HPLC separation and quantification of anionic surfactants using an automated on-line ion pair extraction system

Summary Aliphatic anionic surfactants, like alkylsulfonates, alkyl sulfates, -sulfo alkanoic acids and their esters, were separated with respect to their alkyl chain length by high performance liquid chromatography (HPLC) using reversed phase (RP) columns. For sensitive and specific detection of these classes of compounds the HPLC separation was combined with a post-column ion-pair extraction system. The limit of detection is in the range of 3–30 ng. Previously reported detection systems of this kind were modified by changing the inner set-up of the phase separator and the extraction capillary and integrating a purge function, which led to a higher system stability and made automatization possible. In order to optimize the experimental set-up, the influence of the reagent concentration as well as different sizes and materials of the extraction capillary were evaluated. The calibration curve of surfactant concentrations versus fluorescence emission is discussed for sodium decylsulfonate. Since both the electrolyte concentration and the percentage of organic solvents in the mobile phase may adversely affect the detection system, different eluent compositions were tested.This article is part of the planned dissertation of Markus Schoester at the Mathematical Natural Science Faculty of the University of Düsseldorf     

A new chiral Rh(II) catalyst for enantioselective [2 + 1]-cycloaddition. mechanistic implications and applications

A novel chiral Rh(II) catalyst (1) is introduced for the [2 + 1]-cycloaddition of ethyl diazoacetate to terminal acetylenes and olefins with high enantioselectivity. The catalyst 1 consists of one acetate bridging group and three mono-N-triflyldiphenylimidazoline-2-one bidentate ligands (DPTI) spanning the Rh(II)-Rh(II) metallic center in a structure that was determined by single-crystal X-ray diffraction analysis. A rational mechanism is advanced that provides a straightforward explanation for the enantioselectivity and absolute stereochemical course of the [2 + 1]-cycloaddition reactions. A key element in this explanation is the cleavage of one of the Rh-O bonds of the bridging acetate group in the intermediate Rh-carbene complex to form a new pentacoordinate Rh carbene complex (formally 1.5 valent Rh) that can undergo [2 + 2]-cycloaddition with the C-C pi-bond of the acetylenic or olefinic substrate. Reductive elimination of the resulting adduct affords the cyclopropene or cyclopropane product. The C2-symmetry of the two DPTI ligands orthogonal to the bridging acetate also contributes to the high observed enantioselectivity and mechanistic clarity. The catalyst 1, which functions effectively at 0.5 mol %, can be recovered efficiently for reuse. Its ready availability, robustness, and effectiveness suggest it as a useful addition to the list of practical chiral Rh(II) catalysts for synthesis.     

A certified reference material for radionuclides in the water sample from Irish Sea (IAEA-443)

A new certified reference material (CRM) for radionuclides in sea water from the Irish sea (IAEA-443) is described and the results of the certification process are presented. Ten radionuclides (³H, ⁴⁰K, ⁹⁰Sr, ¹³⁷Cs, ²³⁴U, ²³⁵U, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am) have been certified, and information values on massic activities with 95% confidence intervals are given for four radionuclides (²³⁰Th, ²³²Th, ²³⁹Pu and ²⁴⁰Pu). Results for less frequently reported radionuclides (⁹⁹Tc, ²²⁸Th, ²³⁷Np and ²⁴¹Pu) are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in water samples, for the development and validation of analytical methods and for training purposes. The material is available in 5 L units from IAEA (http://nucleus.iaea.org/rpst/index.htm).     

Maritime inventory routing with multiple products: A case study from the cement industry

This paper considers a maritime inventory routing problem faced by a major cement producer. A heterogeneous fleet of bulk ships transport multiple non-mixable cement products from producing factories to regional silo stations along the coast of Norway. Inventory constraints are present both at the factories and the silos, and there are upper and lower limits for all inventories. The ship fleet capacity is limited, and in peak periods the demand for cement products at the silos exceeds the fleet capacity. In addition, constraints regarding the capacity of the ships’ cargo holds, the depth of the ports and the fact that different cement products cannot be mixed must be taken into consideration. A construction heuristic embedded in a genetic algorithmic framework is developed. The approach adopted is used to solve real instances of the problem within reasonable solution time and with good quality solutions.     

Reference material for radionuclides in sediment IAEA-384 (Fangataufa Lagoon sediment)

A reference material designed for the determination of anthropogenic and natural radionuclides in sediment, IAEA-384 (Fangataufa Lagoon sediment), is described and the results of certification are presented. The material has been certified for 8 radionuclides (⁴⁰K, ⁶⁰Co, ¹⁵⁵Eu, ²³⁰Th, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am). Information values are given for 12 radionuclides (⁹⁰Sr, ¹³⁷Cs, ²¹⁰Pb (²¹⁰Po), ²²⁶Ra, ²²⁸Ra, ²³²Th, ²³⁴U, ²³⁵U, ²³⁹Pu, ²⁴⁰Pu and ²⁴¹Pu). Less reported radionuclides include ²²⁸Th, ²³⁶U, ²³⁹Np and ²⁴²Pu. The reference material may be used for quality management of radioanalytical laboratories engaged in the analysis of radionuclides in the environment, as well as for the development and validation of analytical methods and for training purposes. The material is available from IAEA in 100 g units. Retired from IAEA in 2003.     

Analysis of evolution through competitive selection

Recent studies of in vitro evolution of DNA via protein binding indicate that the evolution behavior is qualitatively different in different parameter regimes. I here present a general theory that is valid for a wide range of parameters, and which reproduces and extends previous results. Specifically, the mean-field theory of a general translation-invariant model can be reduced to the basic diffusion equation with a dynamic boundary condition. The simple analytical form yields both quantitatively accurate predictions and valuable insight into the principles involved.     

The Gravitating Perfect Fluid-Scalar Field Equations: Quintessence and Tachyonic Matter

The system consisting of a self gravitating perfect fluid and scalar field is considered in detail. The scalar fields considered are the quintessence and tachyonic forms which have important application in cosmology. Mathematical properties of the general system of equations are studied including the algebraic and differential identities as well as the eigenvalue structure. The Cauchy problem for both quintessence and the tachyon is presented. We discuss the initial constraint equations which must be satisfied by the initial data. A Cauchy evolution scheme is presented in the form of a Taylor series about the Cauchy surface. Finally, a simple numerical example is provided to illustrate this scheme.     

Insight into on-wafer crystallization of pure-silica-zeolite films through nutrient replenishment

Tetraethylorthosilicate (TEOS) is added to a pure-silica-zeolite MEL nanoparticle suspension and the mixture is subsequently used for preparing spin-on low-dielectric constant (low-k) films. The films are then characterized by ellipsometric porosimetry, transmission electron microscopy (TEM), and nanoindentation. Investigation into the film microstructure indicates that the addition of TEOS significantly increases the fraction of the crystalline domains, decreases the inter-crystal mesopore size, and narrows the pore size distribution. Films with 12% TEOS loading have a mean pore size distribution centered at 3.5 nm (diameter) with a full width at half maximum (fwhm) of 0.8 nm, while those with no TEOS have a distribution at 11.1 nm and fwhm of 7.9 nm. At 12% TEOS loading, the reduced modulus and hardness are 11.0 and 1.12 GPa, respectively; without TEOS, the values are 6.4 and 0.57 GPa.     

On‐Wafer Crystallization of Ultralow‐κ Pure Silica Zeolite Films

A higher goal : An on‐wafer crystallization process to prepare pure silica zeolite (PSZ) MEL‐type films that is superior to the previously used hydrothermal process is reported. These striation‐free MEL‐type films (right, see picture) outperform the traditional spin‐on films (left) in terms of the κ value, mechanical properties, surface roughness, mesopore size, and size distribution.

     

In‐situ Chemiluminescence‐Driven Reversible Addition–Fragmentation Chain‐Transfer Photopolymerization

The power of chemical light generation (chemiluminescence) is used to drive polymerization reactions. A biphasic reaction is developed such that light‐generating reactions are confined to the organic phase and photopolymerization occurs in the aqueous phase. Well‐defined RAFT‐capped polymers are synthesized and the kinetics are shown to be dictated by light generation.