Working Methods Paper: Critical considerations with respect to the identification of tin species in the environment

Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation.     

General base catalysis in the decomposition of N-Cl-Valine in aqueous solution

This article analyzes the kinetics of the decomposition of N-Cl-Valine in aqueous solution, which is formed rapidly by chlorination of Valine with sodium hypochlorite. A general-base catalyzed process not yet described is reported. The experimental evidence shows two competitive decomposition paths: an unimolecular concerted fragmentation process (k = (1.8 ± 0.1) · 10^?4 s^?1 at 298 K) and the other one is an E2 elimination process whose importance increases with pH and depends on the nature and the concentration of the bases present in the medium. © 1994 John Wiley & Sons, Inc.     

Large Sample Properties of Mixture Models with Covariates for Competing Risks

We study the large-sample properties of a class of parametric mixture models with covariates for competing risks. The models allow general distributions for the survival times and incorporate the idea of long-term survivors. Asymptotic results are obtained under a commonly assumed independent censoring mechanism and some modest regularity conditions on the survival distributions. The existence, consistency, and asymptotic normality of maximum likelihood estimators for the parameters of the model are rigorously derived under general sufficient conditions. Specific conditions for particular models can be derived from the general conditions for ready check. In addition, a likelihood-ratio statistic is proposed to test various hypotheses of practical interest, and its asymptotic distribution is provided.     

On error bounds for lower semicontinuous functions

We give some sufficient conditions for proper lower semicontinuous functions on metric spaces to have error bounds (with exponents). For a proper convex function f on a normed space X the existence of a local error bound implies that of a global error bound. If in addition X is a Banach space, then error bounds can be characterized by the subdifferential of f. In a reflexive Banach space X, we further obtain several sufficient and necessary conditions for the existence of error bounds in terms of the lower Dini derivative of f. Received: April 27, 2001 / Accepted: November 6, 2001?Published online April 12, 2002     

Thermoelectric properties of tin clathrates under hydrostatic pressure

We report the temperature dependence of electrical resistance (R) and thermopower (S) of clathrate Cs₈Sn₄₄ under high pressure up to 1.2 GPa. We observe a reversible gap widening, prominent relaxation effect of R, irreversible increase of |S| under high pressure. We also find that the power factor S²σ (σ: electrical conductivity) reaches a maximum at pressure of 0.3 GPa. Comparison of the experimental results with band structure calculations suggests that the intrinsic vacancy in the clathrate structure of Cs₈Sn₄₄ plays an important role in transport properties under high pressure. Measurements on Cs₈Zn₄Sn₄₂, a clathrate which has defects other than vacancies, are compared with Cs₈Sn₄₄. The results indicate that replacing Sn by Zn has similar effect as the intrinsic vacancy on S.     

An efficient lasing action from pyrromethene 556 dye-doped organically modified silicates

Organically modified solid-state silicates (ORMOSILS) doped with a new laser dye 1,3,5,7,8-pentamethylpyrromethene-2,6-disulfonate-BF₂ complex (pyrromethene 556) have been synthesized by a sol-gel method and the compositional effects on pore characteristics, fluorescence and lasing properties have been investigated. It is found that the use of dimethylsulfoxide and γ-glycidoxypropyltrimethoxysilane could greatly change the structure properties of sol-gel derived ORMOSILS cage, and thus the fluorescence and lasing properties of the materials could improve significantly. A successful laser oscillation from this dye-doped ORMOSILS sample has been achieved upon pumping with a Q-switched frequency-doubled Nd:YAG laser at 532 nm. A slope efficiency of 54% with a useful lifetime greater than 10,000 shots has been demonstrated at a pump repetition rate of 1 Hz and a pump intensity of 1 J/cm² by using the new ORMOSILS cage on our newly designed laser system. Our results have shown that it is possible to obtain a high-efficiency with a long-lifetime for a compact new laser device by low cost dye-doped solid-state ORMOSILS.     

Learning Markov chains in fractal compression of image data

In a recent paper [17] we proposed a stochastic algorithm which generates optimal probabilities for the decompression of an image represented by the fixed point of an IFS system (SAOP). We show here that such an algorithm is in fact a non trivial example of Generalized Random System with Complete Connections. We also exhibit a generalization which could represent the solution to the inverse problem for an image with grey levels, if a fixed set of contraction maps is available. Received: 1 July 2002     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.     

泛连通图定理和Ore2条件

记Ore2=min{d(y) d(x)|x,y∈V(G),d(x,y)=2}，本得到：若n阶图G的Ore2≥n 1，则G是[5;n]泛连通图。此是比Faudree等人的定理进一步的结果。