Kinetics of oxidation of some disaccharides in ammoniacal medium

Kinetics of oxidation of lactose, maltose, cellobiose and melibiose has been studied by hexacyanoferrate(III) in the presence of ammonia. A general mechanism involving the formation of intermediate enodiol anion has been suggested. The effects of dielectric constant and salts have been studied in detail. The oxidation products have been characterised by descending paper chromatography. Compensation effects have been observed.     

Effects of pH and Dye Concentration on the Optical and Structural Properties of Coumarin-4 Dye-Doped SiO2-PDMS Xerogels

Optical and structural properties of coumarin-4 dye-doped SiO₂-PDMS xerogels synthesized by acid catalyzed (one-step) and acid-base catalyzed (two-step) sol-gel routes with varying pH (0.6 to 7) and dye content ( 5 × 10^–4 to 5 × 10^–2 mole) are reported. Spectroscopic methods such as photo-luminescence, FT-IR and FT-Raman were used for characterizations. The acid catalyzed xerogels prepared with pH < 2.5 exhibited two fluorescence peaks, I at 390 nm and II at 480 nm. The acid-base catalyzed xerogels synthesized with pH < 2.5 also exhibited two peaks, I at 400 nm and II at 475 nm. Peak II was not observed for the samples with pH 2.5. This phenomenon was attributed to the existence of pH dependent different forms of coumarin-4 molecule. The concentration-quenching phenomenon was observed for the acid catalyzed xerogels prepared with different dye concentration. TheFT-IR spectra indicated the existence of hydrogen bonds between the carbonyl groups of dye molecules and the silanol groups of gel matrix. The hydrogen bonding was the highest for the samples with the extremity pH, 0.6 and 7, resulting in the highest dye/gel matrix interactions, hence, the highest fluorescence peaks. The Raman studies indicated that the samples prepared with pH < 2.5 possessed relatively more number of 3-membered siloxane rings than 4-membered siloxane rings. The ring statistics was reversed for the samples with pH > 2.5. The number of silanol groups was higher for the samples with pH > 2.5.     

Telluro- and seleno-bridged TiIV-MII (M = Ni,Pd, Pt) heterobimetallic complexes

Summary Heterobimetallic complexes of the types [Cp₂Ti(-EAr)₂-M(dppe)] (ClO₄)₂ [(1)–(4); M, E = Ni, Te (1); Ni, Se (2); Pt, Te (3); Pt, Se (4); Ar = Ph (a), C₆H₄-4-Me (b), C₆H₄-4-OMe (c), C₆H₄-4-OEt (d)] and [Cp₂Ti(-TeAr)₂-MCl ₂] [M = Pd (5), Pt (6)] were obtained by the reactions of Cp₂Ti(EAr)₂ with M(dppe)(ClO₄)₂ and M(PhCN)₂Cl₂, respectively. While (1), (5) and (6) are stable in the solid state as well as in solution, (2)–(4) undergo dissociation to M(dppe)(EAr)₂ and Cp₂Ti(ClO₄)₂ in solution, as shown by multinuclear (³¹P{¹H},¹⁹⁵Pt{¹H}, ¹²⁵Te{¹H}) n.m.r. studies. The reaction of Cp₂Ti(SeAr)₂ with M(PhCN)₂Cl₂, however, leads to the formation of Cp₂TiCl₂ and a polymeric material [M(SeAr)₂] _n .     

Melt-polymerizable bisimido-bisphthalonitriles containing silicon,fluoro, and ether groups: Synthesis,characterization, and NMR study

Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (¹H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers.     

Removal of185W,99Mo and125Sb radioisotopes from aqueous solutions using polyamine incorporated polysaccharides

Polyamino group-containing resins act both as chelating ion exchangers and weakly basic anion exchangers depending upon the species in contact in the solution. In the present work, ion exchangers based on polyamine incorporated polysaccharides (cellulose and galactomannan or guaran) have been used for removal of radioisotopes of¹⁸⁵W as WO ₄ ^2– ,⁹⁹Mo as MoO ₄ ^2– and¹²⁵Sb as Sb³⁺ from their separate aqueous solutions. These chelating anion exchangers have been synthesized by reaction of polysaccharides with epichlorohydrin followed by the respective polyamines as nucleophiles in a strongly alkaline medium. WO ₄ ^2– and MoO ₄ ^2– are adsorbed from their aqueous solutions through anion exchange process by chloride form of cellulose-triethylenetetraamine (cellulose-trien), cellulose-tetraethylenepentaamine (cellulose-tetren), guaran-triethylenetetraamine (guar-trien) and guar-tetraethylenepentaamine (guar-tetren) weakly basic anion exchangers. Guar-tetren chelating polymer has been found to be highly selective for¹²⁵Sb isotopes presumably due to the presence of chelating cis-hydroxy and tetren groups in the galactomannan matrix.     

Enantioselective synthesis of tarchonanthuslactone via iterative hydrolytic kinetic resolution

A short and practical enantioselective synthesis of tarchonanthuslactone has been achieved in high diastereomeric excess using iterative Jacobsen’s hydrolytic kinetic resolution and ring closing metathesis as the key steps.     

Quantification of Valerenic Acid in Valeriana jatamansi and Valeriana officinalis by HPTLC

A simple, rapid, cost-effective and accurate high performance thin layer chromatographic method has been developed for quantification of valerenic acid in Valeriana jatamansi and Valeriana officinalis which is one of the stable compounds of Valeriana officinalis and designated as a key marker compound. Valerenic acid makes substantial contribution to the sedative and spasmolytic activity of the essential oil and extract of Valeriana officinalis. Separation and quantification was achieved by HPTLC using ternary mobile phase of hexane: ethyl acetate: acetic acid (80:20:0.5 v/v) on precoated silica gel 60F₂₅₄ aluminium plates and densitometric determination was carried out after derivatization with anisaldehyde-sulphuric acid reagent at 700 nm, in absorption-reflectance mode. The calibration curves were linear in the range of (500 ng–2.5 μg). This is the first HPTLC report for the identification and quantification of valerenic acid in Valeriana jatamansi and Valeriana officinalis.     

Simulation of the Adhesion of Particles to Surfaces

The removal of micrometer and submicrometer particles from dielectric and metal films represents a challenge in postchemical mechanical polishing cleaning. Proper modeling of the adhesive force between contaminant particles and these films is needed to develop optimal solutions to postchemical mechanical polishing cleaning. We have previously developed and experimentally validated a model to describe the adhesion between spherical particles and thin films. This simulation expands previous models to characterize the adhesive interaction between asymmetrical particles, characteristic of a polishing slurry, and various films. Our simulation accounts for the contact area between particles and substrates, as well as the morphology of the surfaces. Previous models fail to accurately describe the contact of asymmetrical particles interacting with surfaces. By properly accounting for nonideal and geometry and morphology, the simulation predicts a more accurate adhesive force than predictions based upon an ideal van der Waals model. The simulation is compared to experimental data taken for both semi-ideal particle-substrate systems (polystyrene latex spheres in contact with silicon films) and asymmetrical systems (alumina particles in contact with various films). Copyright 2001 Academic Press.     

Benzyne cyclisation with carbanion activated aromatic rings1

Attempts to cyclise o-chlorophenyl benzyl ether, sulphide, sulphoxide and sulphone by treatment with KNH₂/NH₃ were unsuccessful. Similar reaction of 1-(o-chlorophenyl)-2,2-diphenylethane led to amination whereas α-(o-chlorobenzyl)phenylacetic acid gave a dihydrocoumarin. Reaction of 4- and 2-(o-chlorophenethyl)-pyridines, however, afforded products comprising benzisoquinolines and 1-pyridylbenzocyclobutenes.