A mew method of synthesis of 1,2,3,4-telrahydro-5H-5-oxo-1,4-benzodiazepines

A new one-step facile method for the synthesis of 1,12,3,4-tetrahydro5H-5-oxo-1,4-benzo-diuzepines is described. The method involves the addition of methyl anlhranilates to elhyl-enimine followed by intramolecular cyclizalion of the resulting intermediate compounds. Another attempted method starting from β-anilinoethylisocyanales is also described.     

Synthesis and conformational analysis of novel N(OCH3)-linked disaccharide analogues

N(OMe)-linked disaccharide analogues, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy-6-methoxyamino-alpha-D-glucopyranoside in an aqueous environment. The coupling reactions were found to be chemo- and stereoselective affording beta-(1-->6) disaccharide mimics when using Glc and GlcNAc; in the case of Gal, the beta-anomer was prevalent (beta:alpha=7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogues was demonstrated, based on the use of an unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds was carried out by using NMR spectroscopy, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe)-linked disaccharide analogues exhibit a slightly different conformational behavior to their parent natural disaccharides.     

Reversible colorimetric probes for mercury sensing

The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit for mercury(II) ions--using UV-vis spectroscopy--in homogeneous aqueous solutions is estimated to be approximately 20 ppb for N719 and approximately 150 ppb for N749. Moreover, the sensor molecules can be adsorbed onto high-surface-area mesoporous metal oxide films, allowing reversible heterogeneous sensing of mercury ions in aqueous solution. The results shown herein have important implications in the development of new reversible colorimetric sensors for the fast, easy, and selective detection and monitoring of mercuric ions in aqueous solutions.     

Optimization of solid-phase clean-up prior to liquid chromatographic analysis of ochratoxin A in roasted coffee

An extraction and clean-up method for ochratoxin A (OA) in roasted coffee has been developed and the HPLC method optimized. An interfering compound with a similar retention time as OA was adsorbed by the aminopropyl (NH2) material at < or = 5% NaHCO3. Residual OA on the column was recovered by washing with the extraction solution followed with methanol. Fractions were mixed together for further clean-up with Ochratest immunoaffinity columns (IACs). Analysis by HPLC resulted in a well resolved OA peak and reduction in matrix interferences. Recoveries ranged from 72 to 84% and the detection limit was 1 ng/g.     

Second-generation mimics of ganglioside GM1 oligosaccharide: a three-dimensional view of their interactions with bacterial enterotoxins by NMR and computational methods

As a step to delineate a strategy of ligand design for cholera toxin (CT), NMR studies were performed on several mimics of the GM1 ganglioside oligosaccharide. The conformation of these analogues was investigated first in solution and then upon binding to cholera toxin by transferred nuclear Overhauser effect (TR-NOE) measurements. It was demonstrated that CT selects a conformation similar to the global minima of the free saccharides from the ensemble of presented conformations. No evidence of major conformational distortions was obtained, but one or two of the available conformers of the hydroxyacid side chain appear to be selected in the bound state. The NMR data were interpreted with the aid of computer models, generated and analyzed by using a combination of different approaches (MacroModels' MC/EM and MC/SD, Autodock, and GRID). Analysis of the NMR data supported by computational studies allowed us to interpret the experimental observations and to derive workable models of the ligand:toxin complexes. These models suggest that the higher affinity of the (R)-lactic acid derivative 3 may stem from lipophilic interactions with a hydrophobic area in the toxin binding site located in the vicinity of the sialic acid side chain binding region of the CT:GM1 complex, and formed by the side chain of Ile-58 and Lys-34. Thus, the models obtained have allowed us to make useful design suggestions for the improvement of ligand affinity.     

Reaction products of W(CO)(6) with formamidines; electronic structure of a W(2)(mu-CO)(2) core with unsymmetric bridging carbonyls

Reactions of W(CO)(6) with formamidines contrast with those of Mo(CO)(6) and Cr(CO)(6) in that the former do not yield quadruply bonded dimetal species. From the reaction of W(CO)(6) with HDAniF (HDAniF = N,N'-di-p-anisylformamidine), several new ditungsten carbonyl compounds (W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(2) (1), W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(eta(2)-CH(2)DAniF) (2), and W(2)(mu-CO)(mu-CNC(6)H(4)OCH(3))(mu-DAniF)(2)(eta(2)-DAniF)(2) (3)) have been isolated and fully characterized. In 2, CH(2)DAniF represents a DAniF ligand in which a methylene group has been added to one of the nitrogen atoms. This ligand binds to the tungsten atom using a nitrogen and a carbon atom. Compound 1 has a tungsten-tungsten bond distance of 2.476(1) A and a planar W(2)(mu-CO)(2) core structure which has C(2)(h)() symmetry with short and long W-C bond distances (1.99(1) and 2.28(1) A, respectively). DFT calculations on a model of 1 indicate that (a) the C(2)(h)() instead of D(2)(h)() symmetry of the ditungsten core may be attributed to W --> CO pi back-bonding interactions and (b) the bond between the tungsten atoms may be formulated as a double bond. The new tetragonal paddlewheel compound W(2)(DAniF)(4) (4) and the edge-sharing bioctahedron W(2)(mu-O)(mu-NC(6)H(3)Cl(2))(mu-D(Cl)PhF)(2)(eta(2)-D(Cl)PhF)(2) (5) (D(Cl)PhF = N,N'-di-(3,5-dichlorophenyl)formamidinate) have also been prepared.     

Rapid screening method for the determination of diethylstilbestrol in edible animal tissue by column liquid chromatography with electrochemical detection

A rapid and sensitive screening method for the determination of residues of diethylstilbestrol in edible animal tissue is described. The analyte was extracted from the tissue with tert.-butyl methyl ether, reextracted with 1 M sodium hydroxide and further cleaned up by solid-phase extraction with C18 cartridges. Analysis was performed by isocratic elution with a phosphate-buffered mobile phase, methanol-0.05 M phosphate buffer pH 3.5 (67:33), on a Nucleosil 5-microns C18 column with electrochemical detection at +0.90 V. The average recovery of trans-diethylstilbestrol in spiked samples is 66%, with a standard deviation of 14% (n = 22) in the range 0.5-2.0 microgram/kg. The detection limit is 0.1-0.2 microgram/kg, although at this level other compounds may interfere and give rise to false positive results.     

Direct asymmetric organocatalytic Michael reactions of alpha,alpha-disubstituted aldehydes with beta-nitrostyrenes for the synthesis of quaternary carbon-containing products

[reaction: see text] Direct asymmetric catalytic Michael reactions have been performed using chiral-amine/acid bifunctional catalysts. Performed with 0.3 equiv of (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine and 0.3 equiv of trifluoroacetic acid as the catalyst, the reaction of alpha,alpha-dialkylaldehydes with (E)-beta-nitrostyrene provided the alpha,alpha-dialkyl Michael products in up to 96% yield with up to 91% ee. With respect to enantioselectivity, l-proline was a poor catalyst of this class of Michael reactions.     

A characteristic redox reaction for N,N′-thiobisamines and some other S(II) compounds

The reaction of copper(II) perchlorate hexahydrate with a number of sulphur(II) compounds in acetonitrile as solvent were studied. It is found that SCl₂, N,N′-thiobisamines S(NR₂)₂, ethoxythiomorpholineC₂H₅O-S-N

and pentacarbonyl (thiobismorpholine) chromium(O)[Cr(CO)₅·S(N

O)₂]reduce Cu(II) with formation of the complex Cu[(CH₃CN)₄]CIO₄ and SO₂.     

Preparation and properties of two indium antimony selenides

Crystals of antimony-doped In₂Se₃ were grown by the Bridgeman method. This compound, whose composition is In_1.8Sb_0.2Se₃, appears to be isostructural with In_1.9As_0.1Se₃. The refined unit cell parameters are a = 3.97(1), c = 18.87(1) Å. Orthorhombic crystals of InSbSe₃ were grown from an isothermal melt. The refined unit cell parameters are a = 9.43(1), b = 14.02(5), and c = 3.96(1) Å. These parameters agree with those determined for α-InSbSe₃ by other studies. The observed densities measured by a hydrostatic technique are 5.98(3) g/cm³ for In_1.8Sb_0.2Se₃ and 6.07(2) g/cm³ for InSbSe₃. The room temperature dc resistivity for In_1.8Sb_0.2Se₃ has been found to be 4.4 × 10⁴ Ω-cm, whereas that of InSbSe₃ has been found to be 15.2(1) Ω-cm. A resistivity versus temperature study has beenn carried out for InSbSe₃ between 230 and 400°K. Optical studies indicate that In_1.8Sb_0.2Se₃ is an n-type semiconductor with a band gap of 1.1 eV and InSbSe₃ is a p-type semiconductor with a band gap of 0.92 eV.