Anodic stripping coulometry with collection for absolute trace analysis of lead, using flow-through electrochemical cells with porous working electrodes

Summary Flow-through electrochemical cells with porous working electrodes made of crushed reticulated vitreous carbon and plated with mercury were used for absolute analysis of trace amounts of lead by anodic stripping coulometry with collection (ASCWC) in a flow system. The role of mercury coating, flow rate and pH were investigated. The coulombic content of the collection peak corresponded to the theoretical values calculated by Faraday's law in a concentration range from about 10^–9 to 10^–6 mol/l. The relative error and the relative standard deviation was +0.15% and 0.8%, respectively for 2×10^–6 mol/l analyte concentration. The absolute detection limit (3 s) was 0.1 ng of Pb, the linear response range 7×10⁴. One leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia     

Crystal and molecular structures of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine.

The crystal structure of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine (C15H19NO3) (I) has been determined by X-ray analysis. It crystallizes orthorhombic space group Pbca with a = 24.295(3), b = 15.086(3), c = 7.552(3)A, V = 2768(1)A3, Z = 8, Dcalc = 1.254 g/cm3, mu = (Mo K(alpha)) = 0.87 cm(-1). The title compound has analgesic activity of cycloaliphatic amine part. The molecule is deviated from planar configuration.     

A p-version finite element method for nonlinear elliptic variational inequalities in 2D

This article introduces and analyzes a p-version FEM for variational inequalities resulting from obstacle problems for some quasi-linear elliptic partial differential operators. We approximate the solution by controlling the obstacle condition in images of the Gauss–Lobatto points. We show existence and uniqueness for the discrete solution u _p from the p-version for the obstacle problem. We prove the convergence of u _p towards the solution with respect to the energy norm, and assuming some additional regularity for the solution we derive an a priori error estimate. In numerical experiments the p-version turns out to be superior to the h-version concerning the convergence rate and the number of unknowns needed to achieve a certain exactness of the approximation.     

Hochschild cohomology and “smoothness” in monoidal categories

We introduce and investigate the properties of Hochschild cohomology of algebras in an abelian monoidal category M. We show that the second Hochschild cohomology group of an algebra in M classifies extensions of A up to an equivalence. We characterize algebras of Hochschild dimension 0 (separable algebras), and of Hochschild dimension ≤1 (formally smooth algebras). Several particular cases and applications are included in the last section of the paper.     

Solution of monotone complementarity problems with locally Lipschitzian functions

The paper deals with complementarity problems CP(F), where the underlying functionF is assumed to be locally Lipschitzian. Based on a special equivalent reformulation of CP(F) as a system of equationsφ(x)=0 or as the problem of minimizing the merit functionΘ=1/2∥Φ∥ ₂ ² , we extend results which hold for sufficiently smooth functionsF to the nonsmooth case. In particular, ifF is monotone in a neighbourhood ofx, it is proved that 0 εδθ(x) is necessary and sufficient forx to be a solution of CP(F). Moreover, for monotone functionsF, a simple derivative-free algorithm that reducesΘ is shown to possess global convergence properties. Finally, the local behaviour of a generalized Newton method is analyzed. To this end, the result by Mifflin that the composition of semismooth functions is again semismooth is extended top-order semismooth functions. Under a suitable regularity condition and ifF isp-order semismooth the generalized Newton method is shown to be locally well defined and superlinearly convergent with the order of 1+p.     

Simulated cosmic strings in a “big bang” in superfluid3He at 100 μK

During studies of the impact of single neutrons on superfluid³He at around 100μK we have measured the thermal energy released in the superfluid following the nuclear reaction, n+³He→p+³H+764keV. However, we find that the measured energy deposited in the quasiparticle system shortly after this reaction is substantially less than what we expect. We believe that this energy deficit represents that energy which has gone into the creation of vortices, in analogy to the creation of cosmic strings in the early universe via the Kibble mechanism. Furthermore, from the magnitude of the deficit, we can infer the vortex density which compares favorably with that predicted in Zurek’s scenairo.     

Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

Monitoring genomic alterations with a panel of oligonucleotide probes specific for various simple repeat motifs

Germline and somatic instability of the human genome was studied, using synthetic oligonucleotides specific for simple repeat motifs. The following probes were used: (GTG)5, (GACA)4, (GATA)4, (CT)8, (TTAGGG)3, (GT)8, (GAA)6 and (GGAT)4. Each of them is unique with respect to the target regions recognized in the genome. Thus compilation of the various fingerprint data provides a complex map of the genome (and its deviations). While the fingerprints of differentiated somatic tissues never showed any alterations, in tumor tissues (namely gliomas) many changes could be detected. Most of the latter reflect secondary karyological aberrations. In nearly one third of the gliomas, drastically amplified and apparently monomorphic DNA fragments were identified. This marker should make it possible to deal with causal pathogenetic mechanisms as well as novel diagnostic strategies.