Cellular hypomethylation is associated with impaired nitric oxide production by cultured human endothelial cells

Hyperhomocysteinemia (HHcy) is a risk factor for vascular disease, but the underlying mechanisms remain incompletely defined. Reduced bioavailability of nitric oxide (NO) is a principal manifestation of underlying endothelial dysfunction, which is an initial event in vascular disease. Inhibition of cellular methylation reactions by S-adenosylhomocysteine (AdoHcy), which accumulates during HHcy, has been suggested to contribute to vascular dysfunction. However, thus far, the effect of intracellular AdoHcy accumulation on NO bioavailability has not yet been fully substantiated by experimental evidence. The present study was carried out to evaluate whether disturbances in cellular methylation status affect NO production by cultured human endothelial cells. Here, we show that a hypomethylating environment, induced by the accumulation of AdoHcy, impairs NO production. Consistent with this finding, we observed decreased eNOS expression and activity, but, by contrast, enhanced NOS3 transcription. Taken together, our data support the existence of regulatory post-transcriptional mechanisms modulated by cellular methylation potential leading to impaired NO production by cultured human endothelial cells. As such, our conclusions may have implications for the HHcy-mediated reductions in NO bioavailability and endothelial dysfunction.

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrene

A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

Iron oxide/gold core/shell nanomagnetic probes and CdS biolabels for amplified electrochemical immunosensing of Salmonella typhimurium

There is an imminent need for rapid methods to detect and determine pathogenic bacteria in food products as alternatives to the laborious and time-consuming culture procedures. In this work, an electrochemical immunoassay using iron/gold core/shell nanoparticles (Fe@Au) conjugated with anti-Salmonella antibodies was developed. The chemical synthesis and functionalization of magnetic and gold-coated magnetic nanoparticles is reported. Fe@Au nanoparticles were functionalized with different self-assembled monolayers and characterized using ultraviolet-visible spectrometry, transmission electron microscopy, and voltammetric techniques. The determination of Salmonella typhimurium, on screen-printed carbon electrodes, was performed by square-wave anodic stripping voltammetry through the use of CdS nanocrystals. The calibration curve was established between 1×101 and 1×106 cells/mL and the limit of detection was 13 cells/mL. The developed method showed that it is possible to determine the bacteria in milk at low concentrations and is suitable for the rapid (less than 1 h) and sensitive detection of S. typhimurium in real samples. Therefore, the developed methodology could contribute to the improvement of the quality control of food samples.

Homogeneous and heterogenised new gold C-scorpionate complexes as catalysts for cyclohexane oxidation

Gold(III) complexes of type [AuCl2{eta(2)-RC(R'pz)(3)}]Cl [R = R' = H (1), R = CH2OH, R' = H (2) and R = H, R' = 3,5-Me-2(3), pz = pyrazol-1-yl] were supported on carbon materials (activated carbon, carbon xerogel and carbon nanotubes) and used for the oxidation of cyclohexane to cyclohexanol and cyclohexanone, with aqueous H2O2, under mild conditions.

Reduced fluoresceinamine as a fluorescent sensor for nitric oxide

A new fluorescent sensor for nitric oxide (NO) is presented that is based on its reaction with a non fluorescent substance, reduced fluoresceinamine, producing the highly fluorescent fluoresceinamine. Using a portable homemade stabilized light source consisting of 450 nm LED and fiber optics to guide the light, the sensor responds linearly within seconds in the NO concentration range between about 10–750 µM with a limit of detection (LOD) of about 1 µM. The system generated precise intensity readings, with a relative standard deviation of less than 1%. The suitability of the sensor was assessed by monitoring the NO generated by either the nitrous acid decomposition reaction or from a NO-releasing compound. Using relatively high incubation times, the sensor also responds quantitatively to hydrogen peroxide and potassium superoxide, however, using transient signal measurements results in no interfering species.

Assessment of the potential of tin sulphide thin films prepared by sulphurization of metallic precursors as cell absorbers

In this work, SnxSy thin films have been grown on soda-lime glass substrates by sulphurization of metallic precursors in a nitrogen plus sulphur vapour atmosphere. Different sulphurization temperatures were tested, ranging from 300 °C to 520 °C. The resulting phases were structurally investigated by X-Ray Diffraction and Raman spectroscopy. Composition was studied using Energy Dispersive Spectroscopy being then correlated with the sulphurization temperature. Optical measurements were performed to obtain transmittance and reflectance spectra, from which the energy band gaps, were estimated. The values obtained were 1.17 eV for the indirect transition and for the direct transition the values varied from 1.26 eV to 1.57 eV. Electrical characterization using Hot Point Probe showed that all samples were p-type semiconductors. Solar cells were built using the structure: SLG/Mo/SnxSy/CdS/ZnO:Ga and the best result for solar cell efficiency was 0.17%.

Revestimento de superfícies metálicas com TiN e AIN produzidos com plasma magnetrão

Este trabalho visa a obtenção e o estudo das características dos revestimentos de AlN e TiN em substratos metálicos, produzidos por pulverização catódica em plasma magnetrão, num equipamento com cátodo oco, desenvolvido no LEF do CEFITEC. Este equipamento foi adaptado para o presente trabalho, através de alguns elementos adicionais, designadamente de um porta-amostras que permitiu o revestimento de provetes em lotes. Deste estudo conclui-se que a aplicação de uma tensão de “bias” na amostra altera a morfologia dos revestimentos e as características dos materiais que constituem o filme, não só no que diz respeito à sua composição, como também proporciona estruturas mais densas e com menos porosidade. As tensões de “bias” típicas foram de –100 V no caso de AlN e de –75 V e com uma potência de 2,0 kW no cátodo no caso de TiN. Neste último foi considerado apenas o objectivo da obtenção da fase d, de estrutura CFC (cor dourada), por ser a única de interesse industrial. Por difracção de raios x verificou-se a obtenção de TiN e TiN0,9 com as características pretendidas. Também se verificou que as tensões residuais dos filmes são de compressão e isotrópicas.

Contributions à la paleontology du Miocène moyen continental du basin du Tage; (IV) Charophytes - Póvoa de Santarém, Pero Filho et Tremês

This study on middle Miocene Charophytes from the Tagus' basin indicates the presence of two species, hitherto undescribed from these strata in Portugal. Correlation diagrams of height and width of gyrogonite demonstrate that the populations of Nitellopsis (Tectochara) etrusca from the localities Póvoa de Santarém and Pêro Filho are identical to that from La Grenatière (Hérault, France), The population of Lychnothamnus duplicicarinatus from Tremês is identical to that already known from Anwill (Switzerland). The age of this flora is therefore suggested as being the upper part of the middle Miocene. The results of Charophyte studies are in accordance with stratigraphical conclusions from previously conducted mammalian studies (Antunes and Mein). A table showing the distribution of species in the three portuguese localities is given.

Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerization

The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.

Redox-active cytotoxic diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes: Reduction behaviour and theoretical interpretation

Two series of new diorganotin(IV) cycloalkylhydroxamate complexes with different ring sizes (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), formulated as the mononuclear [R2Sn(HL)(2)] (1:2) (a, R=Bu-n and Ph) and the polymeric [R2SnL](n) (1:1) (b, R=Bu-n) compounds, were prepared and fully characterized. Single crystal X-ray diffraction for [(Bu2Sn)-Bu-n{C5H9C(O)NHO}(2)] (3a) discloses the cis geometry and strong intermolecular NH center dot center dot center dot O interactions. The in vitro cytotoxic activities of the complexes were evaluated against HL-60, Bel-7402, BGC-823 and KB human tumour cell lines, the greater activity concerning [(Bu2Sn)-Bu-n(HL)(2)] [HL=C3H5C(O)NHO (1a), C6H11C(O)NHO (4a)] towards BGC-823. The complexes undergo, by cyclic voltammetry and controlled-potential electrolysis, one irreversible overall two-electron cathodic process at a reduction potential that does not appear to correlate with the antitumour activity. The electrochemical behaviour of [R2Sn(C5H9C(O)NHO)(2)] [R=Bu-n (3a), Ph (7a)] was also investigated using density functional theory (DFT) methods, showing that the ultimate complex structure and the mechanism of its formation are R dependent: for the aromatic (R = Ph) complex, the initial reduction step is centred on the phenyl ligands and at the metal, being followed by a second reduction with Sn-O and Sn-C ruptures, whereas for the alkyl (R=Bu-n) complex the first reduction step is centred on one of the hydroxamate ligands and is followed by a second reduction with Sn-O bond cleavages and preservation of the alkyl ligands. In both cases, the final complexes are highly coordinative unsaturated Sn-II species with the cis geometry, features that can be of biological significance.

Zinc oxide as an ozone sensor

Journal of Applied Physics, Vol. 96, nº3