Sums of even powers in Archimedean rings

This note is devoted to the study of totally archimedean rings of regular functions. We extend Schmüdgen's theorem to this class of rings. Moreover, we show that, in such rings, every totally positive element is a sum of even powers of totally positive elements, and hence is a sum of even powers of units. Received: 21 October 1999; in final form: 10 November 2000 / Published online: 18 January 2002     

Rate increases in the fluorination of bulky chlorosilanes caused by ultrasound or by water

The conversion of bulky chlorosilanes to fluorosilanes under anhydrous conditions with hexafluorosilicate salts is accelerated by ultrasound. The fluorination of sterically hindered chlorosilanes such as ^tBuPh₂SiCl, in the absence of ultrasound, is greatly accelerated by the addition of water to the reaction mixture.     

Alkali metal reductions of organic molecules: why mediated electron transfer from lithium is faster than direct reduction

Lithium metal reductions are widely employed in organic synthesis, where it is common to employ a "mediator" to speed up the electron transfer kinetics. We present experimental data for the electrode kinetics of the reduction of the most common mediator, 4,4'-di-tert-butyl-1,1'-biphenyl (DBB) in tetrahydrofuran (THF) over a range of temperatures. Using corresponding data for the oxidation of lithium we present quantitative estimates of the kinetic advantage for the use of DBB as a mediator in lithium reductions, over, in particular, direct reduction using lithium metal.     

Development and statistical validation of a quantitative method for the determination of steroid hormones in environmental water by column liquid chromatography/tandem mass spectrometry

This paper presents an analytical method applied to the determination of 3 natural steroid hormones, estrone, 17 beta-estradiol, and 16 alpha-hydroxyestrone, and the contraceptive estrogen, 17 alpha-ethynylestradiol, at the sub-ng/L level in water samples [surface water and wastewater treatment plant (WWTP) samples]. The solid-phase extraction conditions were optimized using C18 cartridges. Identification and quantification were performed using a column liquid chromatographic/tandem mass spectrometric system with electrospray ionization in the negative mode. Before analyzing steroids in complex matrixes, statistical tools permitted a fine validation of the analytical method, and performance was evaluated for spring water in terms of recovery, specificity, trueness, repeatability, and intralaboratory reproducibility. The results showed the accuracy of the method, and limits of detection (LOD) ranged between 0.02 and 0.21 ng/L. The determination of steroids in WWTP effluents, which contain high levels of organic matter, required an additional purification step on silica cartridges. The high efficiency of the purification was proved with LOD < 0.3 ng/L from 200 mL sample. Specificity of the entire analytical procedure was shown by repeatable recoveries at low and high levels of the calibration range.     

Easy access to bio-inspired osmium(II) complexes through electrophilic intramolecular C(sp2)-H bond cyclometalation

Mild electrophilic C(sp2)-H cyclometalation of 2-phenylpyridine and N,N-dimethylbenzylamine by the chloro-bridged osmium(II) dimer [OsCl(micro-Cl)(eta6-C6H6)]2 in acetonitrile affords cyclometalated pseudotetrahedral OsII complexes [Os(C approximately N)(eta6-C6H6)(NCMe)]PF6 (C approximately N=o-C6H4py-kappa C,N (2) and o-C6H4CH2NMe2-kappa C,N (5), respectively) in good to excellent yields. The cyclometalation reactions are super sensitive to the nature of an external base. Sodium hydroxide is essential for cyclometalation of 2-phenylpyridine, but NaOH retards metalation of N,N-dimethylbenzylamine, the tertiary amine being self-sufficient as a base. Further reactions of compounds 2 and 5 with 1,10-phenanthroline or 2,2'-bipyridine (N approximately N) lead to the substitution of the eta6-bound benzene to produce octahedral species [Os(C approximately N)(N approximately N)(NCMe)2]PF6 or [Os(C approximately N)(N approximately N)2]PF6 in MeCN or MeOH as solvent, respectively. The cis configuration of the MeCN ligands in [Os(C approximately N)(phen)(NCMe)2]PF6 has been confirmed by an X-ray crystallographic study. Electrochemical investigation of the octahedral osma(II)cycles by cyclic voltammetry showed a pseudoreversible MIII/II redox feature at (-50)-(+109) and 190-300 mV versus Ag/AgCl in water and MeCN, respectively. As a possible application of the compounds, a rapid electron exchange between the reduced active site of glucose oxidase enzyme from Aspergillus niger and the electrochemically generated OsIII species has been demonstrated. The corresponding second-order rate constants cover the range (0.7-4.8)x10(6) M(-1) s(-1) at 25 degrees C and pH 7.     

Evidence of a broad structure at an invariant mass of 4.32 GeV/c2 in the reaction e+e- --> pi+pi-psi(2S) measured at BABAR

We present a measurement of the cross section of the process e(+)e(-)-->pi(+)pi(-)psi(2S) from threshold up to 8 GeV center-of-mass energy using events containing initial-state radiation, produced at the SLAC PEP-II e(+)e(-) storage rings. The study is based on 298 fb(-1) of data recorded with the BABAR detector. A structure is observed in the cross section not far above threshold, near 4.32 GeV. We also investigate the compatibility of this structure with the Y(4260) previously reported by this experiment.     

Observation of decays B0-->Ds(*)+ pi- and B0-->Ds(*)- K+

We report the observation of decays B{0}-->D{s}{(*)+}pi- and B{0}-->D{s}{(*)-}K+ in a sample of 230 x 10(6) Upsilon(4S)-->BB[over] events recorded with the BABAR detector at the SLAC PEP-II asymmetric-energy e+ e- storage ring. We measure the branching fractions B(B{0}-->D{s}{+}pi-)=(1.3+/-0.3(stat)+/-0.2(syst))x10(-5), B(B{0}-->D{s}{-} K+)=(2.5+/-0.4(stat)+/-0.4(syst))x10(-5), B(B{0}-->D{s}{*+}pi-)=(2.8+/-0.6(stat)+/-0.5(syst))x10(-5), and B(B{0}-->D{s}{*-}K+)=(2.0+/-0.5(stat)+/-0.4(syst))x10(-5). The significances of the measurements to differ from zero are 5, 9, 6, and 5 standard deviations, respectively. This is the first observation of B{0}-->D{s}{+}pi-, B{0}-->D{s}{*+}pi-, and B{0}-->D{s}{*-}K+ decays.     

Measurement of the Time-Dependent CP Asymmetry in B;{0}-->D_{CP};{(*)}h;{0} Decays

We report a measurement of the time-dependent CP-asymmetry parameters S and C in color-suppressed B{0}-->D{(*)0}h{0} decays, where h{0} is a pi{0}, eta, or omega meson, and the decays to one of the CP eigenstates K+K-, K{S}{0}pi{0}, or K{S}{0}omega. The data sample consists of 383 x 10{6} Upsilon(4S)-->BB decays collected with the BABAR detector at the PEP-II asymmetric-energy B factory at SLAC. The results are S=-0.56+/-0.23+/-0.05 and C=-0.23+/-0.16+/-0.04, where the first error is statistical and the second is systematic.