Effects of endogenous flour lipids on the quality of short-dough biscuits

Fractionation and reconstitution techniques were used to study the contribution of endogenous flour lipids to the quality of short-dough (shortcake type) biscuits. Biscuit flour was defatted with chloroform and baked with bakery fat, but without endogenous lipid. Short-dough biscuits baked from defatted flour had smaller diameters, and were flatter, denser and harder than control biscuits. Defatted flour shortcake doughs exhibited different rheological behaviour from the control samples, showing higher storage and loss moduli (G' and G" values), ie higher viscoelasticity. Functionality was restored when total non-starch flour lipids were added back to defatted flour. The polar lipid fraction had a positive effect in restoring flour quality whereas the non-polar lipid fraction had no effect. Both fractions were needed for complete restoration of both biscuit quality and dough rheological characteristics. A study of the microstructure of defatted biscuits revealed that their gluten protein was more hydrated and developed than the gluten of the control biscuits. This conclusion was supported by the higher water absorption of the defatted gluten. (C) 2004 Society of Chemical Industry.

Preparation of (���)-epigallocatechin gallate from commercial green tea by caffeine precipitation and solvent partition

A method has been developed which enables the easy and inexpensive preparation of gram quantities of (���)-epigallocatechin gallate from green tea (Camellia sinensis). A decaffeinated aqueous brew of commercial green tea is treated with caffeine (30 m ). The precipitate is redissolved after decaffeination with chloroform and further purified by solvent partition with ethyl hexanoate and propyl acetate. Commercial leaf (25 g) yields 400 mg (���)-epigallocatechin gallate at better than 80% purity, as judged by reversed phase HPLC.

Synthesis and X-ray crystal structure of the copper(I) dicarboxylic acid complex [Cu(��1-bdoaH)(PPh3)3] (bdoaH2 = benzene-1,2- dioxyacetic acid)

The copper(II) complex [Cu(bdoa)(H2O)2] (bdoaH2 = benzene-1,2-dioxyacetic acid) reacts with triphenylphosphine (1:4 mol ratio) to give the colourless copper(I) complex [Cu(��1-bdoaH)(PPh3)3] (1) in good yield. The X-ray crystal structure of the complex shows the copper atom at the centre of a distorted tetrahedron, and is ligated by the phosphorus atoms of the three triphenylphosphines and one carboxylate oxygen atom of the bdoaH��� ligand. Significant intermolecular hydrogen-bonding exists between the pendant carboxylate OH function of one molecule and the uncoordinated ���ketonic��� oxygen of a neighbouring molecule. Complex 1 is non-conducting in chloroform but ionizes readily in acetonitrile. The cyclic voltammogram of an acetonitrile solution of 1 shows a single irreversible anodic peak for the oxidation of the PPh3 ligands and the copper(I) centre, and a single irreversible cathodic peak for the reduction of the bdoaH��� ion. IR and mass spectral data for 1 are given.

Direct iminization of PEEK

Semi-crystalline poly(ether ketone)s are important high-temperature engineering thermoplastics, but are difficult to characterize at the molecular level because of their insolubility in conventional organic solvents. Here we report that polymers of this type, including PEEK, react cleanly at high temperatures with low-volatility aralkyl amines to afford stable, noncrystalline poly(ether-imine)s, which are readily soluble in solvents such as chloroform, THF and DMF and so characterizable by conventional size-exclusion chromatography.

Intracellular or intercellular localization of the polar pathway of penetration across stratum corneum

A pharmacokinetic hypothesis of stratum corneum with two parallel pathways, lipophilic and porous hydrophilic, is not well documented yet. Still questionable is the localization of the pores, and the present experiments were designed to elucidate the contribution of extracellular lipids and intracellular keratin to the structure of this pathway. Percutaneous penetration of baclofen, a model zwitterion, was studied in vitro using human cadaver skin. Aqueous or ethanolic saturated solutions of the drug (Cs = 4.6 and 0.4 mg/ mL, respectively) were applied on the skin that was pretreated with: methanol/chloroform (Me/Ch) or acetone-chloroform (Ac/Ch) (1:1) mixtures, or with these solvents followed by 0.2% solution of sodium lauryl sulfate (SLS). As controls, baclofen penetration through the intact full-thickness skin was determined, and the fluxes were 0.18 ��0.08 and 0.14 ��0.07 ��g/cm2/h for aqueous and ethanolic solutions, respectively. When Me/Ch was used for 1 h, an expected increase of the penetration was observed, but the lag time, Tlag, was still nearly 20 h. When the less polar mixture, Ac/Ch, was used, no flux enhancement was observed, and with ethanol as the vehicle, decreased penetration was even noted. No effect on baclofen penetration was observed when SLS was used for 1 h after delipidization of the skin was done with either the Me/Ch or Ac/Ch mixture. The results suggest that the polar pathway may be located intercellularly and comprises aqueous regions surrounded by polar lipids, which create the walls of such microchannels.

Formation of vesicles through solvent assisted self-assembly of hydrophobic pentapeptides: encapsulation and pH responsive release of dyes by the vesicles

In the biomimetic design two hydrophobic pentapetides Boc-Ile-Aib-Leu-Phe-Ala-OMe ( I) and Boc-Gly-Ile-Aib-Leu-Phe-OMe (II) (Aib: alpha-aminoisobutyric acid) containing one Aib each are found to undergo solvent assisted self-assembly in methanol/water to form vesicular structures, which can be disrupted by simple addition of acid. The nanovesicles are found to encapsulate dye molecules that can be released by the addition of acid as confirmed by fluorescence microscopy and UV studies. The influence of solvent polarity on the morphology of the materials generated from the peptides has been examined systematically, and shows that fibrillar structures are formed in less polar chloroform/petroleum ether mixture and vesicular structures are formed in more polar methanol/water. Single crystal X-ray diffraction studies reveal that while beta-sheet mediated self-assembly leads to the formation of fibrillar structures, the solvated beta-sheet structure leads to the formation of vesicular structures. The results demonstrate that even hydrophobic peptides can generate vesicular structures from polar solvent which may be employed in model studies of complex biological phenomena.

Radiative forcing and global warming potentials of 11 halogenated compounds

Radiative forcing values have been calculated for 11 halogenated compounds which are in current use or which have been suggested as possible replacements for the chlorofluorocarbons. Absorption cross-sections measured over a range of atmospheric temperature and pressure conditions as part of a multi-laboratory programme have been used together with a narrow band radiative transfer model. We provide a ���best estimate��� radiative forcing taking into account the likely vertical profile of the gas in each case. The Global Warming Potential over a variety of time horizons has also been calculated where the lifetime is available. We present the first such information for 1,2-dichloroethane. For chloroform our radiative forcing is 5 times higher than the value used in previous assessments, possibly because these ignored the effect of absorption outside the 800���1200 cm���1 ���window���. For several of the other compounds considered here, our forcing is between 10 and 30% lower than previous assessments. The perfluorocarbons have been found to have large global warming potentials, many times that of CFC-11, due to both strong absorption and long lifetimes. The importance of absorption features at wavenumbers below 800 cm���1 and the effect of temperature variations in absorption cross-section on the radiative forcing are also investigated.

Thermodynamic Stabillity of Hydrogen-Bonded Systems in Polar and Nonpolar Environments

The thermodynamic properties of a selected set of benchmark hydrogen-bonded systems (acetic acid dimer and the complexes of acetic acid with acetamide and methanol) was studied with the goal of obtaining detailed information on solvent effects on the hydrogen-bonded interactions using water, chloroform, and n-heptane as representatives for a wide range in the dielectric constant. Solvent effects were investigated using both explicit and implicit solvation models. For the explicit description of the solvent, molecular dynamics and Monte Carlo simulations in the isothermal isobaric (NpT) ensemble combined with the free energy perturbation technique were performed to determine solvation free energies. Within the implicit solvation approach, the polarizable continuum model and the conductor-like screening model were applied. Combination of gas phase results with the results obtained from the different solvation models through an appropriate thermodynamic cycle allows estimation of complexation free energies, enthalpies, and the respective entropic contributions in solution. Owing to the strong solvation effects of water the cyclic acetic acid dimer is not stable in aqueous solution. In less polar solvents the double hydrogen bond structure of the acetic acid dimer remains stable. This finding is in agreement with previous theoretical and experimental results. A similar trend as for the acetic acid dimer is also observed for the acetamide complex. The methanol complex was found to be thermodynamically unstable in gas phase as well as in any of the three solvents. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 31: 2046-2055, 2010

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Risk assessment of trihalomethanes from tap water in Fortaleza, Brazil

The cancer risks (CR) by oral ingestion, dermal absorption, and inhalation exposure of trihalomethanes (THM) from tap water of ten districts in Fortaleza, Brazil were estimated. The mean levels of THM compounds were obtained in Fortaleza tap water as follow: 63.9 mu g L(-1) for chloroform (CHCl(3)), 40.0 mu g L(-1) for bromodichloromethane (CHBrCl(2)), and 15.6 mu g L(-1) for dibromochloromethane (CHBr(2)Cl). Bromoform (CHBr(3)) was not detected. The mean CR for THMs in tap water is 3.96 x 10(-4). The results indicate that Fortaleza residents have a higher CR by inhalation than dermal absorption and oral ingestion. The CR for CHCl(3) contributes with 68% as compared with the total CR, followed by CHBrCl(2) (21%), and CHBr(2)Cl (11%). The hazard index (HI) is about ten times lower than unity, not indicating non-cancer effects.

Blends of poly(3-hydroxybutyrate) and poly(p-dioxanone): miscibility, thermal stability and biocompatibility

Conselho Nacional de Desenvolvimento Cient��fico e Tecnol��gico (CNPq)

Comparison of DNA-extraction methods and Selective Enrichment broths on the detection of Salmonella Typhimurium in swine feces by polymerase chain reaction (PCR)

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

Mechanism of anticlastogenicity of Agaricus blazei Murill mushroom organic extracts in wild type CHO (K-1) and repair deficient (xrs5) cells by chromosome aberration and sister chromatid exchange assays

Agaricus blazei Murill is a medicinal mushroom native to Brazil. The present work assessed the clastogenic and anticlastogenic potential of organic extracts (ethanol and chloroform/methanol) from the lineage AB97/11 in chinese hamster CHO-K-1 (wild type) and CHO-xrs5 (repair deficient) cells using the chromosome aberration (CA) and sister chromatid exchange (SCE) assays. In these experimental conditions were observed: (a) anticlastogenic effect at concentrations of 0.06 and 0.09% of the EtOH extract and at the 0.03 and 0.06% concentrations of the C/MetOH extract in CHO-K-1; (b) absence of protector effect on CHO-xrs5 cells; and (c) absence of protector effect in the SCE assay. These results indicate that organic extracts of A. blazei lineage AB97/11 present bio-antimutagenic type protective activity. (C) 2003 Elsevier B.V. B.V. All rights reserved.

DNA extraction from hair shafts of wild Brazilian felids and canids

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)