PubMed · 11443820
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R H Gregg, D K McCarthy. 2001. Laser vs laser.. https://pubmed.ncbi.nlm.nih.gov/11443820/
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Effects of salinity and clay type on the aggregation process of crude oil and clay particles (oil-mineral aggregates--OMA) were studied in the laboratory. OMA were generated by shaking various oil/clay mixtures in water at 20 degrees C and at a pre-determined energy level. Shape, median and maximum sizes, size distribution and concentration of oil droplets forming OMA were measured using epi-fluorescence microscopy. Results showed that the median and maximum sizes and the concentration of mineral-stabilized droplets increase rapidly when salinity increases from zero to a critical aggregation salinity in the range of 1.2-3.5 ppt. The magnitude of the increase of droplet size is controlled by clay type, while the increase of droplet concentration is influenced by oil type. Size distributions of oil droplets are self-similar, but their magnitudes depend on salinity and oil type. The effect of salinity on droplet size distribution is strongly influenced by clay type. Empirical relationships are derived to calculate concentration and size distribution of mineral-stabilized droplets.
A new Brønsted acidic aluminosilicate, AlTUD-1, with ideal characteristics for catalyst immobilisation (mesoporous structure, high surface area, and high Al(tetrahedral)/Si ratio), was used successfully for the noncovalent anchoring of two well-established asymmetric hydrogenation catalysts: [Rh(I)(cod)[(R,R)-MeDuPHOS]]BF4 (1) and [Rh(I)(cod)[(S,S)-DiPAMP]]BF4 (2). The new heterogeneous catalysts, 1-AlTUD-1 and 2-AlTUD-1, prepared by a straightforward ion-exchange procedure, were highly active and selective in the asymmetric reduction of dimethyl itaconate (3) and methyl 2-acetamidoacrylate (4), giving enantiomeric excesses of up to >98%. The catalysts showed similar behaviour to their homogeneous counterparts. Catalyst 2-AlTUD-1 could be re-used multiple times without loss of enantioselectivity or activity. Leaching of Rh showed a significant dependence on the polarity of the solvent in which the catalysis was performed. By applying tert-butylmethyl ether (MTBE) as solvent, the loss of Rh could be reduced to <0.1%. The solvent also had a noteworthy effect on the enantioselectivity in the hydrogenation of 4 (an effect not seen with 3 as substrate), that is, in MeOH the ee was 92%, in MTBE it dropped to 26% when using 2-AlTUD-1 as catalyst.
A method for construction of biosensors with membranous cytochrome P450 isoenzymes was developed based on clay/detergent/protein mixed films. Thin films of sodium montmorillonite colloid with incorporated cytochrome P450 2B4 (CYP2B4) with nonionic detergent were prepared on glassy carbon electrodes. The modified electrodes were electrochemically characterized, and bioelectrocatalytic reactions were followed. CYP2B4 can be reduced fast on clay-modified glassy carbon electrodes in the presence of the nonionic detergent Tween 80. In anaerobic solutions, reversible oxidation and reduction is obtained with a formal potential between -0.292 and -0.305 V vs Ag/AgCl 1 M KCl depending on the preparation of the biosensor. In air-saturated solution, bioelectrocatalytic reduction currents can be obtained with the CYP2B4-modified electrode on addition of typical substrates such as aminopyrine and benzphetamine. This reaction was suppressed when methyrapone, an inhibitor of P450 reactions, was present. Measurement of product formation also indicates the bioelectrocatalysis by CYP2B4.