Galactose Oxidase/Prussian Blue Based Biosensors

This paper describes the development of an amperometric biosensor based on galactose oxidase (GAOx) immobilization within a laponite clay film deposited on Carbon Screen‐Printed Electrodes modified by electrodeposited Prussian Blue and coated with poly‐(O‐phenylenediamine) (PPD/PB/CSPEs). Amperometric performances of GAOx@laponite/PPD/PB/CSPEs bioelectrodes were determined using several GAOx substrates. Using these modified electrodes the reduction of enzymatically generated hydrogen peroxide was performed at ?0.2 V vs. Ag‐AgCl. In an initial attempt, E.Coli transketolase activity on its immobilized form was followed using a bienzymatic GAOx‐TK biosensor.     

On a damage law for creep rupture of clays with accumulated inelastic deviatoric strain as a damage measure

To avoid the dependency on origin of time, an improved damage law for creep rupture of clays is proposed considering the accumulated inelastic deviatoric strain as a measure of damage, instead of incorporating time directly. This law is incorporated into an existing anisotropic elastoplastic-viscoplastic bounding surface model for clays. The performance of the damage law was demonstrated via the simulations of creep rupture tests on undisturbed clays, and generally a good agreement between model simulations and test data was obtained. Discussions on the creep rupture parameters were followed and further improvement was suggested. At present when high quality test data for creep rupture is very limited, the proposed damage law could serve as a practical way to model creep rupture of clays.     

Adsorption of nucleic acid bases on clays: an investigation using Langmuir and Freundlich isotherms and FT-IR spectroscopy

In the present paper, the adsorption of nucleic acid bases (A, adenine; C, cytosine; U, uracil; and T, thymine) on clays (bentonite, kaolinite, and montmorillonite) was studied at different pH (2.00 and 7.20). It should be pointed out there is no reported study of adsorption of nucleic acid bases on clays using seawater (with the major elements), and a wide range of pH. The main finding of this study was that the ratio of A and T adsorbed on clays ranged from 4.68 to 25.1, much higher than the ratio of their occurrence in organisms ranging from 0.95 to 1.05. The weaker adsorption of U and T on clays raises the question of the possibility of a genetic code based on purines only. The FT-IR spectra at pH 2.00 showed that the interaction of A, C, T, and U with the clays occurs through positively charged, protonated groups. Correspondence: Dr. Dimas A. M. Zaia, Departamento de Química-CCE, Universidade Estadual de Londrina, 86051-990 Londrina-PR, Brazil.     

Some novel layered-silicate nanocomposites based on a biodegradable hydroxybutyrate copolymer

This paper describes the preparation, characterization, mechanical properties and thermal stability of layered silicate nanocomposites based on poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-co-PHH, known as Nodax^TM). The dispersed phases were organically modified montmorillonites (clay 20A and clay 25A), mica, and talc, and they were introduced by solution mixing. Wide-angle X-ray scattering results and transmission electron microscopy (TEM) images confirmed that these two clays were intercalated and finely distributed in the Nodax^TM matrix. This type of layered filler led to remarkable improvements in mechanical properties even at very low loadings. Minimizing aggregation was more of a problem in the case of the mica and the talc, at least in this particular matrix. In some cases, these layered fillers slightly decreased the thermal stability of the Nodax^TM.     

Composites based on modified clay assembled Rh(III)–heteropolymolybdates as catalysts in the liquid-phase hydrogenation of cinnamaldehyde

New composites based on the [RhMo₆O₂₄H₆]³⁻ (RhMo₆) heteropolyanion supported on pillared (PILC), heterostructured (PCH) and functionalized(PILC-F) and (PCH-F) systems based on clays were prepared, characterized and tested as catalysts in the liquid-phase hydrogenation of cinnamaldehyde. The original phases and supported systems were characterized using several techniques such as powder X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM–EDS), Raman microprobe studies, X-ray photoelectron spectroscopy (XPS), thermogravimetry and differential thermal analyses (TG-DSC), temperature programmed reduction (TPR), and textural analysis (BET method), which confirmed their functionalization, physicochemical modification and the nature of Mo adsorbed species. Active acidic, basic and redox sites were determined by temperature programmed surface reaction (TPSR). Mo loading reached 7 wt% for the system RhMo₆/PCH-F and 3 wt% for the system RhMo₆/PILC-F, while unfunctionalized clay systems showed a value of 1 wt% of Mo. The catalytic performance showed that PCH-based composites were the most active and reached up to 56% conversion at 360 min of reaction when tested in liquid-phase cinnamaldehyde hydrogenation. The selectivity for all the systems was mainly toward hydrocinnamic aldehyde (HCAL) and reached 77% for the RhMo₆/PCH-F catalyst at 25% conversion.     

An Overview of the High‐Pressure Vibrational Spectra of Clays and Related Minerals

Abstract

An overview of the effect of high external pressures on clays and related minerals is presented. The results show that this is an area that will welcome further investigation in the future, especially in view of the importance of clay minerals in the Earths's mantle and, possibly, even in prebiotic chemistry in the formation of amino acids and the mineralogy of the Martian surface.     

Regioselective bromination of aromatic compounds with Br2/SO2Cl2 over microporous catalysts

A new selective brominating system Br₂/SO₂Cl₂/zeolite, has been discovered. Partially cation-exchanged Ca²⁺-Y zeolite efficiently catalyzes the selective para-bromination of neat chlorobenzene (CB) by Br₂/SO₂Cl₂ affording a CB conversion of ∼89% and a para-selectivity of ∼97%. During the bromination reaction, SO₂Cl₂ oxidizes HBr, prevents its accumulation within the zeolite pores and yields a more active brominating species. The Ca²⁺-Y catalyst was found to be stable under the bromination conditions, and can easily be regenerated by calcination. The Br₂/SO₂Cl₂/Ca²⁺-Y brominating system could be applicable to other activated aromatic compounds such as o-xylene, toluene and fluorobenzene.     

X-ray microtomography for studying localized deformation in fine-grained geomaterials under triaxial compressionUtilisation de la microtomographie rayon X pour l'étude de la localisation des déformations dans les géomatériaux argileux sous sollicitation axisymétrique.

This Note presents a few selected results of an experimental testing program carried out at the ESRF in Grenoble, France. X-ray microtomography (with a spatial resolution of 14 μm) has been used to evaluate the onset and evolution of shear banding in a fine-grained stiff soil under deviatoric loading. It allowed detailed observations of strain localization in a specimen during the test, including the presence of more than one shear zone and a varying degree of dilatancy and/or crack opening. To cite this article: G. Viggiani et al., C. R. Mecanique 332 (2004).     

Preparation and characterization of microporous SiO2-ZrO2 pillared montmorillonite

SiO₂-ZrO₂ pillared montmorillonite (SZM) was prepared by the reaction of Na-montmorillonite with colloidal silica-zirconia particles which were prepared by depositing zirconium hydroxy cations on silica particles. By pillaring with the colloidal particles, the basal spacing of montmorillonite was expanded to ca. 45 Å and the calcined SZM samples showed large specific surface areas up to 320 m²/g at 400 °C. In spite of large interlayer separation, adsorption results indicated the presence of micropores generated between the colloidal particles. The microporous structure was maintained at least up to 600 °C and exhibited specific shape selectivity for the adsorption of large organic molecules, especially between toluene and mesitylene. According to the temperature-programmed-desorption (TPD) spectra of ammonia, the calcined SZM showed weakly acidic sites.     

Polystyrene nanocomposites based on an oligomerically-modified clay containing maleic anhydride

An oligomerically-modified clay containing maleic anhydride was used to prepare polystyrene-clay nanocomposites by melt blending and the effect of this modified clay on the thermal stability and fire performance was studied. These nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis and cone calorimetry. The results show a mixed immiscible/intercalated/delaminated morphology. The maleic anhydride modified clay improved the compatibility between the clay and the polystyrene.