Electrostatic catalysis by ionic aggregates: scope and limitations of Mg(ClO4)2 as acylation catalyst

Alkali and alkaline earth metal perchlorates exhibit electrostatic catalysis in the activation of anhydrides for the acylation reaction. Perchlorates with higher values of the charge-size function of the metal ion exhibit better catalytic activity following the order Mg(ClO₄)₂>Ba(ClO₄)₂>LiClO₄. Acylation of structurally diverse phenols, thiols, alcohols, and amines have been carried out with stoichiometric amounts of anhydride at room temperature under solvent free conditions in the presence of catalytic amount of Mg(ClO₄)₂. Sterically hindered and electron deficient phenols are efficiently acylated. Acylation with sterically hindered anhydrides such as iso-butyric, pivalic, and benzoic anhydrides are carried out with phenols and alcohols in excellent yields. Acid-sensitive alcohols are acylated in excellent yields without any competitive side reactions.     

Optimised isolation of polysaccharides from Lentinula edodes strain NCBI JX915793 using response surface methodology and their antibacterial activities

Mycelial growth in a defined medium by submerged fermentation is a rapid and alternative method for obtaining fungal biomass of consistent quality. Biomass, exopolysaccharides (EPS) and intracellular polysaccharides (IPS) production were optimised by response surface methodology in Lentinula edodes strain LeS (NCBI JX915793). The optimised conditions were pH 5.0, temperature 26°C, incubation period of 25 days and agitation rate of 52 r/min for L. edodes strain LeS. Under the calculated optimal culture conditions, biomass production (5.88 mg mL^? 1), EPS production (0.40 mg mL^? 1) and IPS production (12.45 mg g^? 1) were in agreement with the predicted values for biomass (5.93 mg mL^? 1), EPS (0.55 mg mL^? 1) and IPS production (12.64 mg g^? 1). Crude lentinan exhibited highest antibacterial effects followed by alcoholic, crude and aqueous extracts. The results obtained may be useful for highly effective yield of biomass and bioactive metabolites.     

RP-LC Resolution of (R,S)-Atenolol via Diastereomerization with Marfey’s Reagent and Its Structural Variants Under Conventional and Microwave Heating

(R,S)-Atenolol was derivatized with Marfey’s reagent, (MR; 1-fluoro-2,4-dinitrophenyl-5-l-alanine amide or FDNP-l-Ala-NH₂) and its four structural variants (FDNP-l-Phe-NH₂, FDNP-l-Val-NH₂, FDNP-l-Leu-NH₂ and FDNP-l-Pro-NH₂). MR reacts quantitatively with 1° and 2° amino groups and atenolol has a secondary amino group. The derivatization reactions were carried out under conventional and microwave heating and compared. The resulting diastereomers were separated on RP-TLC and on a C18 column with detection at 340 nm. (R)-Isomer eluted before (S). The conditions of derivatization and chromatographic separation were optimized. The method was validated for linearity, repeatability, limits of detection and limit of quantification.     

Mechanistic study of the oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-phenylalanine by hexacyanoferrate(III) catalyzed by iridium(III) in aqueous alkaline medium

The oxidation of l-phenylalanine by hexacyanoferrate(III) (abbreviated as HCF) catalyzed by Ir(III) has been studied spectrophotometrically at 35 °C and at a constant ionic strength of 0.50 mol dm⁻³. The main oxidation product was identified as phenylpyruvic acid by physico-chemical and spectroscopic methods. The stoichiometry was found to be 2:1, i.e. 2 mol of hexacyanoferrate(III) reacted with 1 mol of phenylalanine. The reaction was first order with respect to both HCF and alkali concentration. The order with respect to [Phe] changed from first to zero as the concentration was increased. The effect of ionic strength was also investigated. Thermodynamic parameters were evaluated by studying the reaction at four different temperatures between 35 and 50 °C. Based on the experimental results, a suitable mechanism involving complex formation has been proposed.     

Direct TLC Resolution of the Enantiomers of Three β-Blockers by Ligand Exchange with Cu(II)–l-Amino Acid Complex, Using Four Different Approaches

TLC experiments have been performed to resolve the enantiomers of three β-blockers by complexation chiral TLC with Cu(II) cation and five l amino acids. Loading was carried out by using the Cu(II)–l amino acid complex as chiral mobile phase additive with untreated silica gel plates; by mixing the Cu complex with silica gel before preparing the TLC plates; by ascending development of untreated plates with solutions of the Cu complex; and by using a solution of Cu(II) acetate as mobile phase additive for plates prepared by mixing the l amino acid with silica gel. Spots were located by use of iodine vapour.     

Nano-sized polycrystalline bismuth silicon oxide powder by sol–gel technique

Bismuth silicon oxide (Bi₁₂SiO₂₀, BSO) nano crystalline powder was prepared by sol–gel technique using bismuth nitrate and tetraethyl orthosilicate as starting materials. The prepared samples were sintered at various temperatures (750 °C maximum) and characteristic sillenite single cubic phase with crystallite size ~38 nm (calculated from room temperature powder XRD measurements) was realized at 750 °C sintering temperature. SEM analysis showed that the powder contains the nano-sized particles with almost spherical morphology. The observed frequencies in room temperature FTIR spectrum could be assigned to Bi–O, Si–O and Bi–O–Si bonds. The FWHM (full width at half maximum) of the diffraction peaks decreased while the intensity of FTIR absorption lines increased with the increase in the sintering temperature indicating better bond formation and crystallization. The thermograph of the samples recorded in the temperature range 50–1,000 °C showed almost no weight loss after ~575 °C further confirmed the conclusion arrived at from XRD and FTIR analysis. The samples sintered at 750 °C showed about 50% absorbance in 400–600 nm region which was consistent with the pale yellow color of the sample. Broad blue emission centered ~478 nm was observed when excited by 350 nm radiation from a Xe-lamp. The intensity of this broad emission band increased while its FWHM decreased with the increase in sintering temperature. Self-trapped excitons could be responsible for this emission.     

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO₂) nano-photocatalysts, with different phases, prepared using a modified sol?Cgel process were employed in the degradation of rhodamine at 10?mg?L^?1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450?°C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K _app) of 0.023?min^?1. The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024?min^?1 for 450, 500, 550 and 600?°C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017?min^?1, which is similar to that of the commercial titania.