UV light‐mediated alkylation of inorganic selenium

In the presence of low molecular weight organic acids (formic, acetic, propionic and malonic), inorganic selenium(IV) is converted by UV irradiation to volatile selenium carbonyl, dimethylselenide and diethylselenide, depending on the acid used. Gas chromatography–mass spectrometry analysis of the volatile products shows that, in 0.7 M formic acid solution, approximately 60–70% (v/v) SeH₂ and 30–40% (v/v) SeCO are formed. The presence of nitrate ion appears to increase threefold the formation of SeCO while completely suppressing formation of SeH₂. Copyright © 2003 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.     

Homogenization of the Three-dimensional Hall Effect and Change of Sign of the Hall Coefficient

The notion of a Hall matrix associated with a possibly anisotropic conducting material in the presence of a small magnetic field is introduced. Then, for any material having a microstructure we prove a general homogenization result satisfied by the Hall matrix in the framework of the H-convergence of Murat–Tartar. Extending a result of Bergman, we show that the Hall matrix can be computed from the corrector associated with the homogenization problem when no magnetic field is present. Finally, we give an example of a microstructure for which the Hall matrix is positive isotropic almost everywhere, while the homogenized Hall matrix is negative isotropic.     

Poly(arylene sulfide)s by nucleophilic aromatic substitution polymerization of 2,7‐difluorothianthrene

Poly(thianthrene phenylene sulfide) and poly(thianthrene sulfide) have been prepared by nucleophilic aromatic substitution polymerization of the activated monomer 2,7‐difluorothianthrene with bis thiophenoxide and sulfide nucleophiles, respectively. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) mass spectrometry, UV‐Vis spectroscopy, refractometry, and intrinsic viscosity (IV) measurements. The polymers produced exhibit 5% weight loss values approaching 500 °C in inert and air atmospheres and glass transition temperatures that range from 149 to 210 °C. Poly(thianthrene phenylene sulfide) with a number average molecular weight of 22,100 g/mol has been synthesized with an IV in DMPU of 0.62 dL/g at 30 °C. Creasable films of this polymer have been prepared by solvent casting and melt pressing at 250 °C. Films of poly(thianthrene phenylene sulfide) exhibit transparencies greater than 50% at wavelengths exceeding 400 nm and a high refractive index value of 1.692 at a wavelength of 633 nm, making the polymer interesting for optical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2453–2461, 2009     

Outputs and time lags for linear bioreactors

Linear systems of convection reaction-diffusion equations for bioreactors are shown to have a structure which allows a geometric factorization of steady state problems giving a significant reduction in their dimensionality. Moreover, convection dominated linear systems with quasisymmetric reaction terms may be further simplified by matrix transformations, which uncouple the differential equations. The boundary conditions are also uncoupled when the diagonal diffusivity matrix D governing diffusion in the bioparticle is a scalar multiple of the corresponding matrix H describing the diffusivity characteristic of the fluid boundary layers around the bioparticles. The dominant transient behaviour of the systems may be handled by establishing an analogous system of time independent equations for mean action time variables and higher moments. These equations have the same amenable structure. Outputs, time lags and various mean residence and first passage times, associated with establishing steady outputs from a concentration free initial state, can be expressed in terms of the steady state solutions and mean action time variables.     

Applications of ICP-MS in marine analytical chemistry

Summary The versatility of ICP-MS in marine analytical chemistry is illustrated with applications to the multielement trace analysis of two recently released marine reference materials, the coastal seawater CASS-2 and the non-defatted lobster hepatopancreas tissue LUTS-1, and to the determination of tributyltin and dibutyltin in the harbour sediment reference material PACS-1 by HPLC-ICP-MS. Seawater analyses were performed after separation of the trace elements either by adsorption on immobilized 8-hydroxy-quinoline or by reductive coprecipitation with iron and palladium. Simultaneous determination of seven trace elements in LUTS-1, including mercury, by isotope dilution ICP-MS, was achieved after dissolution by microwave digestion with nitric acid and hydrogen peroxide. Butyltin species in PACS-1 were separated by cation exchange HPLC of an extract of the sediment; method detection limits for tributyltin and dibutyltin in sediment samples are estimated to be 5 ng Sn/g and 12 ng Sn/g, respectively.Summer assistant 1988Summer assistant 1989     

An Extremal Problem Arising in the Dynamics of Two-Phase Materials That Directly Reveals Information about the Internal Geometry

In two-phase materials, each phase having a non-local response in time, it has been found that for some driving fields the response somehow untangles at specific times, and allows one to directly infer useful information about the geometry of the material, such as the volume fractions of the phases. Motivated by this, and to obtain an algorithm for designing appropriate driving fields, we find approximate, measure independent, linear relations between the values that Markov functions take at a given set of possibly complex points, not belonging to the interval [-1,1] where the measure is supported. The problem is reduced to simply one of polynomial approximation of a given function on the interval [-1,1] and, to simplify the analysis, Chebyshev approximation is used. This allows one to obtain explicit estimates of the error of the approximation, in terms of the number of points and the minimum distance of the points to the interval [-1,1]. Assuming this minimum distance is bounded below by a number greater than 1/2, the error converges exponentially to zero as the number of points is increased. Approximate linear relations are also obtained that incorporate a set of moments of the measure. In the context of the motivating problem, the analysis also yields bounds on the response at any particular time for any driving field, and allows one to estimate the response at a given frequency using an appropriately designed driving field that effectively is turned on only for a fixed interval of time. The approximation extends directly to Markov-type functions with a positive semidefinite operator valued measure, and this has applications to determining the shape of an inclusion in a body from boundary flux measurements at a specific time, when the time-dependent boundary potentials are suitably tailored. © 2022 Wiley Periodicals, Inc.     

Radiofluorination of a Pre‐formed Gallium(III) Aza‐macrocyclic Complex: Towards Next‐Generation Positron Emission Tomography (PET) Imaging Agents

As part of a study to investigate the factors influencing the development of new, more effective metal‐complex‐based positron emission tomography (PET) imaging agents, the distorted octahedral complex, [GaCl(L)]?2 H₂O has been prepared by reaction of 1‐benzyl‐1,4,7‐triazacyclononane‐4,7‐dicarboxylic acid hydrochloride (H₂L?HCl) with Ga(NO₃)₃?9 H₂O, which is a convenient source of Ga^III for reactions in water. Spectroscopic and crystallographic data for [GaCl(L)]?2 H₂O are described, together with the crystal structure of [GaCl(L)]?MeCN. Fluorination of this complex by Cl^?/F^? exchange was achieved in high yield by treatment with KF in water at room temperature over 90 minutes, although the reaction was complete in approximately 30 minutes if heated to 80 °C, giving [GaF(L)]?2 H₂O in good yield. The same complex was obtained by hydrothermal synthesis from GaF₃?3 H₂O and Li₂L, and has been characterised by single‐crystal X‐ray analysis, IR, ¹H and ¹⁹F{¹H} NMR spectroscopy and ESI⁺ MS. Radiofluorination of the pre‐formed [GaCl(L)]?2 H₂O has been demonstrated on a 210 nanomolar scale in aqueous NaOAc at pH 4 by using carrier‐free ¹⁸F^?, leading to 60–70 % ¹⁸F‐incorporation after heating to 80 °C for 30 minutes. The resulting radioproduct was purified easily by using a solid‐phase extraction (SPE) cartridge, leading to 98–99 % radiochemical purity. The [Ga¹⁸F(L)] is stable for at least 90 minutes in 10 % EtOH/NaOAc solution at pH 6, but defluorinates over this time scale at pH of approximately 7.5 in phosphate buffered saline (PBS) or human serum albumin (HSA). The subtle role of the Group 13 metal ion and co‐ligand donor set in influencing the pH dependence of this system is discussed in the context of developing potential new imaging agents for PET.