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     

On the vector field problem for O(n)/O(1)xO(1)xO(n-2)

We prove new results about the vector field problem on the real flag manifolds O(n)/O(1) x O(1) x O(n - 2). For some infinite families of these manifolds, we completely solve the vector field problem.     

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.     

Division and <Emphasis Type="Italic">k</Emphasis>-th root theorems for <Emphasis Type="Italic">Q</Emphasis>-manifolds

We prove that a locally compact ANR-space X is a Q-manifold if and only if it has the Disjoint Disk Property (DDP), all points of X are homological Z _∞-points and X has the countable-dimensional approximation property (cd-AP), which means that each map f: K → X of a compact polyhedron can be approximated by a map with the countable-dimensional image. As an application we prove that a space X with DDP and cd-AP is a Q-manifold if some finite power of X is a Q-manifold. If some finite power of a space X with cd-AP is a Q-manifold, then X ² and X × [0, 1] are Q-manifolds as well. We construct a countable family χ of spaces with DDP and cd-AP such that no space X ∈ χ is homeomorphic to the Hilbert cube Q whereas the product X × Y of any different spaces X, Y ∈ χ is homeomorphic to Q. We also show that no uncountable family χ with such properties exists. This work was supported by the Slovenian-Ukrainian (Grant No. SLO-UKR 04-06/07)     

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.     

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.     

Nonlinear and chaotic oscillations of a constrained cantilevered pipe conveying fluid: A full nonlinear analysis

In this paper, the planar dynamics of a nonlinearly constrained pipe conveying fluid is examined numerically, by considering the full nonlinear equation of motions and a refined trilinear-spring model for the impact constraints—completing the circle of several studies on the subject. The effect of varying system parameters is investigated for the two-degree-of-freedom (N=2) model of the system, followed by less extensive similar investigations forN=3 and 4. Phase portraits, bifurcation diagrams, power spectra and Lyapunov exponents are presented for a selected set of system parameters, showing some rather interesting, and sometimes unexpected, results. The numerical results are compared with experimental ones obtained previously. It is found that in the parameter space that includesN, there exists a subspace wherein excellent qualitative, and reasonably good (N=2) to excellent (N=4) quantitative agreement with experiment. In the latter case, excellent agreement is not only obtained in the threshold flow velocities (u) for the key bifurcations, but the inclusion of the nonlinear terms improves agreement with experiment in terms of amplitudes of motion and by capturing features of behaviour not hitherto predicted by theory.     

Algorithms for ham-sandwich cuts

Given disjoint setsP ₁,P ₂, ...,P _d inR ^d withn points in total, ahamsandwich cut is a hyperplane that simultaneously bisects theP _i . We present algorithms for finding ham-sandwich cuts in every dimensiond>1. Whend=2, the algorithm is optimal, having complexityO(n). For dimensiond>2, the bound on the running time is proportional to the worst-case time needed for constructing a level in an arrangement ofn hyperplanes in dimensiond−1. This, in turn, is related to the number ofk-sets inR ^d−1 . With the current estimates, we get complexity close toO(n ^3/2 ) ford=3, roughlyO(n ^8/3 ) ford=4, andO(n ^d−1−a(d) ) for somea(d)>0 (going to zero asd increases) for largerd. We also give a linear-time algorithm for ham-sandwich cuts inR ³ when the three sets are suitably separated. A preliminary version of the results of this paper appeared in [16] and [17]. Part of this research by J. Matoušek was done while he was visiting the School of Mathematics, Georgia Institute of Technology, Atlanta, and part of his work on this paper was supported by a Humboldt Research Fellowship. W. Steiger expresses gratitude to the NSF DIMACS Center at Rutgers, and his research was supported in part by NSF Grants CCR-8902522 and CCR-9111491.     

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.