Etude de la chloration du polychlorure de vinyle en fonction de sa tacticite

Polyvinyl chloride samples of various tacticity have been prepared and photochlorinated in CCl₄ for 4 hr. The chlorination degree correlates directly with the degree of syndiotacticity. Initial PVC with syndiotacticity about 56 per cent, which can be regarded as alternate sequences of syndiotactic and isotactic diads, is quickly chlorinated. The mechanism of chlorine attack on the macromolecula is directly connected with the stereoregularity.     

On-line sorbent extraction, preconcentration and determination of lead by atomic absorption spectrometry

A method for the quantitative preconcentration of lead based on an existing batch process was developed for implementation in a flow system including a flame AAS detector. Lead can be quantitatively preconcentrated as pyrrolidinedithiocarbamate or dithizonate on an activated carbon minicolumn. The chelates are eluted in methyl isobutyl ketone and introduced directly into the nebuliser-burner. An enrichment factor of 50 is typically obtained for a preconcentration time of 2 min (lead can be determined at concentrations between 15 and 400 ng/ml), which results in a throughput of ca. 25 samples per hr. The sensitivity achieved with the two reagents is similar, but the selectivity provided by APDC exceeds that of dithizone. Based on the results obtained in the determination of lead in reference materials (minerals and skim milk), the proposed APDC method is applicable to real samples.     

Statistical approach to bistable behaviour of a nonlinear system in a stationary field

Conclusions This discussion concerning the probability density confirms in a new way the results obtained in paper [1] in which a two-peak behaviour of the photocount distribution has been found. This general result depends on the particular nonlinear interaction scheme, and the bistable behaviour is caused by quantum fluctuations produced by the nonlinear interaction.As losses are not taken into account, other kinds of fluctuations that can modify the bistable behaviour are not accounted for in this paper.     

Micellar electrokinetic capillary chromatography for the determination of Viagra and its metabolite (UK-103,320) in human serum

Micellar electrokinetic capillary chromatography (MEKC) was investigated for the determination of Viagra (sildenafil citrate, SC) and its metabolite (UK-103,320) in human serum in a concentration range of clinical interest. For MEKC, human serum samples spiked with SC and UK were obtained directly after elution with methanol from a tC18 cartridge. The extract was evaporated and regenerated in a solution 1 mM of phosphate buffer (pH 12.3) which contained a methanol percentage of 20% that was analyzed using phosphate buffer (pH 12.3, 10 mM) containing 30 mM sodium dodecyl sulfate (SDS) as separation electrolyte and a fused-silica capillary. This method gave satisfactory interday precision with respect to migration times relative standard deviation (RSD < 1%) and linear responses for the concentration ranges investigated (0.50-3.50 mg L(-1) for the compound SC and 0.90-4.60 mg L(-1) for UK). An intraday RSD (n = 5 graphs) between the slopes of the calibration graphs was acceptable (6.40%) for SC and (3.37%) for UK. A satisfactory interday precision between slopes was also obtained (RSD 4.10% for SC and a RSD 2.72% for UK) which demonstrated the ruggedness of this method. Detection limits (S/N = 3) were about 200 ng/mL for both compounds in human serum. MEKC was shown as a good method with regards to simplicity, precision and sensitivity.     

A density functional theory study on the electrocyclization of 1,2,4,6-heptatetraene analogues: converting a pericyclic to a pseudopericyclic reaction

A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth.     

Some Landau's type inequalities for infinitesimal generators

Summary Lett T(t) be a strongly continuous contraction semigroup on a complex Banach space and letA be its infinitesimal generator. We prove that, forx D(A ³), the following inequalities hold true: Ax³ 243/8 x²A ³ x, A ² x 24 xA ³ x². Ift T(t) is a contraction group (resp. cosine function) we get the analogous but better inequalities with constants 9/8 and 3 (resp. 81/40 and 72/25) instead of 243/8 and 24. We consider also uniformly bounded semigroups, groups and cosine functions.     

On Hadamard Inequality for Log-Concave Functions

Some improvements and generalizations of Finks results about Hadamards inequality for log-concave functions are given.AMS Subject Classification: 26D07, 26D15, 26A51.     

Observation of an excited charm baryon Omega c* decaying to Omega c0gamma

We report the first observation of an excited singly charmed baryon Omega c* (css) in the radiative decay Omega c0gamma, where the Omega c0 baryon is reconstructed in the decays to the final states Omega(-)pi+, Omega(-)pi+pi0, Omega(-)pi+pi(-)pi+, and Xi(-)K(-)pi+pi+. This analysis is performed using a data set of 230.7 fb(-1) collected by the BABAR detector at the PEP-II asymmetric-energy B factory at the Stanford Linear Accelerator Center. The mass difference between the Omega c* and the Omega c0 baryons is measured to be 70.8+/-1.0(stat)+/-1.1(syst) MeV/c2. We also measure the ratio of inclusive production cross sections of Omega c* and Omega c0 in e+e(-) annihilation.