Facile optical resolution of amino acid esters via hydrolysis by an industrial enzyme in organic solvents

Racemic amino acid esters were optically resolved via hydrolysis in organic solvents by the catalysis of an industrial alkaline protease, “Alcalase”. The products which were composed mainly of L-amino acids were insoluble and easily separated by filtration. The activity of the enzyme and enantiomeric excess of the products were significantly dependent on the nature of solvent and the water content in the reaction media. Generally, high values of enantiomeric excess were obtained at low water contents. Many natural and unnatural amino acids were resolved by this method.     

Studies on Catalytic Side-Chain Oxidation of Nitroaromatics to Aldehydes with Oxygen

The side-chain oxidation of 2-nitrotoluene in liquid phase in the presence of catalytic amount of manganese sulfate and stoichiometric amount of potassium hydroxide with oxygen was studied. In the most favorable conditions, over 80% of conversion of 2-nitrotoluene and 50% of selectivity to 2-nitrobenzaldehyde was achieved. Effects of the reaction parameters on the conversion of the reactant and the selectivity of the product were examined. These results, together with EPR spectroscopic study, show that a benzyl anion was formed in the early stage of the reaction, which was then converted to the final product via a free radical mechanism.     

The effect of cooking on proteins from acha (Digitaria exilis) and durum wheat

The effect of cooking on proteins from acha and durum wheat was assessed from an analysis of protein extractability, gel electrophoretic profiles, in-vitro protein digestibility (IVPD) and the amino acid compositions of wholemeal flour and residue proteins. Heating wholemeal flour samples at 100–140°C (t = 10–40 min) resulted in 0–30% and 45–55% decreases in acha and durum protein solubility, respectively. In general, high molecular weight (30–70 k Da) protein subunits were more susceptible to heat damage. For both cereals, sodium dodecyl sulphate (SDS; 10 g litre^?1) and/or dithiothrcitol (DTT; 10 mM ) increased protein solubility in unheated and heated samples. The IVPD index was 90–91% and was not significantly altered by cooking (100–120°C, t = 40 min). Cooking at extreme temperatures (140°C, t = 40 min) reduced the IVPD by 8% (P = 0.05). Osborne fractionation resulted in a durum or acha residue level of 7.8% or 55.2%. Treatment with solvent containing propanol, SDS and/or DTT at room temperature followed by SDS-polyacrylamide gel electrophoresis of non-solubilised proteins showed that the glutelin fraction of acha, with the exception of a 65 kDa subunit, was insoluble owing to strong inter-subunit hydrophobic and disulphide interactions. Wholemeal acha flour and residue protein showed a significantly greater level of hydrophobic and sulphur amino acids as well as glutamine which is associated with H-bonding. The possibility that cereal protein solubility is also dependent on protein-carbohydrate links is discussed.     

Candida and Pseudomonas Lipase-Catalyzed Hydrolysis of Butteroil in the Absence of Organic Solvents

Candida rugosa lipase (CRL) and Pseudomonas fluorescein lipase (PFL) were used to hydrolyze a low-melting point butteroil fraction in the absence of orgaic solvents. CRL and PFL displayed pH activity optima of 6.7 and 7.8, and temperature-activity optima of 40–50°C and 35°C, respectively. Maximum activity for PFL was observed at 5% (v/v) water content. CRL showed higher specificity towards butyric acid relative to PFL after 3 hours of hydrolysis at 40°C (22.3 mol% vs 7.8 mol%, respectively). Both enzymes displayed, however, high specificities towards palmitic and oleic acids. CRL's inherent specificity towards butyric acid makes it an ideal choice for a biological catalyst to generate useful dairy flavor profiles.     

Prebiotic synthesis of sequential peptides on the Hadean beach by a molecular engine working with nitrogen oxides as energy sources

Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.     

Antioxidant activity of anacardic acids

Anacardic acids, 6-pentadec(en)ylsalicylic acids isolated from the cashew Anacardium occidentale L. (Anacardiaceae) nut and apple, were found to possess preventive antioxidant activity while salicylic acid did not show this activity. These anacardic acids prevent generation of superoxide radicals by inhibiting xanthine oxidase (EC 1.1.3.22, Grade IV) without radical-scavenging activity. Notably, the inhibition kinetics of anacardic acids do not follow hyperbolic dependence of enzyme inhibition on inhibitor contents (Michaelis–Menten equation) but follow the Hill equation instead. Anacardic acid (C_15:1) inhibited the soybean lipoxygenase-1 (EC 1.13.11.12, Type 1) catalyzed oxidation of linoleic acid with an IC₅₀ of 6.8 μM. The inhibition is a slow and reversible reaction without residual enzyme activity. The inhibition kinetics indicate that anacardic acid (C_15:1) is a competitive inhibitor and the inhibition constant, K_I, was 2.8 μM. Anacardic acids act as antioxidants in a variety ways, including inhibition of various prooxidant enzymes involved in the production of the reactive oxygen species and chelate divalent metal ions such as Fe²⁺ or Cu²⁺, but do not quench reactive oxygen species. The C₁₅-alkenyl side chain is largely associated with the activity.     

The analysis of solvation in ionic liquids and organic solvents using the Abraham linear free energy relationship

The contentions made in an earlier paper [J Chem Technol Biotechnol 80 : 133–137 (2005)] that the coefficients of the Abraham solvation equation do not provide meaningful information on the molecular properties of ionic liquid solvents is refuted. The objections noted in the earlier paper disappear when the solvation equation model is correctly applied to the experimental data. It is further shown that the coefficients of the Abraham solvation equations can be used to characterize ionic liquids and can be used to select solvents for the solubility of gaseous solutes. Copyright © 2006 Society of Chemical Industry     

Influence of Gaseous Atmosphere on Morphology and Cellular Fatty Acid Composition of Campylobacter jejuni

ABSTRACT: We evaluated the effect of growth environment on morphology and fatty acid (FA) profiles of 2 strains of C ampylobacter jejuni (ATCC 29428 and 33560) grown under various gaseous conditions. Viable counts were determined by plate count and percentages of coccoid cells. FA profiles were measured by gas chromatography. Plate counts were lowest when cultures were grown in air and highest in CO₂ (10%), O₂ (5%), and N₂ (85%). For 29428, percentages of coccoid cells did not differ among treatments. For 33560, percentages of coccoid cells were greater than for 29428 and varied among treatments (13% to 87%). There were no significant ( P > 0.05) relationships between percentages of coccoid cells and amounts of individual or combinations of FA either between or within strains.     

An Electron Spin Resonance Study of Evolution of Organic Free Radicals in Irradiated Pepper During Heat Treatment

ABSTRACT: The thermal evolution behavior of the organic free radicals induced in irradiated black pepper was studied by electron spin resonance spectroscopy. To analyze the time-dependent evolution process, we used the theory of transient phenomena, that is, an ordinal differential equation, as well as the nonlinear least squares numerical method. We found that the radical evolution that occurred in the irradiated pepper obeys a single exponential function and yields a unique time constant. The evolution of the organic free radical undergoes a simple reaction process of a single radical species.