An ESR study of some group IVB free radical adducts of diethylketomalonate

The formation of the compound RSnX(acac)₂ (acac = 2,4-pentanedionato) by reaction of bis(2,4-pentanedionato)tin(II) on a halide RX with R = CH₃, C₂H₅, C₄H₉, C₆H₅, CH₂I, (C₆H₅)₃SnCH₂, (C₂H₅)₃SnCH₂ and X = I, Br has been studied by polarography. At 25°C, it is in fact an equilibrium whose constant has been measured. The intermediate formation of the ion-pair [RSn(acac)₂⁺X^?] has allowed us to explain the experimental results.     

Direct quantitative analysis of peptides using matrix assisted laser desorption ionization

The protocol and various matrices were examined for quantification of biomolecules in both the low ca. 1200 amu and mid mass 6000-12000 amu ranges using an internal standard. Comparative studies of different matrices of MALDI quantitative analysis showed that the best accuracy and standard curve linearity were obtained for two matrices: (a) 2,5-dihydroxybenzoic acid (DHB) combined with a comatrix of fucose and 5-methoxysalicylic acid (MSA) and (b) ferulic acid/fucose. In the low mass range, the quantitative limit was in the 30 fmol range and in the mid mass range the quantitative limit was in the 250 fmol range. Linear response was observed over 2-3 decades of analyte concentration. The relative error of the standard curve slope was 1.3-1.8% with correlation coefficients of 0.996-0.998.The main problem for quantitative measurement was suppression of the signal of the less concentrated component (analyte or internal standard) by the more concentrated component. The effect was identified with saturation of the matrix by the analyte. The threshold of matrix saturation was found to be in the range of 1/(3000-5000) analyte/matrix molar ratio. To avoid matrix saturation the (analyte+internal standard) to matrix molar ratio should be below this threshold. Thus the internal standard concentration should be as low as possible.DHB/MSA/fucose and ferulic acid/fucose matrices demonstrated good accuracy and linearity for standard curves even when the internal standard had chemical properties different from the analyte. However, use of an internal standard with different chemical properties requires highly stable instrumental parameters as well as constant (analyte+internal standard)/matrix molar ratio for all samples.     

Structures and synthesis of framework Rb and Cs uranyl arsenates and their relationships with their phosphate analogues

Two hydrated uranyl arsenates, Cs₂(UO₂)[(UO₂)(AsO₄)]₄(H₂O)₂ (CsUAs) and Rb₂(UO₂)[(UO₂)(AsO₄)]₄(H₂O)_4.5 (RbUAs), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using MoKα radiation and a CCD-based area detector. The crystal structure of RbUAs was solved by direct methods, whereas the structure model of the phosphate Cs₂(UO₂)[(UO₂)(PO₄)]₄(H₂O)₂ was used for CsUAs; both were refined by full-matrix least-squares techniques on the basis of F² to agreement indices (CsUAs, RbUAs) wR₂=0.061,0.041, for all data, and R₁=0.032,0.021, calculated for 5098, 4991 unique observed reflections (|F_o|>4σ_F), respectively. The compound CsUAs is orthorhombic, space group Cmc2₁, Z=4, a=15.157(2), b=14.079(2), c=13.439(2) Å, V=2867.9(1) Å³. RbUAs is monoclinic, space group C2/m, Z=4, a=13.4619(4), b=15.8463(5), c=14.0068(4) Å, β=92.311(1)°, V=2985.52(2) Å³. The structures consist of sheets of arsenate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO₂)(AsO₄)]⁻, that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two arsenate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H₂O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. CsUAs is isostructural with its phosphate analogue, and has two Cs atoms and a H₂O group in its structural cavities. RbUAs is not isostructural with its phosphate analogue, although it has a homeotypic framework. Its structural cavities are occupied by three Rb atoms and four H₂O groups; one Rb position and three of the interstitial H₂O groups are half-occupied. The partial occupancies of these positions probably result from the accommodation of the larger As atoms (relative to P) in the framework and resultant larger cavities.     

Methylmethacrylate complexes of sterically hindered aluminum aryloxides: activation of methacrylic esters

The interaction of AlR₂(BHT)(OEt₂) and AlMe(BHT)₂ with methylmethacrylate (MMA) leads to the formation of the Lewis acid-base complexes AlR₂(BHT)(MMA) [R = Me (1), Et (2)] and AlMe-(BHT)₂(MMA) (3), respectively. The molecular structure of 1 has been determined by X-ray crystallography. The decrease in the C=O and C=C stretching frequencies in the IR spectrum, and downfield shift in the ¹³C NMR spectrum of the - and γ-carbons of the MMA, when compared to free MMA, is presented with respect to the activator ability of sterically crowded aryloxide compounds of aluminum to aluminum-porphyrin catalyzed (Inoue) polymerization of MMA.     

Kinetic studies of laser-induced synthesis of thin vanadium pentoxide films

The kinetics of Ar⁺ laser-induced oxidation of 100 nm thick vanadium films on glass substrates is followed by measuring time-dependent changes in reflected and transmitted intensity of a He-Ne probe beam. The growth rate of the vanadium pentoxide layer increases with increasing laser powerP as = ₀ exp(-a/P). At power densities above kW/cm² vanadium pentoxide crystallizes from the melt.     

Three-photon near-threshold photoionization dynamics of isooctane

The electron survival probability following three-photon (9.3 eV total) near-threshold photoionization of neat isooctane is measured with sub-50 fs time resolution. The measured dynamics are nonexponential in time and are well described by a diffusion-controlled electron-cation recombination model. Excitation-power-dependent studies indicate that the unperturbed three-photon threshold ionization is only observed for pump irradiance below 0.5 TW cm2. At excitation fields above this level, the signal is no longer cubic in the excitation irradiance, and the observed electron survival probability dramatically changes, decaying as a single exponential in time.     

Topotactic oxidation of TiGaPO-1, a pyridine-templated titanium gallophosphate with a new octahedral-tetrahedral 3-D framework structure containing Ti(III)/Ti(IV)

The first 3-D open-framework TiGaPO complex, constructed from Ti(III)O(6), Ti(IV)O(6), GaO(4), and PO(4) polyhedra, contains pyridinium cations in a 1-D pore network and can be oxidized in air at 543 K with retention of the original framework structure.