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Viscosity,particle size distribution,and structural investigation of tetramethyloxysilane/2‐hydroxyethyl methacrylate sols during the sol–gel process with acid and base catalysts

The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004     

Influence of surfactant and lipid chain length on the solubilisation of phosphatidylcholine vesicles by micelles comprised of polyoxyethylene sorbitan monoesters

Photon correlation spectroscopy and freeze-fracture electron microscopy have been used to determine the ability of a range of micelle-forming, polyoxyethylene (20) sorbitan monoesters (Tweens) to solubilise vesicles prepared from phosphatidylcholines of different acyl chain lengths and degrees of saturation with a view to rationalising (in terms of their membrane toxicity) which of the micelle-forming surfactants to use as drug delivery vehicles. The phosphatidylcholines used were dimyristoyl-, dipalmitoyl-, distearoyl- and dioleoylphosphatidylcholine (DMPC, DPPC, DSPC and DOPC, respectively) while the nonionic polyoxyethylene sorbitan monoesters studied were polyoxyethylene (20) sorbitan monolaurate (Tween 20), a 9:1 weight ratio mixture of polyoxyethylene (20) sorbitan monopalmitate and monostearate (Tween 40), a 1:1 weight ratio mixture of polyoxyethylene (20) sorbitan monopalmitate and monostearate (Tween 60), and polyoxyethylene (20) sorbitan monooleate (Tween 80). The ability of the Tween micelles to solubilise phospholipid vesicles was found to depend both upon the length of the surfactant acyl chain and the length of the acyl chains of the phospholipid comprising the vesicle. Vesicles composed of long saturated diacyl chain phospholipids, namely DSPC and DPPC, were the most resistant to solubilisation, while those prepared from the shorter acyl chained DMPC were more readily solubilised. In terms of their solubilisation behaviour, vesicles made from phospholipids containing long, unsaturated acyl chains, namely DOPC behaved more akin to those vesicles prepared from DMPC. None of the Tween surfactants were effective at solubilising vesicles prepared from DPPC or DSPC. In contrast, there were clear differences in the ability of the various surfactants to solubilise vesicles prepared from DMPC and DOPC, in that micelles formed from Tween 20 were the most effective solubilising agent while those formed by Tween 60 were the least effective. As a consequence of these observations it was considered that Tween 60 was the surfactant least likely to cause membrane damage in vivo and, therefore, is the most suitable surfactant for use as a micellar drug delivery vehicle.     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.     

New Classes of Toda Soliton Solutions

We provide a detailed investigation of limits of N–soliton solutions of the Toda lattice as N tends to infinity. Our principal results yield new classes of Toda solutions including, in particular, new kinds of soliton–like (i.e., reflectionless) solutions. As a byproduct we solve an inverse spectral problem for one–dimensional Jacobi operators and explicitly construct tri–diagonal matrices that yield a purely absolutely continuous spectrum in (-1,1) and give rise to an eigenvalue spectrum that includes any prescribed countable and bounded subset of . Received: 16 October 1995/Accepted: 23 July 1996     

Chemical composition and reaction analysis of single aerosol particles

In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.     

A Primitive Non-symmetric 3-Class Association Scheme on 36 Elements with p11 = 0 Exists and is Unique

In this paper we construct a primitive, non-symmetric 3-class association scheme with parameters v = 36, v₁ = 7, p¹₁₁ = 0 and p²₁₁ = 4 and show that such a scheme is determined by its parameters.     

On practical metrology and chemical analysis: etalons and traceability systems

 National measurement systems are infrastructures to ensure, for each nation, a consistent and internationally recognised basis for measurement. Such complex systems have historical, technical, legal, organisational and institutional aspects to connect scientific metrology with practical measurements. Underlying any valid measurement is a chain of comparisons linking the measurement to an accepted standard. The ways the links are forged and the etalons (measurement standards) to which they connect are defining characteristics of all measurement systems. This is often referred to as traceability which aims at basing measurements in common measurement units – a key issue for the integration of quantitative chemical analysis with the evolving physical and engineering measurement systems. Adequate traceability and metrological control make possible new technical capabilities and new levels of quality assurance and confidence by users in the accuracy and integrity of quantitative analytical results. Traceability for chemical measurements is difficult to achieve and harder to demonstrate. The supply of appropriate etalons is critical to the development of metrology systems for chemical analysis. An approach is suggested that involves the development of networks of specialised reference laboratories able to make matrix-independent reference measurements on submitted samples, which may then be used as reference materials by an originating laboratory using its practical measurement procedures. Received: 31 July 1995 Accepted: 19 August 1995