Biochemical properties of an extracellular beta-D-fructofuranosidase II produced by Aspergillus phoenicis under Solid-Sate Fermentation using soy bran as substrate

The filamentous fungus A. phoenicis produced high levels of beta-D-fructofuranosidase (FFase) when grown for 72 hrs under Solid-State Fermentation (SSF), using soy bran moistened with tap water (1:0.5 w/v) as substrate/carbon source. Two isoforms (I and II) were obtained, and FFase II was purified 18-fold to apparent homogeneity with 14% recovery. The native molecular mass of the glycoprotein (12% of carbohydrate content) was 158.5 kDa with two subunits of 85 kDa estimated by SDS-PAGE. Optima of temperature and pH were 55 degrees C and 4.5. The enzyme was stable for more than 1 hr at 50 degrees C and was also stable in a pH range from 7.0 to 8.0. FFase II retained 80% of activity after storage at 4 degrees C by 200 hrs. Dichroism analysis showed the presence of random and beta-sheet structure. A. phoenicis FFase II was activated by Mn(2+), Mg(2+) and Co(2+), and inhibited by Cu(2+), Hg(2+) and EDTA. The enzyme hydrolyzed sucrose, inulin and raffinose. K(d) and V(max) values were 18 mM and 189 U/mg protein using sucrose as substrate.

One-pot synthesis of mixed (Z)-1,2-bis(organylchalcogene)-1-alkenes precursors of the novel beta-organylthio vinyllithium intermediates

One-pot hydrochalcogenation of 1-phenylthioacetylenes using organylselenolate and organyltellurolate anions generated by the insertions of selenium and tellurium in n-organyl lithium produced (Z)-1,2-bis(organylchalcogene)-1-alkenes. The chemical reactivity of these mixed 1,2-bis(organylchalcogene)-1-alkenes was studied by Te/Li and Se/Li stereoretentive exchanges carried out with n-butyl lithium, furnishing the new intermediate species (Z)-beta-organylthio vinyllithium anions, which were trapped with aldehydes, to give the (Z)-3-hydroxy vinyl thioethers with total control of the regio- and stereochemistry. (c) 2010 Elsevier Ltd. All rights reserved.

Homocysteine-lowering treatment with folic acid, cobalamin, and pyridoxine does not reduce blood markers of inflammation, endothelial dysfunction, or hypercoagulability in patients with previous transient ischemic attack or stroke - a randomized substudy

Background and Purpose - Epidemiological and laboratory studies suggest that increasing concentrations of plasma homocysteine ( total homocysteine [tHcy]) accelerate cardiovascular disease by promoting vascular inflammation, endothelial dysfunction, and hypercoagulability. Methods - We conducted a randomized controlled trial in 285 patients with recent transient ischemic attack or stroke to examine the effect of lowering tHcy with folic acid 2 mg, vitamin B-12 0.5 mg, and vitamin B-6 25 mg compared with placebo on laboratory markers of vascular inflammation, endothelial dysfunction, and hypercoagulability. Results - At 6 months after randomization, there was no significant difference in blood concentrations of markers of vascular inflammation (high-sensitivity C-reactive protein [P = 0.32]; soluble CD40L [ P = 0.33]; IL-6 [P = 0.77]), endothelial dysfunction ( vascular cell adhesion molecule-1 [P = 0.27]; intercellular adhesion molecule-1 [P = 0.08]; von Willebrand factor [P = 0.92]), and hypercoagulability (P-selectin [P = 0.33]; prothrombin fragment 1 and 2 [P = 0.81]; D-dimer [P = 0.88]) among patients assigned vitamin therapy compared with placebo despite a 3.7-mumol/L (95% CI, 2.7 to 4.7) reduction in total homocysteine (tHcy). Conclusions - Lowering tHcy by 3.7 mumol/L with folic acid-based multivitamin therapy does not significantly reduce blood concentrations of the biomarkers of inflammation, endothelial dysfunction, or hypercoagulability measured in our study. The possible explanations for our findings are: ( 1) these biomarkers are not sensitive to the effects of lowering tHcy (eg, multiple risk factor interventions may be required); ( 2) elevated tHcy causes cardiovascular disease by mechanisms other than the biomarkers measured; or ( 3) elevated tHcy is a noncausal marker of increased vascular risk.

Bioreduction of beta-carboline imines to amines employing Saccharomyces bayanus

beta-Carboline imine reductions mediated by Saccharomyces bayanus have been described achieving moderate to good enantiomeric excesses of the amine products. The enantiomeric excesses of the bioreduction showed a dependence on the imine substituents. Compounds presenting C(1)-C(11) aliphatic substituent groups afforded amines with an (S)-configuration, whereas C(15) and higher aliphatic, and aromatic substituted B-carboline imines achieved inversion of the configuration in the final (R)-2 amine products. Based on this data, a model for the Saccharomyces reduction is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Study of spectroscopic properties of Europium (III) Tris(beta-diketonate) complex and alpha-Cyclodextrin in aqueous medium

The solubilization of an europium (III) beta-diketonate chelate in aqueous medium and the changes in its photophysical properties upon its inclusion into an alpha-cyclodextrin hydrophobic cavity are described. The complex [Eu(tta)(3)center dot(H(2)O)(2)] (tta = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione) was synthesized, characterized, and incorporated into the hydrophobic cavity by stirring in an alpha-cyclodextrin aqueous solution. The inclusion was confirmed by (1)H NMR, and the stoichiometry of association was obtained by the Job method. The maximum in the excitation spectrum of the alpha-CD inclusion compound in aqueous solution was shifted 28 nm compared with the maximum of non alpha-CD complex. The emission spectrum of the association is similar to that of the free solid complex and displays the characteristic (5)D(0) -> (7)F(0-4) Eu(3+) transitions.

Electrochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions: Effect of current density, pH, and chloride ions

The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-doped diamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds. (C) 2009 Elsevier Ltd. All rights reserved.

Pt/TiO(2)/poly(vinyl sulfonic acid) Layer-by-Layer Films for Methanol Electrocatalytic Oxidation

One major challenge for the widespread application of direct methanol fuel cells (DMFCs) is to decrease the amount of platinum used in the electrodes, which has motivated a search for novel electrodes containing platinum nanoparticles. In this study, platinum nanoparticles were electrodeposited on layer-by-layer (LbL) films from TiO(2) and poly(vinyl sulfonic) (PVS), by immersing the films into a H(2)PtCl(6) solution and applying a 100 mu A current during different electrode position times. Scanning tunnel microscopy (STM) and atomic force microscopy (AFM) images showed increased platinum particle size and electrode roughness for increasing electrodeposition times. The potentiodynamic profile of the electrodes indicated that oxygen-like species in 0.5 mol L(-1) H(2)SO(4) were formed at less positive potentials for the smallest platinum particles. Electrochemical impedance spectroscopy measurements confirmed the high reactivity for the water dissociation and the large amount of oxygen-like species adsorbed on the smallest platinum nanoparticles. This high oxophilicity of the smallest nanoparticles was responsible for the electrocatalytic activity of Pt-TiO(2)/PVS systems for methanol electrooxidation, according to the Langmuir-Hinshelwood bifunctional mechanism. Significantly, the approach used here combining platinum electrodeposition and LbL matrices allows one to both control the particle size and optimize methanol electrooxidation, being therefore promising for producing membrane-electrode assemblies of DMFCs.

Solvent Effects in Optical Spectra of ortho-Aminobenzoic Acid Derivatives

We investigated three amino derivatives of ortho-aminobenzoic or anthranilic acid (o-Abz): a) 2-Amino-benzamide (AbzNH(2)); b) 2-Amino-N-methyl-benzamide (AbzNHCH(3)) and c) 2-Amino-N-N`-dimethyl-bezamide (AbzNH(CH(3))(2)), see Scheme 1. We describe the results of ab-initio calculations on the structural characteristics of the compounds and experimental studies about solvent effects in their absorption and steady-state and time-resolved emission properties. Ab-initio calculations showed higher stability for the rotameric conformation in which the oxygen of carbonyl is near to the nitrogen of ortho-amino group. The derivatives present decrease in the delocalization of pi electron, and absorption bands are blue shifted compared to the parent compound absorption, the extent of the effect increasing from to Abz-NH(2) to Abz-NHCH(3) Abz-NH(CH(3))(2). Measurements performed in several solvents have shown that the the dependence of Stokes shift of the derivatives with the orientational polarizability follows the Onsager-Lippert model for general effects of solvent. However deviation occurred in solvents with properties of Bronsted acids, or electron acceptor characteristics, so that hydrogen bonds formed with protic solvents predominates over intramolecular hydrogen bond. In most solvents the fluorescence decay of AbzNH(2) and AbzNHCH(3) was fitted to a single exponential with lifetimes around 7.0 ns and no correlation with polarity of the solvent was observed. The fluorescence decay of AbzN(CH(3))(2) showed lifetimes around 2.0 ns, consistent with low quantum yield of the compound. The spectroscopic properties of the monoamino derivative AbzNHCH(3) are representative of the properties presented by Abz labelled peptides and fatty acids previously studied.

Synthesis, X-ray analysis and DFT study of 2-amino-3-(N-oxipiridin-4-ilsulfanil)-propionic acid dihydrate

The title compound, C(8)H(14)N(2)O(5)S 2(H(2)O), 2-amino-3-(N-oxipiridin-4-ilsulfanil)-propionic acid dihydrate, is obtained by the reaction of cysteine and 4-nitropyridine N-oxide in dimethylformamide, removing the NO(2) group from the benzene ring and releasing nitrous acid into the solution. The molecule exists as a Zwitterion. Hydrogen bond interactions involving the title molecule and water molecules allow the formation of R(5)(5)(23) edge fused rings parallel to (010). Water molecules are connected independently, forming infinite chains (wires), in square wave form, along the b-axis. The chirality of the cysteine molecule used in the synthesis is retained in the title molecule. A density functional theory (DFT) optimized structure at the B3LYP/6-311G(3df,2p) level allows comparison of calculated and experimental IR spectra.

Bovine mammary epithelial cells, initiators of innate immune responses to mastitis

Innate immunity plays a vital role in the protection of the bovine mammary gland against mastitis. Until recently, the migration of effector cells such as neutrophils and monocytes into the mammary gland was thought to provide the only defence against invading pathogens. However, mammary epithelial cells may also play an important role in the immune response, contributing to the innate defence of the mammary tissue through secretion of antimicrobial peptides and attraction of circulating immune effector cells. This paper reviews the innate immune pathways in mammary epithelial cells and examines their role in the initiation of an innate immune response to Gram-positive and Gram-negative bacteria.

Amphiphilic cerium(III) beta-diketonate as a catalyst for reducing diesel/biodiesel soot emissions

This work reports on the synthesis, characterization and applications of the new cerium(III) beta-diketonate Ce(hdacac)(3)(Hhdacac)(3)center dot 2H(2)O (where hdacac and Hhdacac denote, respectively, the hexadecylpentane-2,4-dionate and hexadecylpentane-2,4-dione ligands) as catalyst for the reduction of automotive emissions. Due to its amphiphilic character, this complex can be solubilized in non-polar fuels, thus generating cerium(IV) oxide particles, which efficiently catalyze the oxidation of diesel/biodiesel soot. The synthesized complex was characterized by microanalysis (C, H), thermal analysis, and infrared spectroscopy. Scanning electron microscopy, X-ray diffractometry, and specific surface area measurements attested that the complex can act as a soluble precursor of homogeneous CeO(2) spherical nanoparticles. The efficiency of this compound as catalyst for the reduction of soot emission was evaluated through static studies (comprising carbon black oxidation), which confirmed that increasing concentrations of the complex result in lower carbon black oxidation temperatures and lower activation Gibbs free energies. Dynamic studies, which embraced the combustion of diesel/biodiesel blends containing different amounts of the solubilized complex in a stationary motor, allowed a comparative evaluation of the soot emission through diffuse reflectance spectroscopy. These analyses provided very emphatic evidences of the efficiency of this new cerium complex for the control of soot emission in diesel/biodiesel motors. (c) 2009 Published by Elsevier B.V.

Luminescent Langmuir-Blodgett film of a new amphiphilic Eu(3+) beta-diketonate

This work reports on the synthesis and characterization of the ligand 3-hexadecylpentane-2,4-drone (Hhdacac) and its Eu(3+) complexes Eu(hdacac)(6) center dot 2H(2)O, Eu(hdacac)(6) center dot phen and Eu(hdacac)(6) center dot tta, where phen and tta denote 1,10-phenanthroline and thenoyltrifluoroacetone, respectively. These new compounds present long carbon chains and their expected miscibility into non-polar ambients is confirmed by the emission spectra of Eu(hdacac)6 center dot tta in hexane. Moreover, the amphiphilic properties of Eu(hdacac)6 complexes allow the obtainment of thin luminescent films by the Langmuir-Blodgett technique. In both cases (solids and films), the typical antenna effect of beta-diketonates is observed. The alluring characteristics of these compounds raise great interest in many fields of Materials Science, like photo- and electro-luminescent materials (mainly thin ""organic"" films), metal catalysts or probes in non-polar solutions, and Langmuir-Blodgett films of several compositions. For the characterization of these products, nuclear magnetic resonance spectroscopy ((1)H NMR), thermogravimetric analysis, elementary analyses (C, H), scanning electron microscopy (energy dispersive X-ray spectroscopy), absorption (UV-vis/FT-IR) and photoluminescence spectroscopies were used. (c) 2008 Elsevier B.V. All rights reserved.