Catalytic Asymmetric Dihydroxylation of Aliphatic Olefins with Reusable Resin‐Osmium Tetroxide

Asymmetric dihydroxylation of aliphatic olefins to chiral diols with good yields and ees by a heterogeneous Resin‐OsO₄ catalyst using ferricyanide as cooxidant is disclosed for the first time. The catalyst was recovered quantitatively by simple filtration and reused for several times without significant loss of activity.     

Bifunctional Catalysts Stabilized on Nanocrystalline Magnesium Oxide for One‐Pot Synthesis of Chiral Diols

New bifunctional catalysts composed of PdCl₄²⁻, OsO₄²⁻ and OsO₄²⁻, WO₄²⁻ designed and prepared by a counterionic stabilization technique involving the reactions of Na₂PdCl₄‐K₂OsO₄ and K₂OsO₄‐Na₂WO₄ with nanocrystalline MgO are well characterized. These bifunctional catalysts, NAP‐Mg‐PdOs and NAP‐Mg‐OsW perform tandem Heck asymmetric dihydroxylation and asymmetric dihydroxylation‐N‐oxidation reactions, respectively, in the presence of the chiral ligand 1,4‐bis(9‐o‐dihydroquinidinyl)phthalazine [(DHQD)₂PHAL] in a single pot. It is quite impressive to note that H₂O₂ is used as a terminal oxidant to provide N‐methylmorpholine N‐oxide (NMO) in situ by the oxidation of N‐methylmorpholine (NMM) in the asymmetric dihydroxylation‐N‐oxidation catalyzed by NAP‐Mg‐OsW.     

Microwave‐Assisted Synthesis and Characterization of Succinate Derivatives of Cassava (Manihot esculenta Crantz) Starch

The use of microwave heating to prepare very rapidly cassava starch succinates with high viscosity is described. A response surface design was used for the experiment and different factors affecting the succinylation of cassava starch, including concentration of succinic anhydride, reaction time, temperature and moisture content of the medium were investigated. The degrees of substitution of the modified starches increased with an increase in reaction time and were in the range 0.007 – 0.051. The products exhibited higher viscosity, lower pasting temperature, enhanced water binding capacity and reduced swelling and paste clarity than unmodified cassava starch. The results of this study indicated that succinylation of starch can be achieved in shorter reaction times, which offers a benefit to laboratories and industries involved in developing newer and more versatile uses for cassava starch.     

Synthesis and Characterization of low DS Succinate Derivatives of Cassava (Manihot esculenta Crantz) Starch

Succinylation of cassava starch was carried out in aqueous medium to prepare derivatives with low degree of substitution (DS) and the physicochemical properties of the products were determined. A response surface design was used for the experiment with three levels of each of the three variables viz., concentration of succinic anhydride, reaction time and pH of the reaction medium. The reaction was followed in terms of the DS of the products and reaction efficiency (RE). The degree of substitution of the derivatives varied from 0.001 to 0.022 and reaction efficiency from 2.2 to 46.8%. The DS and RE showed an adequate fit to a second order polynomial model of the variables used. Succinylation brought about increase in the swelling volume, peak viscosity and paste clarity of the starch. However, the pasting temperature and solubility did not show any significant change. The in‐vitro α‐amylase digestibility of the succinylated derivatives decreased in comparison to that of native starch and this decrease correlated with a corresponding increase in DS.     

Formation of anisaldehyde via hydroxymethylation of anisole over SnO2–CeO2 catalysts

Hydroxymethylation of anisole has been carried out over SnO₂–CeO₂ catalysts in the temperature range 623–723 K. Methoxybenzaldehyde (anisaldehyde) and condensation products were formed along with minor quantities of methoxybenzyl alcohol, o‐cresol, phenol and 2,6‐xylenol. A maximum anisaldehyde selectivity of 64% was obtained at 623 K at an anisole conversion of 46% under optimized conditions. Catalytic activity of these systems in the formation of aldehyde is ascribed to the presence of weak acid sites and redox metal sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

Physical and Functional Properties of Arrowroot Starch Extrudates

ABSTRACT:  Arrowroot starch, a commercially underexploited tuber starch but having potential digestive and medicinal properties, has been subjected to extrusion cooking using a single screw food extruder. Different levels of feed moisture (12%, 14%, and 16%) and extrusion temperatures (140, 150, 160, 170, 180, and 190 °C) were used for extrusion. The physical properties—bulk density, true density, porosity, and expansion ratio; functional properties such as water absorption index, water solubility index, oil absorption index, pasting, rheological, and textural properties; and in vitro enzyme digestibility of the extrudates were determined. The expansion ratio of the extrudates ranged from 3.22 to 6.09. The water absorption index (6.52 to 8.85 g gel/g dry sample), water solubility index (15.92% to 41.31%), and oil absorption index (0.50 to 1.70 g/g) were higher for the extrudates in comparison to native starch (1.81 g gel/g dry sample, 1.16% and 0.60 g/g, respectively). The rheological properties, storage modulus, and loss modulus of the gelatinized powdered extrudates were significantly lower ( P < 0.05) and these behaved like solutions rather than a paste or a gel. Hardness and toughness were more for the samples extruded at higher feed moisture and lower extrusion temperature, whereas snap force and energy were higher at lower feed moisture and temperature. There was a significant decrease in the percentage digestibility of arrowroot starch (30.07% after 30 min of incubation with the enzyme) after extrusion (25.27% to 30.56%). Extrusion cooking of arrowroot starch resulted in products with very good expansion, color, and lower digestibility, which can be exploited for its potential use as a snack food.     

Bacteriogenic synthesis of selenium nanoparticles by Escherichia coli ATCC 35218 and its structural characterisation

A biosynthetic method for the production of selenium nanoparticles under ambient temperature and pressure from sodium selenite was developed using Gram‐negative bacterial strain Escherichia coli ATCC 35218. Bacteriogenic nanoparticles were methodologically characterized employing UV‐vis, XRD, Raman spectroscopy, SEM, TEM, DLS and FTIR techniques. Generation of nanoparticles was visualized from the appearance of red colour in the selenite supplemented culture medium and broad absorption bands in the UV‐vis. Biofabricated nanoparticles were spherical, polydisperse, ranged from 100‐183 nm and the average particle size was about 155 nm. Based on selected‐area electron diffraction, XRD patterns; and Raman spectroscopy the nanospheres were found to be amorphous. IR spectrum revealed the involvement of bacterial proteins in the reduction of selenite and stabilization of nanoparticles. Used bacterial strain demonstrated efficient selenite reduction capability which was evident from 89.2% of selenium removal within 72 h at a concentration of 1 mM. Observation noted in the current study highlight the importance of bacterial reduction in selenium nanoparticle generation which can be scaled up for commercial production. Also, the bacteriogenic, amorphous nanoparticles can also be used as nutritional supplements for humans since selenium nanoparticles of 5‐200 nm are bioavailable and known to induce seleno enzymes involved in antioxidant defence.Inspec keywords: Fourier transform infrared spectra, transmission electron microscopy, scanning electron microscopy, electron diffraction, ultraviolet spectra, microorganisms, X‐ray diffraction, nanofabrication, Raman spectra, visible spectra, nanoparticles, particle size, seleniumOther keywords: bacteriogenic synthesis, selenium nanoparticles, Escherichia coli ATCC 35218, structural characterisation, biosynthetic method, gram negative bacterial strain, UV–visible spectroscopy, X‐ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, particle size, selected area electron diffraction, bacteriological reduction, seleno enzymes, size 100 nm to 183 nm, Se     

Pitting corrosion of titanium by a freshwater strain of sulphate reducing bacteria (Desulfovibrio vulgaris)

Pitting corrosion of titanium (ASTM Grade 2) was investigated by exposing coupons (2.0 × 1.5 cm) to a semi-continuous culture of sulphate reducing bacteria (SRB) strain Desulfovibrio vulgaris. The coupons were exposed to the SRB culture for 90 days along with a control set in uninoculated medium. During the course of the experiment sulphide was estimated at intervals of 4 days and the concentrations ranged from 0.2 to 0.4 mM in the bulk medium. Epifluorescence microscopy revealed extensive colonization by the SRB and the cell count ranged from 10⁴ to 10⁵ cells cm⁻². Optical microscopy revealed the presence of two types of pits; large hemispherical pits of ∼2 mm diameter and many micropits. Pitting was not observed in control coupons exposed to SRB free medium. SEM and CSLM pictures showed the corroded titanium surface with several micropits, along with typical rod shaped SRB cells in the pitted regions. EDAX analysis revealed peaks for Ti, O, N, C, Fe and P in the pitted region. XPS data showed clear peaks for titanium sulphur (three states) and phosphorous. The study reveals that at room temperature and in the presence of 0.2-0.4 mM of sulphide, as well as the putative phosphine, SRB can promote pitting corrosion of titanium by formation of titanium sulphide.     

Mechanistic Aspects of Os(VIII)/Ru(III) Catalysed Oxidation of L-phenylalanine by Ag(III) Periodate Complex in Aqueous Alkaline Medium

The kinetics of oxidation of ruthenium(III) (Ru(III)) and osmium(VIII) (Os(VIII)) catalysed oxidation of L-phenylalanine (L-Pal) by diperiodatoargentate(III) (DPA) in aqueous alkaline medium at 27 °C and a constant ionic strength of 0.25 mol dm^?3 was studied spectrophotometrically. The involvement of free radicals was observed in the reactions. The reaction between DPA and L-Pal in alkaline medium exhibits stoichiometry as [L-Pal]:[DPA] = 1:1. The reaction is of first order in [Os(VIII)], [Ru(III)] and [DPA] and has negative fractional order in [IO₄ ^?]. It has less than unit order in [L-Pal] and [OH^?]. However, the order in [L-Pal] and [OH^?] changes from first order to zero order as their concentrations increase. The main oxidation products were identified by spot test and spectral studies. The probable mechanisms were proposed and discussed. The catalytic constant (K _c) was also calculated for Os(VIII) and Ru(III) catalysis at different temperatures. The activation parameters with respect to slow step of the mechanisms were computed and discussed and thermodynamic quantities were also calculated. It has been observed that the catalytic efficiency for the present reaction is in the order of Os(VIII) > Ru(III). The active species of catalyst and oxidant have been identified.     

Layered Double Hydroxide Supported Nanoplatinum and Nanopalladium Catalyzed Allylation of Aldehydes: A Mechanistic Study

Layered double hydroxide (LDH)‐supported nanoplatinum(0) and nanopalladium(0) catalysts were prepared by a simple ion exchange technique and subsequent reduction with hydrazine hydrate and used for the allylation of aldehydes to give moderate to good yields of homoallylic alcohols. Detailed mechanistic studies of LDH‐Pd(0)‐catalyzed allylation using XPS and TGA‐MS reveal that a monoallyl‐palladium complex is the key intermediate for the catalytic cycle.