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.     

Total synthesis of (-)- and (+)-lentiginosine

Total synthesis of (-)-lentiginosine was achieved from D-mannitol using highly stereoselective reactions. Similarly, (+)-lentiginosine was synthesized from L-tartaric acid.     

Reactions of titanium(IV) isopropoxide with aliphatic and aromatic hydroxy esters,part I. 5-, 6-, 7- and 8-coordinate titanium(IV) complexes

Summary Reactions of titanium(IV) isopropoxide with ethyl 1-hydroxycyclohexylacetate, ethyl 2-hydroxy-2-arylpropionate, ethyl 2-hydroxy-2-arylbutyrate and ethyl 2-hydroxy-2-arylhydrocinnamate have been studied in dry benzene in different molar ratios under strictly anhydrous conditions. The Ti(OPr-i)₄-_nL_n type compounds, where L = hydroxy ester and n = 1 to 4, have been isolated and characterised by elemental analysis, molecular weight, i.r. and n.m.r. spectral studies. These products may be distilled unchanged under reduced pressure.Reprints of this are not available.     

P and H NMR studies of the transesterification polymerization of polyphosphonate oligomers

Polymeric phosphonate esters are an interesting class of organophosphorus polymers because both the polymer backbone and phosphorus substituents can be modified. These polymers have been prepared by ring-opening polymerizations of cyclic phosphites, stoichiometric polycondensations of dimethyl phosphonate with diols in conjunction with diazomethane treatment and by transesterification of polyphosphonate oligomers. Our initial attempts to prepare high molecular weight polymeric phosphonate esters by the transesterification methods were unsuccessful. Results indicate that the reactions of dimethyl phosphonate with diols to form polyphosphonate oligomers with only methyl phosphonate end groups are plagued by a serious side reaction that forms phosphonic acid end groups. These end groups do not participate in the transesterification reaction and limit the molecular weights of the polymers that can be obtained. The phosphonic acid end groups can be converted into reactive methyl phosphonate end groups by treatment with diazomethane, however diazomethane is explosive and the polymerization is slow. An alternative route for the production of high molecular weight polymers is the transesterification of the 1,12-bis(methyl phosphonato)dodecane, formed by the reaction of excess dimethyl phosphonate and 1,12-dodecanediol, with a Na₂CO₃ promoter. This allows polymers with molecular weights of up to 4.5×10⁴ to be prepared, and no phosphonic acid end groups are observed in these polymers. Thermal analyses of the poly(1,12-dodecamethylene phosphonate) have shown that this polymer has reasonable thermal stability (onset of thermal decomposition at 273 °C). This polymer also undergoes a cold crystallization process at 15 °C similar to that which has been observed in some polyesters, polyamides and elastomers.     

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.     

alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds using (dichloroiodo)benzene-lead(II) thiocyanate

The combination reagent (dichloroiodo)benzene and lead(II) thiocyanate in dichloromethane effects oxidation of various enol silyl ethers, ketene silyl acetals, and beta-dicarbonyl compounds, thereby providing an efficient and convenient method for alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds.     

Spectrophotometric and potentiometric studies of oxovanadium(IV) chelates with Eriochrome black T and Solochrome black 6 BN

Vanadium(IV) forms colored chelates with Erio T and Solo 6 BN (λ_max 570 and 580 nm, respectively) at pH 3.8. The composition MR₂ of the chelates investigated was established by continuous variation, mole ratio, slope ratio and straight-line methods spectrophotometrically. For photometric determination of V(IV) with these reagents Sandell's sensitivity, Beer's law range, Ringbom optimum range were also determined. Bjerrum and Calvin potentiometric titration technique was employed to determine the stepwise formation constants of each system. For V(IV)-Erio T system values of log K₁ = 14.4, log K₂ = 10.9 and for V(IV)-Solo 6 BN system log K₁ = 16.1, log K₂ = 11.8 were obtained.     

2-(2-Selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione, synthesis photophysics and interaction with bovine serum albumin: a spectroscopic approach

The compound 2-(2-selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione (SEBID), a ubiquitous, bioactive naphthalimide derivative is expected to possess an anticancer, anti-tumor and other important therapeutic activities of significant potency with low systematic toxicity. In this paper, the synthesis of the compound, photophysics of the newly prepared naphthalimide derivative and its interaction with model transport protein Bovine serum albumin (BSA) have been reported using the absorption and steady state fluorescence spectroscopic techniques exploiting the intrinsic fluorescence emission properties of BSA as a probe. Interaction of this organoselenium compound in different dioxane-water mixtures with increase in the polarity of the medium has been studied spectroscopically. Interaction of SEBID with BSA leads to a dramatic decrease in the fluorescence intensity of BSA, which suggests the binding of SEBID with the tryptophan residue of BSA. Furthermore, different thermodynamic parameters for SEBID-BSA interaction have been calculated. Rationalization of the data has been attempted, particularly in relation to prospective applications in the biomedical research.