First preparative synthesis of a 3-acetamido-3,6-dideoxy-d-galactopyranose glycosyl donor via intramolecular cyclization of an epoxytrichloroacetimidate

The preparative synthesis of a 3-acetamido-3,6-dideoxy-d-galactopyranose N-phenyl-trifluoroacetimidate donor has been accomplished using as key step a silica gel mediated cyclization of an epoxytrichloroacetimidate, while other more conventional routes to aminosugars failed. Test glycosylations with the N-phenyl-trifluoroacetimidate donor are also reported.     

Tensor polarizabilities of the 4f 7(8 S)5d6s 2 9 D 2,3,4,5,6 levels in Gd I

The optical pumping method with rf detection and the nonlinear level crossing technique were used in parallel electric and magnetic fields to investigate the Stark splitting of all the fine structure levels of the ground multiplet 4f ⁷ (⁸ S) 5d6s ^{2 9} D in Gd I. The tensor polarizabilities were deduced from the level crossing and the rf signals. The variation of the tensor polarizabilities is well reproduced by the LS coupling approximation, except for the small value of the⁹ D ₅ level. A value of the tensor polarizability of the 5d electron is evaluated from the experimental results, ₂(5d)=2.00(6) kHz(kV/cm)². It is shown that the ratio between the electric quadrupole constant and the tensor polarizability is constant, except for the⁹ D ₅ ratio, which is caused by a breakdown of the central field model.     

Compatibility Studies of Multicomponent Tablet Formulations. DSC and experimental mixture design

An experimental mixture design was applied to a differential scanning calorimetry (DSC) study performed to evaluate naproxen compatibility in tablet formulations consisting of four classic excipients (sorbitol, sodium carboxymethylcellulose, poly(ethylene glycol) 20000 and Veegum) each in adequate concentration ranges accounting for the relevant values actually used in pharmaceutical formulations. Twenty-seven different tablets were obtained from as many mixtures prepared according to the experimental design plan and analyzed in a random order by DSC. Statistical evaluation of experimental data enabled correlation of both enthalpy and onset temperature variations of drug melting endotherm (selected as responses indicative of the presence of drug-excipient interactions) with the mixture composition. Variance analysis (Anova) confirmed the reliability of the postulated polynomial model in providing adequate prediction of true system behaviour. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation of Tyr-C-peptide from genetically altered human insulin precursor

C-peptide radioimmunoassay (C-peptide RIA) is widely used in determination of pancreatic B-cell secretion activity.¹²⁵I labeled TyrC-peptide is indispensable in C-peptide RIA kit. Herein we discuss a way of obtaining recombinant Tyr-C-peptide. Arg32Tyr human proinsulin mutant (R32Y-proinsulin) gene was constructed by site-directed mutagenesis and overexpressed inEscherichia coli. Purified R32Y-proinsulin was converted to insulin and Tyr-C-peptide by trypsin and carboxypeptidase B codigestion. Tyr-C-peptide was isolated through reverse-phase HPLC (RP-HPLC) and identified by C-peptide RIA and amino acid analysis.     

Study of metal-loaded activated charcoals for the separation and determination of selenium species by energy dispersive X-ray fluorescence analysis

Conversion of adsorption properties of activated charcoal (C^∗) by metal modification towards selenite, selenate and seleno-dl-methionine (Se-Met) was studied. Several metals were included in modification studies and also a procedure was developed for the separation and independent determination of microgram quantities of these selenium species in aqueous solution. Selenium species were collected one by one from the same sample solution onto collector material by adsorbing them directly or after complex formation onto different metal-loaded activated charcoals (MgC^∗ and FeC^∗). The mass of selenium in these collectors was measured directly by energy dispersive X-ray fluorescence spectrometry (EDXRF). Detection limits for all three selenium species were better than 6 μg corresponding to concentration of 60 μg/l with 0.100 l of initial sample volume.     

Synthesis of homochiral 2-C-perfluoroalkyl substituted d- and l-riboses

Homochiral 2-C-perfluoroalkyl substituted d- and l-riboses were synthesized via Barbier, Grignard and Ruppert type reactions. The influence of the size of the perfluoroalkyl groups, attached to C-2, on the furanose/pyranose as well as on the α-furanose/β-furanose and α-pyranose/β-pyranose ratio in solution was studied.     

Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

The simultaneous saccharification and fermentation of pretreated woody crops to ethanol

Four promising woody crops (Populusmaximowiczii x nigra (NE388), P.trichocarpa x deltoides (Nll), P.tremuloides, and SweetgumLiquidambar styraciflua) were pretreated by dilute sulfuric acid and evaluated in the simultaneous saccharification and fermentation (SSF) process for ethanol production. The yeastSaccharomyces cerevisiae was used in the fermentations alone, and in mixed cultures with β -glucosidase producingBrettanomyces dausenii. Commercial Genencor 150L cellulase enyme was either employed alone or supplemented with β- glucosidase. All SSFs were run at 37 …C for 8 d and compared to saccharifications at 45…C under the same enzyme loadings.S. cerevisiae alone achieved the highest ethanol yields and rates of hydrolysis at the higher enzyme loadings, whereas the mixed culture performed better at the lower enzyme loadings without β -glucosidase supplementation. The best overall rates of fermentation (3 d) and final theoretical ethanol yields (86–90%) were achieved with P.maximowiczii x nigra (NE388) and SweetgumLiquidambar styraciflua, followed by P.tremuloides and P.trichocarpa xdeltoides (N1l) with slightly slower rates and lower yields. Although there were some differences in SSF performance, all these pretreated woody crops show promise as substrates for ethanol production.     

Fouling and protein adsorption effect of low-temperature plasma treatment of membrane surfaces

Adsorption of proteins and the effect of the chemical nature of membrane surfaces on protein adsorption were investigated using¹⁴C-tagged albumin and several microporous membranes (polyvinilydene fluoride, PVDF; nylon; polypropylene, PP; and polycarbonate, PC). The membrane surfaces were modified by exposing them to low-temperature plasma of several different monomers (n-butane, oxygen, nitrogen alone or as mixtures) in a radiofrequency plasma reactor. Transients in the permeability of albumin solutions through the membranes and changes in flux of distilled water through the membranes before and after adsorption of albumin were used to investigate the role of protein adsorption on membrane fouling. The results show that the extent of adsorption of albumin on hydrophobic membranes was considerably more than that on hydrophilic membranes. The hydrophilic membranes were susceptible to electrostatic interactions and less prone to fouling. A pore-blocking model was successfully used to correlate the loss of water flux through pores of defined geometry