Stark shifts and fine structure of the Li 3 D states

⁶Li 3²D _{3/2, 5/2} states were studied using a diode laser to first excite the 2P _3/2 state and a dye laser to populate the 3²D _{3/2, 5/2} states. The dye laser was modulated by an electro-optic modulator and intersected an atomic beam that passed through a field free region and subsequently through a uniform electric field. A value of 1084.24±0.20 MHz was found for the 3²D fine structure splitting. The scalar and tensor polarizabilities were determined to be α (3D _3/2 ) = - 3.753±0.015, α ₂ (3D _3/2 ) = 2.893±0.017, α (3D _5/2 ) = - 3.772±0.008 and α ₂ (3D _5/2 ) = 4.058±0.013 MHz/(kV/cm)². Received 26 September 2002 / Received in final form 22 January 2003 Published online 11 March 2003 RID="a" ID="a"e-mail: wlaser@yorku.ca     

Reactive sulfur species: kinetics and mechanisms of the reaction of cysteine thiosulfinate ester with cysteine to give cysteine sulfenic acid

The kinetics and mechanisms of the reaction of cysteine with cysteine thiosulfinate ester in aqueous solution have been studied by stopped-flow spectrophotometry between pH 6 and 14. Two reaction pathways were observed for pH > 12: (1) an essentially pH-independent nucleophilic attack of cysteinate on cysteine thiosulfinate ester, and (2) a pH-dependent fast equilibrium protonation of cysteine sulfenate that is followed by rate-limiting comproportionation of cysteine sulfenic acid with cysteinate to give cystine. For 6 < pH < 12, the rate-determining reaction between cysteinate and cysteine thiosulfinate ester becomes pH-dependent due to the protonation of their amine groups. Hydrolysis of cysteine thiosulfinate ester does not play a role in the aforementioned mechanisms because the rate-determining nucleophilic attack by hydroxide is relatively slow.     

Redox buffering of hypochlorous acid by thiocyanate in physiologic fluids

The major antimicrobial products of neutrophilic myeloperoxidase (MPO) in physiologic fluids are hypochlorous acid (HOCl) and hypothiocyanite (OSCN-), and the former is generally believed to be the killing agent. However, we have determined that HOCl oxidizes SCN- in a facile nonenzymic reaction. The observed kinetics and computational models substantiate the hypothesis that SCN- serves to moderate the potential autotoxicity of HOCl by restricting its lifetime in physiologic fluids. Furthermore, the oxidizing equivalents of HOCl are preserved in OSCN-, a more discriminate biocide that is not lethal to mammalian cells.     

Adaptive polynomial preconditioning for hermitian indefinite linear systems

This paper explores the use of polynomial preconditioned CG methods for hermitian indefinite linear systems,Ax=b. Polynomial preconditioning is attractive for several reasons. First, it is well-suited to vector and/or parallel architectures. It is also easy to employ, requiring only matrix-vector multiplication and vector addition. To obtain an optimum polynomial preconditioner we solve a minimax approximation problem. The preconditioning polynomial,C(), is optimum in that it minimizes a bound on the condition number of the preconditioned matrix,C(A)A. We also characterize the behavior of this minimax polynomial, which makes possible a thorough understanding of the associated CG methods. This characterization is also essential to the development of an adaptive procedure for dynamically determining the optimum polynomial preconditioner. Finally, we demonstrate the effectiveness of polynomial preconditioning in a variety of numerical experiments on a Cray X-MP/48. Our results suggest that high degree (20–50) polynomials are usually best.This research was supported in part by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Dept. of Energy, by Lawrence Livermore National Laboratory under contract W-7405-ENG-48.This research was supported in part by the Dept. of Energy and the National Science Foundation under grant DMS 8704169.This research was supported in part by U.S. Dept. of Energy grant DEFG02-87ER25026 and by National Science Foundation grant DMS 8703226.     

Review: Experiments in Fundamental Physics Scheduled and in Development for the ISS

This is a review of those experiments in the area of Fundamental Physics that are either approved by ESA and NASA, or are currently under development, which are to be performed in the microgravity environment of the International Space Station. These experiments cover the physics of liquid Helium (SUE, BEST, MISTE, DYNAMX, and EXACT), ultrastable atomic clocks (PHARAO, PARCS, RACE), ultrastable microwave resonators (SUMO), and particle detectors (AMS and EUSO). The scientific goals are to study more precisely the universality properties of liquid Helium under microgravity conditions, to establish better time standards and to test the universality of the gravitational red shift, to make more precise tests of the constancy of the speed of light, and to measure the particle content in space directly without disturbances from the Earth's inner atmosphere.     

The synthesis of thiaolivacine and related compounds

1,5-Dimethylbenzothieno[2,3-g]isoquinoline (thiaolivacine) has been prepared from the nitro-vinyl derivative of 4-methyl-3-dibenzothiophenecarboxaldehyde. Using the same aldehyde, 4-des-methylisothiaolivacine was prepared by formation of the Schiff's base with aminoacetaldehyde diethyl acetal followed by cyclization. Similar methods yielded the pyrido-N-isomer, 1-des-methylthiaolivacine, from 4-methyl-2-dibenzothiophenecarboxaldehyde. The thiaolivacine parent unsubstituted ring system, benzothieno[2,3-g]isoquinoline, was prepared from 2-dibenzothio-pheneearboxaldehyde by the aminoacetaldehyde approach, as was the corresponding oxygen analog, benzofuro[2,3-g]isoquinoline, from 2-dibenzofurancarboxaldehyde. The 100 MHz spectra of these fused isoquinolines are recorded and correlated.     

The transformation of saccharin into derivatives of lmidazo[1,2-b] [1,2]-benzisothiazole and benzo[g] [1,2,5]thiadiazocine

Reaction of 3-(2-hydroxyethylamino) benzo[d]isothiazole 1,1-dioxide ( 5a ) with thionyl chloride gives a mixture of the expected chloroethyl derivative ( 5h ) and the rearranged saccharin 2-(2-aminoethyl)-3-oxo-2,3-dihydrobenzo[d]isothiazole 1,1-dioxide hydrochloride ( 6a ). Separate treatment of the chloroethyl compound ( 5h ) with dilute alkali gives the expected cyclization product 2,3-dihydroimidazo[1,2-b] [1,2] benzisothiazole 5, 5-dioxide ( 7a ). Acidification of the liquors of the above reaction yields the ring expanded derivative 6-oxo-3,4,5,6-tetrahydro-[2H]benzo[g][1,2,5]thiadiazocine 1,1-dioxide ( 12f ), a representative of a new ring-system. Treatment of the imidazo derivative ( 7a ) with concentrated hydrochloric acid again yields the N-substituted saccharin ( 6a ) which upon treatment with alkali also produces the thiadiazocine ( 12f ). In contrast, treatment of the imidazo compound ( 7a ) with alkali leads to attack on the sulphonamide function to give 2-(2-imidazolin-2-yl)benzenesulphonic acid ( 8 ). It is suggested that the multitude of chemical interconversions which can be induced within this series of compounds (Scheme II) can only be accounted for if two separate cyclol intermediates are invoked. Related reactions observed with variously substituted derivatives of the starting saccharin derivative ( 5a ) are discussed as are the spectral properties and chemical reactivity of the new compounds prepared.     

The synthesis of some benzo[d1]furo[3,2-e] [1,4] diazepin-2-ones

Reaction of 3-amino-2-benzoylbenzo[b]furan with bromoacetyl bromide followed by cyclization in methanolic ammonia gave 5-phenyl-1,3-dihydrobenzo[d′] furo[3,2-e] [1,4]diazepin-2-one, a representative of a new ring-system. The corresponding chloro substituted diazepin-2-one was similarly prepared from 3-amino-2-(4-chlorobenzoyl) benzo[b] furan. Some alkylation and thionation reactions of these diazepines have been investigated.     

The Role of the Inner Product in Stopping Criteria for Conjugate Gradient Iterations

Two natural and efficient stopping criteria are derived for conjugate gradient (CG) methods, based on iteration parameters. The derivation makes use of the inner product matrix B-defining the CG method. In particular, the relationship between the eigenvalues and B-norm of a matrix is investigated, and it is shown that the ratio of largest to smallest eigenvalues defines the B-condition number of the matrix. Upper and lower bounds on various measures of the error are also given. The compound stopping criterion presented here is an obvious default in software packages because it does not require any additional norm computations.