MP2) and B3-PMP2 levels of theory and in combination with Rice-Ramsperger-Kassel-Marcus (RRKM) kinetic calculations are used to assign the major and some minor pathways for 1 dissociations. The major (approximately 90%) pathway is initiated by cleavage of the ring C-5[bond]O bond in 1 and proceeds to form ethylene and *CH(2)COOH as main products, whereas loss of a hydrogen atom forms 4-hexenoic acid as a minor product. Loss of the OH hydrogen atom forming butyrolactone (2, approximately 9%) and cleavage of the C-3[bond]C-4 bonds (<1%) in 1 are other minor pathways. The major source of excitation in 1 is by Franck-Condon effects that cause substantial differences between the adiabatic and vertical ionization of 1 (5.40 and 6.89 eV, respectively) and vertical recombination in the precursor ion 1(+) (4.46 eV). (+)NR(+) mass spectra distinguish radical 1 from isomeric radicals 2-oxo-(1H)oxolanium (3), 1,3-dioxan-2-yl (9), and 1,3-dioxan-4-yl (10) that were generated separately from their corresponding ion precursors.     

Charge transfer across a polymer gel/liquid interface: determination of ionophores

An electrochemical method for the determination of the ionophores monensin and lasalocid was developed, based on the polarization of an agar gel/nitrobenzene electrolyte interface. The measured current corresponding to the facilitated ion transfer across this interface is directly proportional to the concentration of an ionophore dissolved in the organic phase. Using cyclic voltammetry in a three-electrode system the detection limit for both ionophores is about 3 × 10^?5 M.     

Electronic and crystalline structure of Si/SiO2 interface modified by ArF excimer laser

The native oxide layers on Si(100) surface were irradiated under UHV conditions by an ArF excimer laser pulses with energy density varied between melting and evaporating thresholds. The resulting changes were studied by LEED, AES and UPS. The increase of the energy density up to evaporation threshold results in the recrystallisation of native oxide layer. The pulses with energy densities just above the evaporation threshold ablate the top layer leaving an ordered and atomicaly clean surface. The observed (1x1) surface reconstruction is probably stabilised by strains introduced during rapid melting and quenching of the topmost layers. The surface electronic structure is dominated by random satisfaction of dangling bonds swearing a well defined surface states observed on (2x1)Si(100) surface.     

Preparation and NMR spectra of substituted 2-phenyl-5,5-dialkylimidazolinones

Eighteen substituted 2-phenyl-5,5-dialkylimidazolinones 2 have been prepared by cyclizations of substituted 2-(N-benzoylamino)alkanamides 1. The cyclization of methylamides 1 proceeds at room temperature whereas primary amides are cyclized on boiling. The ¹H and ¹³C nmr spectra of the imidazolinones are presented and the changes in their spectra connected with their protonation in hexadeuteriodimethyl sulfoxide-trifluoroacetic acid mixtures are discussed.     

Use of x-ray fluorescence spectrometry in ion-exchange studies of leach liquors

Equilibrium and kinetic studies of ion exchange of a complex leach liquor from coal ash, with strongly basic resins and a liquid ion exchanger are reported. The multi-component system was studied by determining the composition of the effluents and by non-destructive analysis of the loaded ion exchangers by XRF spectrometry. In the case of column operation, the elution processes were investigated by the same method, which was very appropriate for non-destructive monitoring of resin regeneration steps done repeatedly with the same resin sample.     

Thermal decomposition of N2H6GeF6 · H2O,isolation and characterization of intermediates

The thermal behaviour of N₂H₆GeF₆ · H₂O was investigated by TG, DTG and DTA measurements. The decomposition proceeded in three steps, in which anhydrous N₂H₆GeF₆ and N₂H₅GeF₅; were isolated and characterized by chemical analysis and vibrational spectroscopy. The X-ray powder photographs of the intermediates were indexed, namely, for N₂H₆GeF₆ on the basis of a monoclinic cell with a = 8.86(9), b = 9.29(2), c =7.40(0) Å, β = 85° and for N₂H₅GeF₅ on the basis of an ortrhorhombic cell with a = 8.43(5),b = 9.19(9), c = 7.43(6) Å.     

Substitution of phosphine in the complex [RhCl(cyclooctadiene)(phosphine)] by 1-hexene

Summary The substitution of phosphine in the [RhCl(COD)(phosphine)] complex (1), where phosphine is PPh₃ or 1/2 BPS-2 [bis(diphenylphosphinoethyl)tetramethyldisiloxane] and COD is cycloocta-1,5-diene, by 1-hexene is a two-step reversible reaction. All individual rate constants and equilibrium constants were determined spectrophotometrically and associative mechanism occurring via the formation of five-coordinated [RhCl(COD)(phosphine)(1-hexene)] (2) was inferred. The rate-determining step changes from the first- to the second-one as the concentration of 1-hexene increases. An excess of phosphine shifts the equilibrium towards complex (2).     

Exchange of halogen bonded on aromatic core. Heterogeneous catalysis—I : Reaction mechanism of iodine exchange in o-iodobenzoic acid

Reaction mechanism of halogen exchange between arylhalogenide and halogenide anion is studied in a case when the aromatic core is inactivated with respect to the S_NAr substitution by other substituents. The exchange of iodine between o-iodobenzoic acid and ¹³¹I labelled NaI serves as a modelling reaction. The reaction was found to proceed heterogeneously on a glass surface. In the case of a rapid course of the surface reaction the reaction mechanism is more complicated and the equation derived by McKay cannot be applied for expressing the time dependence of the degree of isotopic exchange. Reaction mechanism was proposed for this reaction and compared with experimental data.     

Preparation and properties of yttrium complexes with alkanodicarboxylic acids

Malonate, succinate and glutarate of yttrium were obtained by dissolving Y(OH)₃ in a solution of the corresponding acid and crystallization, whereas adipate, pimelate, suberate, azelate and sebacate in the reaction of YCl₃ with the ammonium salt of the acid. Yttrium alkanodicarboxylates were prepared as crystalline solids with general formula Y₂O₃.nH₂O, wheren=3, 4, 6, 7. On the basis of IR spectra the way of coordination COO^– - Y³⁺ was established. Yttrium malonate, succinate, glutarate, azelate and sebacate heated lose crystallization water and next anhydrous complexes are transformed to Y₂O₃, whereas yttrium adipate, pimelate and suberate on heating lose some water molecules and, the mono- or dihydrates formed are decomposed to Y₂O₃. The properties of the studied complexes change discretely according to odd or even number of carbon atoms in the chain.

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Zusammenfassung Durch Auflösen von Y(OH)₃ in einer Lösung der entsprechenden Säure und anschliessendem Kristallisieren wurden Yttriummalonat,-succinat und -glutarat dargestellt, das Yttriumadipat, -pimelat-, -suberat und -azelainat und sebacate hingegen in der Reaktion von YCl₃ mit dem Ammoniumsalz der Säure. In Form kristalliner Feststoffe wurden Yttriumalkanodicarboxylate der allgemeinen Formel Y₂L₃,nH₂O mitn=3, 4, 6 bzw. 7 hergestellt. Ausgehend von den IR-Spektren konnte die Art der Koordinierung als COO^– y³⁺ festgestellt werden. Beim Erhitzen geben Ytrriummalonat, -succinat, -glutarat, azelainat und -sebazat ihr Kristallwasser ab, aus den anhydratierten Komplexen bildet sich anschliessend Y₂O₃, während Yttriumadipet, pimelat und -suberat einige Wassermoleküle verlieren und die monooder dihydratierten Formen sich dann zu Y₂O₃ zersetzen. Die Eigenschaften der untersuchten Komplexe variieren eindeutig in Abhängigkeit davon, ob sich in der Kette eine gerade oder ungerade Anzahl von Kohlenstoffatomen befindet.

     

Simple <Emphasis Type="Italic">b</Emphasis> ions have cyclic oxazolone structures. A neutralization-reionization mass spectrometric and computational study of oxazolone radicals

The 2-methyloxazol-5-on-2-yl radical (3) and its deuterium labeled analogs were generated in the gas-phase by femtosecond electron-transfer and studied by neutralization-reionization mass spectrometry and quantum chemical calculations. Radical 3 undergoes fast dissociation by ring opening and elimination of CO and CH(3)CO. Loss of hydrogen is less abundant and involves hydrogen atoms from both the ring and side-chain positions. The experimental results are corroborated by the analysis of the potential energy surface of the ground electronic state in 3 using density functional, perturbational, and coupled-cluster theories up to CCSD(T) and extrapolated to the 6-311 ++ G(3df,2p) basis set. RRKM calculations of radical dissociations gave branching ratios for loss of CO and H that were k(CO)/k(H) > 10 over an 80-300 kJ mol(-1) range of internal energies. The driving force for the dissociations of 3 is provided by large Franck-Condon effects on vertical neutralization and possibly from involvement of excited electronic states. Calculations also provided the adiabatic ionization energy of 3, IE(adiab) = 5.48 eV and vertical recombination energy of cation 3(+), RE(vert) = 4.70 eV. The present results strongly indicate that oxazolone structures can explain fragmentations of b-type peptide ions upon electron capture, contrary to previous speculations.