Chemical and in vitro study of the potential of 3-(aryl)-2-sulfanylpropenoic acids and their Zn(II) complexes as protective agents against cadmium toxicity

The free H(2)xspa ligands [xspa = pspa, Clpspa, tspa or fspa where p = 3-(phenyl), Clp = 3-(2-chlorophenyl), t = 3-(2-thienyl), f = 3-(2-furyl) and spa = 2-sulfanylpropenoato], their Zn(II) complexes of formula [HQ](2)[Zn(xspa)(2)] (HQ=diisopropylammonium) and the Cd(II) equivalents were prepared and characterized by elemental analysis and by IR, Raman and NMR ((1)H, (13)C) spectroscopy. X-Ray studies of the crystal structures of [HQ](2)[Zn(pspa)(2)], [HQ](2)[Zn(Clpspa)2], [HQ](2)[Zn(tspa)(2)] and [HQ](2)[Zn(fspa)(2)] show that the zinc atom is coordinated to two O atoms and two S atoms of the ligands in a distorted tetrahedral ZnO(2)S(2) environment. In the structures of [HQ](2)[Cd(pspa)(2)] and [HQ](2)[Cd(Clpspa)(2)] the cadmium atom is coordinated to three S atoms and two carboxylato O atoms of the ligands in a distorted trigonal bipyramidal environment. The interchange of ligands between Zn( II) and Cd( II) was studied by (113)Cd NMR spectroscopy. The in vitro protective effect of H(2)xspa and their Zn( II) complexes against Cd toxicity was investigated using the human hepatocarcinoma HepG2 cell line and the pig renal proximal tubule LLC-PK1 cell line. The incorporation of Zn( II) was found to be relevant in the case of H(2)pspa, with an increase observed in the cell viability of the LCC-PK1 cells with respect to the value for the free ligand.

A monohydrate pseudopolymorph of 3,4-dihydroxybenzophenone and the role of water in the crystal assembly of benzophenones

During a polymorphism screening of hydroxybenzophenone derivatives, a monohydrate pseudopolymorph of (3,4-dihydroxyphenyl)(phenyl)methanone, C(13)H(10)O(3)center dot H(2)O, (I), was obtained. Structural relationships and the role of water in crystal assembly were established on the basis of the known anhydrous form [Cox, Kechagias & Kelly (2008). Acta Cryst. B64, 206-216]. The crystal packing of (I) is stabilized by classical intermolecular O-H...O hydrogen bonds, generating a three-dimensional network.

JORDAN BIMODULES OVER THE SUPERALGEBRAS P(n) AND Q(n)

We extend the Jacobson's Coordinatization theorem to Jordan superalgebras. Using it we classify Jordan bimodules over superalgebras of types Q(n) and JP(n), n >= 3. Then we use the Tits-Kantor-Koecher construction and representation theory of Lie superalgebras to treat the remaining case Q(2).

Screening of Microorganisms Producing Cold-Active Oxidoreductases to Be Applied in Enantioselective Alcohol Oxidation. An Antarctic Survey

Several microorganisms were isolated from soil/sediment samples of Antarctic Peninsula. The enrichment technique using (RS)-.1-(phenyl) ethanol as a carbon source allowed us to isolate 232 psychrophile/psychrotroph microorganisms. We also evaluated the enzyme activity (oxidoreductases) for enantioselective oxidation reactions, by using derivatives of (RS)-.1-(phenyl) ethanol as substrates. Among the studied microorganisms, 15 psychrophile/psychrotroph strains contain oxidoreductases that catalyze the (S)-.enantiomer oxidation from racemic alcohols to their corresponding ketones. Among the identified microorganisms, Flavobacterium sp. and Arthrobacter sp. showed excellent enzymatic activity. These new bacteria strains were selected for optimization study, in which the (RS)-.1-(4-.methyl-.phenyl) ethanol oxidation was evaluated in several reaction conditions. From these studies, it was observed that Flavobacterium sp. has an excellent enzymatic activity at 10 degrees C and Arthrobacter sp. at 15 and 25 degrees C. We have also determined the growth curves of these bacteria, and both strains showed optimum growth at 25 degrees C, indicating that these bacteria are psychrotroph.

(5R)-3-(2-Chloroacetyl)-4-methyl-5phenyl-1,3,4-oxadiazinan-2-one

The 1,3,4-oxadiazinan-2-one ring in the title compound, C(12)H(13)ClN(2)O(3), is in a distorted half-chair conformation. The phenyl and chloroacetyl groups occupy axial and equatorial positions, respectively, and lie to the opposite side of the molecule to the N-bound methyl substituent. Molecules are consolidated in the crystal structure by C-H center dot center dot center dot O interactions.

2-Bromo-2-methyl-N-p-tolylpropanamide

In the title molecule, C(11)H(14)BrNO, there is twist between the mean plane of the amide group and the benzene ring [C(=O)-N-C...;C torsion angle = -31.2 (5)degrees]. In the crystal, intermolecular N-H...O and weak C-H...O hydrogen bonds link molecules into chains along [100]. The methyl group H atoms are disordered over two sets of sites with equal occupancy.

Blocked diisocyanates as reactive coupling agents: Application to pine fiber-polypropylene composites

In this paper, composites from polypropylene and Kraft pulp (from Pinus radiata) were prepared. Phenyl isocyanate, unblocked and phenol blocked derivatives of 4,4`-methylenebis (phenyl isocyanate) (MDI) were used as coupling agents and the mechanical properties of the obtained composites analyzed. The results showed that the addition of such compatibilizers readily improved the tensile and flexural strengths of the composites. However, no significant variation in the mechanical properties was observed for composite formulations comprising different isocyanate compounds. Accordingly, the chemical structure of isocyanate derivatives did not affect extensively the mechanical properties of MDI-coupled pine fiber reinforced composites. These results were similar to those obtained in previous studies regarding the efficiency of organosilane coupling agents. In comparison to monoreactive isocyanates, the addition of MIDI increased considerably the mechanical properties of pine fiber-polypropylene composites. The mechanical anchoring of polymeric PP chains onto the irregular reinforcement surface supported this result. Non-isothermal DSC analysis showed a slowing effect of MDI on the crystallization kinetics of the coupled composites. This may have been the result of diminished polymer chain mobility in the matrix due to mechanical anchoring onto the fiber surface. Considering these results, the occurrence of strong bonds between the composite components was stated, rather than the unique existence of Van der Waals interactions among the non-polar structures. (c) 2008 Elsevier Ltd. All rights reserved.

Controlling the luminescence properties of poly(p-phenylene vinylene) entrapped in Langmuir and Langmuir-Blodgett films of stearic acid

Properties of hybrid films can be enhanced if their molecular architecture is controlled. In this paper, poly (p-phenylene vinylene) was mixed with stearic acid in order to form stable hybrid Langmuir monolayers. Surface properties of these films were investigated with measurements of surface pressure, and also with polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The films were transferred from the air-water interface to solid supports through the Langmuir-Blodgett technique, and the viability of the film as optical device was investigated with fluorescence spectroscopy. Comparing the fluorescent spectra for the polymer in solution, as a casting film, and as an LB film, the emission bands for LB films were narrower and appeared at lower wavelengths. The interactions between the film components and the design for the LB film may take advantage of the method to immobilize luminescent polymers in mixed ultrathin films adsorbed in solid matrices. (C) 2011 Elsevier B.V. All rights reserved.

Novel blue emitters based on pi-conjugated block copolymers

A series of new phenyl-based conjugated copolymers has been synthesized and investigated by vibrational and photoluminescence spectroscopy (PL). The materials are: poly( 1,4-phenylene-alt-3,6-pyridazine) (COP-PIR), poly(9,9-dioctylfluorene)-co-quaterphenylene (COP-PPP) and poly[(1,4-phenylene-alt-3,6-pyridazine)-co-(1,4-phenylene-alt-9,9-dioctylfluorene)] (COP-PIR-FLUOR), with 3.5% of fluorene. COP-PPP and COP-PIR-FLUOR have high fluorescence quantum yields in solution. Infrared and Raman spectra were used to check the chemical structure of the compounds. The copolymers exhibit blue emission ranging front 2.8 to 3.6 eV when excited at E(exc)=4.13 eV. Stokes-shift Values were estimated on pristine samples in their condensed state from steady-state PL-emission and PL-excitation spectra. They suggest a difference in the torsional angle between the molecular configuration of the polymer blocks at the absorption and PL transitions and also in the photoexcitation diffusion. Additionally, the time-resolved PL of these materials has been investigated by using 100 fs laser pulses at E(exc)=4.64 eV and a streak camera. Results show very fast biexponential kinetics for the two fluorene-based polymers with decay times below 300 ps indicating both intramolecular, fast radiative recombination and migration of photogenerated electron-hole pairs. By contrast, the PL of COP-PIR is less intense and longer lived, indicating that excitons are confined to the chains in this polymer. (C) 2008 Elsevier B.V. All rights reserved.

Low-frequency noise and static analysis of the impact of the TiN metal gate thicknesses on n- and p-channel MuGFETs

The impact of the titanium nitride (TIN) gate electrode thickness has been investigated in n and p channel SOI multiple gate field effect transistors (MuGFETs) through low frequency noise charge pumping and static measurements as well as capacitance-voltage curves The results suggest that a thicker TIN metal gate electrode gives rise to a higher EOT a lower mobility and a higher interface trap density The devices have also been studied for different back gate biases where the GIFBE onset occurs at lower front-gate voltage for thinner TIN metal gate thickness and at higher V(GF) In addition it is demonstrated that post deposition nitridation of the MOCVD HfSiO gate dielectric exhibits an unexpected trend with TIN gate electrode thickness where a continuous variation of EOT and an increase on the degradation of the interface quality are observed (C) 2010 Elsevier Ltd All rights reserved

Material properties and nondestructive evaluation of laminated veneer lumber (LVL) made from Pinus oocarpa and P. kesiya

This study aimed at evaluating the mechanical, physical and biological properties of laminated veneer lumber (LVL) made from Pinus oocarpa Schiede ex Schltdl (PO) and Pinus kesiya Royle ex Gordon (PK) and at providing a nondestructive characterization thereof. Four PO and four PK LVL boards from 22 randomly selected 2-mm thickness veneers were produced according to the following characteristics: phenol-formaldehyde (190 g/m(2)), hot-pressing at 150A degrees C for 45 min and 2.8 N/mm(2) of specific pressure. After board production, nondestructive evaluation was conducted, and stress wave velocity (v (0)) and dynamic modulus of elasticity (E (Md) ) were determined. The following mechanical and physical properties were then evaluated: static bending modulus of elasticity (E (M) ), modulus of rupture (f (M) ), compression strength parallel to grain (f (c,0)), shear strength parallel to glue-line (f (v,0)), shear strength perpendicular to glue-line (f (v,90)), thickness swelling (TS), water absorption (WA), and permanent thickness swelling (PTS) for 2, 24, and 96-hour of water immersion. Biological property was also evaluated by measuring the weight loss by Trametes versicolor (Linnaeus ex Fries) Pilat (white-rot) and Gloeophyllum trabeum (Persoon ex Fries.) Murrill (brown-rot). After hot-pressing, no bubbles, delamination nor warping were observed for both species. In general, PK boards presented higher mechanical properties: E (M) , E (Md) , f (M) , f (c,0) whereas PO boards were dimensionally more stable, with lower values of WA, TS and PTS in the 2, 24, and 96-hour immersion periods. Board density, f (v,0), f (v,90) and rot weight loss were statistically equal for PO and PK LVL. The prediction of flexural properties of consolidated LVL by the nondestructive method used was not very efficient, and the fitted models presented lower predictability.

Enantioselective Arylations Catalyzed by Carbohydrate-Based Chiral Amino Alcohols

The application of carbohydrate-derived amino alcohols in the asymmetric arylation of aldehydes by using arylboronic acids as the source of transferable aryl groups is described. The best ligand is derived from the readily available sugar D-xylose and it mediates the addition of a range of arylboronic acids to various aromatic aldehydes in excellent yields and high enantiomeric excesses.

HPLC-UV determination of metformin in human plasma for application in pharmacokinetics and bioequivalence studies

In this study, a simple, rapid and sensitive HPLC method with UV detection is described for determination of metformin in plasma samples from bioequivalence assays. Sample preparation was accomplished through protein precipitation with acetonitrile and chromatographic separation was performed on a reversed-phase phenyl column at 40 degrees C. Mobile phase consisted of a mixture of phosphate buffer and acetonitrile at flow rate of 1.0 ml/min. Wavelength was set at 236 nm. The method was applied to a bioequivalence study of two drug products containing metformin, and allowed determination of metformin at low concentrations with a higher throughput than previously described methods. (c) 2007 Elsevier B.V. All rights reserved.

Generation and Analysis of Interaction Energy Maps of p-Substituted Benzoic Acid [(5-Nitro-thiophen-2-yl)-methylene]-Hydrazides Active against MRSA

In this preliminary study eighteen p-substituted benzoic acid [(5-nitro-thiophen-2-yl)-methylene]-hydrazides with antimicrobial activity were evaluated against multidrug-resistant Staphylococcus aureus, correlating the three-dimensional characteristics of the ligands with their respective bioactivities. The computer programs Sybyl and CORINA were used, respectively, for the design and three-dimensional conversion of the ligands. Molecular interaction fields were calculated using GRID program. Calculations using Volsurf resulted in a statistically consistent model with 48 structural descriptors showing that hydrophobicity is a fundamental property in the analyzed biological response.

Application of hydrophobic resin adhesives to acid-etched dentin with an alternative wet bonding technique

Hydrophilic dentin adhesives are prone to water sorption that adversely affects the durability of resin-dentin bonds. This study examined the feasibility of bonding to dentin with hydrophobic resins via the adaptation of electron microscopy tissue processing techniques. Hydrophobic primers were prepared by diluting 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane/triethyleneglycol dimethacrylate resins with known ethanol concentrations. They were applied to acid-etched moist dentin using an ethanol wet bonding technique that involved: (1) stepwise replacement of water with a series of increasing ethanol concentrations to prevent the demineralized collagen matrix from collapsing; (2) stepwise replacement of the ethanol with different concentrations of hydrophobic primers and subsequently with neat hydrophobic resin. Using the ethanol wet bonding technique, the experimental primer versions with 40, 50, and 75% resin exhibited tensile strengths which were not significantly different from commercially available hydrophilic three-step adhesives that were bonded with water wet bonding technique. The concept of ethanol wet bonding may be explained in terms of solubility parameter theory. This technique is sensitive to water contamination, as depicted by the lower tensile strength results from partial dehydration protocols. The technique has to be further improved by incorporating elements of dentin permeability reduction to avoid water from dentinal tubules contaminating water-free resin blends during bonding. (c) 2007 Wiley Periodicals, Inc. J Biomed Mater Res 84A: 19-29, 2008.