Asymptotic properties of computationally efficient alternative estimators for a class of multivariate normal models

Parameters of Gaussian multivariate models are often estimated using the maximum likelihood approach. In spite of its merits, this methodology is not practical when the sample size is very large, as, for example, in the case of massive georeferenced data sets. In this paper, we study the asymptotic properties of the estimators that minimize three alternatives to the likelihood function, designed to increase the computational efficiency. This is achieved by applying the information sandwich technique to expansions of the pseudo-likelihood functions as quadratic forms of independent normal random variables. Theoretical calculations are given for a first-order autoregressive time series and then extended to a two-dimensional autoregressive process on a lattice. We compare the efficiency of the three estimators to that of the maximum likelihood estimator as well as among themselves, using numerical calculations of the theoretical results and simulations.     

Lyapunov-type inequalities for nonlinear systems

In this paper, by using elementary analysis, we establish some new Lyapunov-type inequalities for nonlinear systems of differential equations, special cases of which contain the well-known equations such as Emden-Fowler-type and half-linear equations. The inequalities obtained here can be used as handy tools in the study of qualitative behaviour of solutions of the associated equations.     

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.     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

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.     

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.