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.     

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.     

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.     

π π andK¯K channel coupling

We investigate the origin of the attraction in theK¯K channel around the threshold by introducing an additional channel to theππ andK¯K channels in a separable potential formalism assuming, in general, no direct interaction in theK¯K channel. To reproduce the features of the data, we find that the threshold of the additional channel is much above thef ₀(975) meson position. We show that this three-channel problem can be reduced to an effective two-channel problem where thef ₀(975) behaves as if it were aK¯K molecule bound by the coupling to the exotic channel. This picture is also supported by the fact that a single pole only, in the complexK¯K momentum plane, is associated to thef ₀(975) meson. Various physical observables, like the decay branching ratio and theK¯K scattering length, are then discussed in an effective two-channel framework.     

An invariance of geometric mean with respect to Lagrangian means

The invariance of the geometric mean G with respect to the Lagrangian mean-type mapping (Lf,Lg), i.e. the equation G○(Lf,Lg)=G, is considered. We show that the functions f and g must be of high class regularity. This fact allows to reduce the problem to a differential equation and determine the second derivatives of the generators f and g.     

Monotonic solutions of a quadratic integral equation of fractional order

In the paper we indicate an error made in the proof of the main result of the paper [M.A. Darwish, On quadratic integral equation of fractional orders, J. Math. Anal. Appl. 311 (2005) 112-119]. Moreover, we provide correct proof of a slightly modified version of the mentioned result. The main tool used in our proof is the technique associated with the Hausdorff measure of noncompactness.     

Nonlinear second-order equations with functional implicit impulses and nonlinear functional boundary conditions

In this paper we deal with nonlinear second-order boundary value problems with impulses. The impulsive functions depend implicitly on the different considered variables and the boundary value conditions are nonlinear. In both cases functional dependence on the solution is allowed. The existence results follow from the existence of a pair of well-ordered lower and upper solutions.     

A Fubini theorem

Let I₀ be the σ-ideal of subsets of a Polish group generated by Borel sets which have perfectly many pairwise disjoint translates. We prove that a Fubini-type theorem holds between I₀ and the σ-ideals of Haar measure zero sets and of meager sets. We use this result to give a simple proof of a generalization of a theorem of Balcerzak-Ros?anowski-Shelah stating that I₀ on N² strongly violates the countable chain condition.