Effects of cetylpyridinium bromide micelles on the spectrofluorimetric characteristics of polycyclic aromatic hydrocarbons

The presence of a micellar medium of cetylpyridinium bromide (CPB) causes, in relation to the aqueous medium, important bathochromic shifts in the excitation spectra of a considerable number of polycyclic aromatic hydrocarbons (PAHs). Furthermore, the CPB acts as a quencher, provoking inhibitions of the fluorescence intensity emitted by PAHs. The micellar inhibition factors show that, generally, the quenching affects alternant hydrocarbons to a greater extent. Some interesting relationships between the hydrocarbon structure and both the characteristic wavelengths of fluorescence spectra and the values of Deltalambda are established.     

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.     

Determination of polycyclic aromatic hydrocarbons in seawater by high-performance liquid chromatography with fluorescence detection following micelle-mediated preconcentration

In this work, the nonionic surfactant polyoxyethylene-10-lauryl ether has been used for the extraction and preconcentration of 14 polycyclic aromatic hydrocarbons, classified as priority pollutants by the US Environmental Protection Agency, from seawater samples. The cloud-point preconcentration previous separation by HPLC and quantification using fluorimetric detection and wavelength programming allow to determine these pollutants with detection limits ranging from 1.0 to 1.5 x 10(2) ng/l with RSDs better than 10.4%. The methodology is evaluated using well-established extraction and preconcentration methods and GC-MS.     

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.     

Electrospray ionization quadrupole time-of-flight and matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometric analyses to solve micro-heterogeneity in post-translationally modified peptides from Phoneutria nigriventer (Aranea, Ctenidae) venom

Previous studies of the fractionated venom of the Brazilian armed spider Phoneutria nigriventer, obtained by gel filtration, have demonstrated the presence of a fraction PhM, a pool of small peptides (up to 2000 Da) that provoke contractions in smooth muscle of guinea pig ileum. Initial attempts to sequence these peptides were largely unsuccessful because of the low purification yield and the fact that the majority seemed to be blocked at their N-termini. In the present work, analysis of this venom fraction by mass spectrometry has revealed the existence of a highly complex mixture of peptides with molecular weights corresponding to those observed for the muscle-active peptides previously described (800-1800 Da). These peptides appear to be a family of isoforms with some particular features. The amino acid sequences of 15 isoforms have been determined by tandem mass spectrometry (MS/MS) using both electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q/ToFMS) and matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometry (MALDI-ToF/ToFMS). These molecules contain post-translational modifications such as proteolysis and C-terminal amidation, which combine to generate additional isoforms. All the isoforms sequenced in this study possess an N-terminal pyroglutamic acid residue. A search for sequence similarities with other peptides in databanks revealed that these peptides are structurally related to the tachykinins, a family of neuro-hormone peptides. The data obtained in this study will be essential for the subsequent steps of this research, the synthesis of these peptides and pharmacological characterization of their biological activity.     

Properties of a recombinant β-glucosidase from polycentric anaerobic fungus Orpinomyces PC-2 and its application for cellulose hydrolysis

A β-glucosidase (BglA, EC 3.2.1.21) gene from the polycentric anaerobic fungus Orpinomyces PC-2 was cloned and sequenced. The enzyme containing 657 amino acid residues was homologous to certain animal, plant, and bacterial β-glucosidases but lacked significant similarity to those from aerobic fungi. Neither cellulose- nor protein-binding domains were found in BglA. When expressed in Saccharomyces cerevisiae, the enzyme was secreted in two forms with masses of about 110 kDa and also found in two forms associated with the yeast cells. K _m and V _max values of the secreted BglA were 0.762 mM and 8.20 μmol/(min·mg), respectively, with p-nitrophenyl-β-d-glucopyranoside (pNPG) as the substrate and 0.310 mM and 6.45 μmol/(min·mg), respectively, for the hydrolysis of cellobiose. Glucose competitively inhibited the hydrolysis of pNPG with a K _i of 3.6 mM. β-Glucosidase significantly enhanced the conversion of cellulosic materials into glucose by Trichoderma reesei cellulase preparations, demonstrating its potential for use in biofuel and feedstock chemical production. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may be suitable.     

Chemisorption of atomic hydrogen on rhodium: An ab initio cluster-model approach

Interaction of atomic hydrogen with cluster models simulating the Rh(111) surface has been studied at the ab initio SCF level using relativistic non-empirical pseudopotentials and moderately large basis sets. From the bonding parameters, it is seen that chemisorption on the threefold open position is five times more favoured than on the threefold eclipsed one, and the bonding picture is rather different for both active sites. Since two different kinds of adsorbed hydrogen atoms should exist according to various experimental techniques, the present work adds further evidence to the existence of these two types of adsorption and reports some structural parameters which can help to a more detailed characterization in the near future.     

Analogs of propranolol. Synthesis of 3-alkylamino-1-(3-benzo[b]thienyloxy)-2-propanols

The synthesis by two alternative routes of 1-(3-benzo[b]thienyloxy)-3-isopropylamino-2-propanol hydrochloride ( 1a HCl), a thiophenic isoster of Propranolol, and related compounds, is reported. The protecting and enolizing properties of the 2-methoxycarbonyl group on benzo[b]thiophene-3-one, along with its facile removal, are utilized in the first route. In the second one, conversion of 3-bromobenzo[b]thiophene in 1-(3-benzo[b]thienyloxy)-2,3-o-isopropylidenepropane is the key step. On the other hand, hydrolysis of 1-(3-benzo[b]furanyloxy)-2,3-o-isopropylidenepropane to the corresponding diol, in order to obtain a furanic isoster of Propranolol (17a ), was unsuccessful.