Spectrophotometric determination of copper(II) with carbon disulfide,a secondary amine and triton X-100

Copper(II) is determined by non-extractive spectrophotometry as a complex of butylene dithiocarbamate formed in situ by reaction between carbon disulfide and pyrrolidine in aqueous Triton X-100 medium. This method is similar to that with butylene dithiocarbamate as starting material in the sense of simplicity, sensitivity, precision and accuracy. Pyrrolidine is the best of seven secondary amines tested in this way for copper determinations.     

Thin-layer chromatographic behaviour and separation of rare earths in silica gel-aqueous alkali metal chloride systems

Summary The thin-layer chromatographic behaviour of all the rare earths except Pm on silica gel in aqueous solutions of five alkali metal chlorides has been surveyed. The Rf-values and the logarithms of the separation factors relative to Gd vary in a regular and peculiar way with increasing atomic number, through a reflection of the strong tetrad effect. A discussion concerning the effects on the Rf-values of the solvent cations and the solvent anions, and typical chromatograms for the separations of multi-component mixtures containing adjacent lanthanoids are also presented.     

Monte Carlo and quasi-Monte Carlo sampling methods for a class of stochastic mathematical programs with equilibrium constraints

In this paper, we consider a class of stochastic mathematical programs with equilibrium constraints introduced by Birbil et al. (Math Oper Res 31:739–760, 2006). Firstly, by means of a Monte Carlo method, we obtain a nonsmooth discrete approximation of the original problem. Then, we propose a smoothing method together with a penalty technique to get a standard nonlinear programming problem. Some convergence results are established. Moreover, since quasi-Monte Carlo methods are generally faster than Monte Carlo methods, we discuss a quasi-Monte Carlo sampling approach as well. Furthermore, we give an example in economics to illustrate the model and show some numerical results with this example. The first author’s work was supported in part by the Scientific Research Grant-in-Aid from Japan Society for the Promotion of Science and SRF for ROCS, SEM. The second author’s work was supported in part by the United Kingdom Engineering and Physical Sciences Research Council grant. The third author’s work was supported in part by the Scientific Research Grant-in-Aid from Japan Society for the Promotion of Science.     

Simultaneous kinetic determination of secondary amines and their isomers by a spectrophotometric stopped-flow method based on the formation of dialkyldithiocarbamates

Secondary amines react with carbon disulphide to form stable dialkyldithiocarbamates at high pH in aqueous Triton X-100 solution. The formation rates of dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n-butyl- and diisobutyldithiocarbamates and pyrrolidinedithiocarbamate were measured by a stopped-flow spectrophotometric method. The reaction rates were a function of the pH of the solution and depended on the size and structure of the amines. The rate of isoalkylamines was far slower than that of the n-alkyl analogues. Individual concentrations of amines were determined in a mixture of di-n- and diisopropylamine and in a mixture of diiso- and di-n-butylamine.     

A successive quadratic programming algorithm with global and superlinear convergence properties

This paper presents a successive quadratic programming algorithm for solving general nonlinear programming problems. In order to avoid the Maratos effect, direction-finding subproblems are derived by modifying the second-order approximations to both objective and constraint functions of the problem. We prove that the algorithm possesses global and superlinear convergence properties.This work was supported in part by a Scientific Research Grant-in-Aid from the Ministry of Education, Science and Culture, Japan.     

An efficient solid‐state polycondensation method for synthesizing stereocomplexed poly(lactic acid)s with high molecular weight

Simultaneous solid‐state polycondensation (SSP) of the powdery prepolymers of poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) can produce entire stereocomplexed poly(lactic acid)s (sc‐PLA) with high molecular weight and can be an alternative synthetic route to sc‐PLA. Ordinary melt polycondensations of L ‐ and D ‐lactic acids gave the PLLA and PDLA prepolymers having medium molecular weight which were pulverized for blending in 1:1 ratio. The resultant powder blends were then subjected to SSP at 130–160 °C for 30 h under a reduced pressure of 0.5 Torr. Some of the products thus obtained attained a molecular weight (M_w) as high as 200 kDa, consisting of stereoblock copolymer of PLLA and PDLA. A small amount of the stereocomplex should be formed in the boundaries of the partially melted PLLA and PDLA where the hetero‐chain connection is induced to generate the blocky components. The resultant SSP products showed predominant stereocomplexation after their melt‐processing in the presence of the stereoblock components in spite of containing a small amount of racemic sequences in the homo‐chiral PLLA and PDLA chains. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3714–3722, 2008