Use of the64Ni(36S,34,35Si)66,65Zn reactions to measure the masses of34Si and35Si

The ground-state masses of³⁵Si and³⁴Si have been measured using the reactions⁶⁴Ni(³⁶S,^35,34Si)^65,66Zn at a³⁶S beam energy of 198 MeV.^34,35Si¹⁴⁺ ions were analysed and identified in a QMG/2 magnetic spectrometer and gas-filled focal-plane detector. The experimental mass excess of³⁵Si was determined to be ?14.58± _0.12 ^0.07 MeV while that of³⁴Si was measured as ?19.961±0.034 MeV. A comparison is made with the results of mass model predictions.     

The esterolytic activity of poly(N-alkylimidazoles). The effect of ester chain length in the substrate and alkyl chain length in the catalyst on the esterolytic activity of poly(N-alkylimidazoles).

In an effort to exploit the enhancement in catalytic activity which might be derived through hydrophobic interactions between polymeric catalyst and substrate, 1-methyl-5-vinylimidazole (1-Me-5-VIm), 1-methyl-4-vinylimidazole (1-Me-4-VIm), 1-butyl-5-vinylimidazole (1-Bu-5-VIm), and 1-butyl-4-vinylimidazole (1-Bu-4-VIm) have been synthesized and polymerized. In 28.5% ethanol-water, poly(1-alkyl-5-vinylimidazoles)proved to be efficient catalysts for the hydrolysis of various 3-nitro-4-acyloxybenzoic acids (Sn-, where n denotes the acyl chain length). Order of magnitude rate enhancements, as compared to the model compound, 1,5-dimethylimidazole (1,5-DMIm) were observed in the poly(1-alkyl-5-vinylimidazole)-catalyzed solvolysis of S12- and S18-. Poly(1-Me-5-VIm) catalyzes the hydrolysis of S18-88 times faster than does 1,5-DMIm. The poly(1-Me-5-VIm)-catalyzed hydrolysis of S18- in ethanol-water was analyzed in terms of a simple Michaelis-Menten type mechanism. Vmax and Km were determined to be 40.2 X 10(-7) M min-1 and 2.20 X 10(-5) M, respectively.     

Characterization of the Phosphoryl-Nitrogen Linkages in Histone H4

In earlier work we nave described and partially characterized two histone kinases from regenerating rat liver and other tissues which catalyze the transfer of the γ-phosphoryl group from ATP to histones. The histone phosphates thus formed were observed to be acid-labile and base-stable. In the present study we report on the specificity of one of these enzymes, namely, the kinase which is optimally active at pH 9. This enzyme appears to be relatively specific for the two histidine residues of histone H4. These histidines occur at positions 18 and 75, and both are phosphorylated. However, when regenerating rat liver was the source of enzyme, the product was 1-phosphohistidine, whereas the enzyme from Walker-256 carcinosarcoma catalyzed the formation of 3-phosphohistidine.     

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol(1)

The reaction of the title diketone (3) with phenyl Grignard produces (with rate constant k(1)) the conjugate base (6-M) of 10-hydroxy-10-phenylcyclooctadecanone (6), which is subsequently converted (with rate constant k(2)) to the conjugate base of the title diol, as a mixture of the cis (7, 55%) and trans (8, 45%) isomers. The ratio k(2)/k(1), 2.2 +/- 0.4, indicates that the carbonyl group in 6-M is 4.4 times as reactive as each carbonyl in 3. Competition experiments further demonstrate that the relative rates (per carbonyl) for addition of phenylmagnesium bromide to 3, 10-methylenecyclooctadecanone (11), and cyclopentadecanone (12) are 1.0:0.60:1.92. Possible reasons for this order of reactivity are discussed. Diols 7 and 8 undergo facile double dehydration to form the title diene 13, which is predicted by molecular mechanics calculations to be the most stable of the four possible symmetrical diene isomers. The structures of 7, 8, and 13 were secured by single-crystal X-ray studies.     

Oxidation of organic sulfides by vanadium haloperoxidase model complexes

In addition to halide oxidation, the vanadium haloperoxidases are capable of oxidizing sulfides to sulfoxides. Four vanadium complexes with tripodal amine ligands, K[VO(O(2))(heida)] (1), VO(2)(bpg) (2), K[VO(2)(ada)] (3), and K(2)[VO(O(2))(nta)] (4), previously shown to perform bromide oxidation (Colpas, G. J.; Hamstra, B. J.; Kampf, J. W.; Pecoraro, V. L. J. Am. Chem. Soc. 1996, 118, 3469-3477), have now been shown to oxidize aryl alkyl sulfides to the corresponding sulfoxides. The oxidation was observed by the disappearance of thioanisole's ultraviolet absorption at 290 nm, by the change in the aromatic region of the (1)H NMR spectrum of the sulfides, and by changes in the complexes' (51)V NMR spectra. The amount of methyl phenyl sulfide oxidized in 3 h was 1000 equiv (per metal complex). The oxidation product is almost exclusively sulfoxide, with very little sulfone (less than 3% over a 3 h experiment) formed. This is consistent with an electrophilic oxidation mechanism, as had been proposed for oxidation of bromide by 1-4. The rate was found to be first order in substrate concentration, similar to the rate law observed for bromide oxidation. Unlike the bromide oxidation, the equivalent of acid required for peroxovanadium complex activation is not consumed. The complexes 1-4 are not reactive with styrene or cyclooctene. The relevance of these reactions to the mechanism of the vanadium haloperoxidases and, more generally, peroxovanadium oxygenation of sulfides will be discussed.     

Phase transition in single crystal Cs2Nb4O11

We studied temperature dependence of complex capacitance, impedance, and polarized Raman spectra of single crystal Cs2Nb4O11. First, we observed a sharp lambda-shaped peak at 165 degrees C in the complex capacitance, then found drastic changes in the Raman spectra in the same temperature range. Utilizing the pseudosymmetry search of structure space group, we attributed the observed anomalies to a structural change from the room temperature orthorhombic Pnn2 to another orthorhombic Imm2. We also measured room temperature polarized Raman spectra in different symmetries of normal vibrations and assigned high wavenumber Raman bands to the internal vibrations of NbO6 octahedra and NbO4 tetrahedra.     

Physical/chemical separations in the break-up of highly charged droplets from electrosprays

Highly-charged droplets, as formed by an electrospray process, are known to undergo asymmetric fission to form smaller droplets. We have observed a chemical and physical separation phenomenon that occurs in the droplet break-up process and is related to a compound's surface activity in solution. Two experimental approaches demonstrated that the smaller satellite droplets and the progeny droplets generated by the spray formation and asymmetric fission processes to be surfactant-enriched. These smaller droplets were also effectively separated from the larger primary and residual droplets because of their smaller inertia and high surface charge density, and a region attributed to the initially formed smaller satellite droplets was found to be strikingly confined in a narrow periphery region of the electrospray. The phenomenon may have utility for chemical separations and have significant implications for the sensitivity and selectivity of electrospray ionization-mass spectrometry.