Confinement of chiral molecules in reverse micelles:FT-IR,polarimetric and VCD investigation on the state of dimethyl tartrate in sodium bis(2-ethylhexyl) sulfosuccinate reverse micelles dispersed in carbon tetrachloride

The state of d and l-dimethyl tartrate confined within dry sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles dispersed in CCl4 has been investigated by FT-IR spectroscopy, polarimetry, and vibrational circular dichroism (VCD). Measurements have been performed at 25 ◦C as a function of the solubilizate-to-surfactant molar ratio (R) at a fixed AOT concentration (0.158 M). The analysis of experimental data is consistent with the hypothesis that both enantiomers of dimethyl tartrate are mainly entrapped in the reverse micelles and located in proximity to the surfactant head-group region. The formation of this interesting self-organized chiral nanostructure involves some changes of the typical H-bonding of dimethyl tartrates in the pure solid state or as monomers dispersed in CCl4 attributable to the establishment of specific solubilizate/surfactant head-group interactions and confinement effects

The interaction of native calf thymus DNA with FeIII-dipyrido[3,2-a:2\u2019,3\u2019-c]phenazine

The mono and bis dipyrido[3,2-a:20,30-c]phenazine (dppz) adducts of iron(III) chloride, i.e. [Fe(dppz)]Cl3 and [Fe(dppz)2]Cl3, have been synthesized and characterized. The interaction of the FeIIIdppz hydrolyzed aquo complex with native calf thymus DNA has been monitored as a function of the metal complex\u2013DNA molar ratio, by variable temperature UV absorption spectrophotometry, circular dichroism (CD) and fluorescence spectroscopy. The results obtained in solution at various ionic strength values give support for a tight intercalative binding of the FeIIIdppz cation with DNA. In particular, the appearance of induced CD bands, caused by the addition of FeIIIdppz, indicate the existence of a rigid metal complex\u2013DNA-binding leading to dominating chiral organization of FeIIIdppz species within the DNA double helix. The trend of selected CD bands with the molar concentration of FeIIIdppz emphasizes that the presence of high amounts of metal complex induces also the formation of DNA\u2013FeIIIdppz supramolecular aggregates in solution. The analysis of fluorescence measurements allowed us to calculate a value of the intercalative binding constant comparable to that obtained by UV spectrophotometric titration. Finally, the temperature dependence of the absorbance at 258 nm shows that the metal complex strongly increases the DNA melting temperature already at metal complex\u2013DNA molar ratio equal to 0.25 suggesting that metal complex intercalation effectively hinders DNA denaturation. Overall, the results of the present study point out that the FeIIIdppz aquo complex has DNA-binding properties analogous to those previously reported for the tris-chelate FeII(phen)2dppz complex (phen = 1,10-phenantroline)

Structural Characterization of Surfactant-Coated Bimetallic Cobalt/Nickel Nanoclusters by XPS, EXAFS, WAXS, and SAXS

Cobalt nickel bimetallic nanoparticles were synthesized by changing the sequence of the chemical reduction of Co(II) and Ni(II) ions confined in the core of bis(2-ethylhexyl)phosphate (2)., and Ni(DEHP)(2). The reduction was carried out by mixing, sequentially or contemporaneously, fixed amounts of n-heptane solution of Co(DEHP)2 and Ni(DEHP)2 micelles with a solution of sodium borohydride in ethanol at a fixed (reductant)/(total metal) molar ratio. This procedure involves the rapid formation of surfactant-coated nanoparticles, indicated as Co/Ni (Co after Ni), Ni/Co (Ni after Co), and Co + Ni (simultaneous), followed by their slow separation as nanostructures embedded in a sodium bis(2-ethylhexyl)phosphate matrix. The resulting composites, together with those obtained by reducing the n-heptane solutions of pure Co(DEHP)(2) or Ni(DEHP)(2), were characterized by XPS, EXAFS, WAXS, and SAXS. The data analysis confirms the presence of nanometer-sized surfactant-coated cobalt, nickel, and cobalt/nickel particles. As expected, the composition and internal structure of cobalt/nickel bimetallic nanoparticles are influenced by the preparation sequence as well as by the "chemical affinity" between the surfactant and the metal. However, some atomic-scale physicochemical processes play a subtle role in determining the structural features of bimetallic nanoparticles. Further effects due to the competition between nanoparticle growing process and surfactant adsorption at the nanoparticle surface were observed

Gas chromatographic determination of gallopamil and norgallopamil in human plasma

A highly sensitive gas chromatographic assay is described for the simultaneous determination of gallopamil, a calcium channel blocking agent, and its major metabolite, norgallopamil. A multi-step extraction procedure is employed followed by on-column capillary gas chromatographic analysis using nitrogen-selective detection. Acetylation of norgallopamil is performed to enable accurate quantification of the metabolite. Linearity was achieved over the range 1-50 ng/ml for both analytes. Assay specificity, precision and accuracy were investigated.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/28122/1/0000572.pd

Nitrate stable isotopes and major ions in snow and ice samples from four Svalbard sites

Increasing reactive nitrogen (N-r) deposition in the Arctic may adversely impact N-limited ecosystems. To investigate atmospheric transport of N-r to Svalbard, Norwegian Arctic, snow and firn samples were collected from glaciers and analysed to define spatial and temporal variations (1 10 years) in major ion concentrations and the stable isotope composition (delta N-15 and delta O-18) of nitrate (NO3-) across the archipelago. The delta N-15(NO3-) and delta O-18(NO3-) averaged -4 parts per thousand and 67 parts per thousand in seasonal snow (2010-11) and -9 parts per thousand and 74 parts per thousand in firn accumulated over the decade 2001-2011. East-west zonal gradients were observed across the archipelago for some major ions (non-sea salt sulphate and magnesium) and also for delta N-15(NO3-) and delta O-18(NO3-) in snow, which suggests a different origin for air masses arriving in different sectors of Svalbard. We propose that snowfall associated with long-distance air mass transport over the Arctic Ocean inherits relatively low delta N-15(NO3-) due to in-transport N isotope fractionation. In contrast, faster air mass transport from the north-west Atlantic or northern Europe results in snowfall with higher delta N-15(NO3-) because in-transport fractionation of N is then time-limited

El sector de la construcción en persepectiva : internalización e impacto en el mercado de trabajo

La construcción es considerada a nivel mundial dentro de las actividades económicas más demandantes de mano de obra y ejerce un efecto multiplicador en la economía.1 El presente trabajo tiene por objeto analizar la situación del Sector de la Construcción en los contextos nacionales e internacionales, ponderando fundamentalmente su impacto sobre la economía doméstica. El informe cuenta con una revisión del impacto del sector en el contexto internacional. Se busca registrar los aspectos de la realidad internacional que permitan comparar y evaluar las condiciones del sector en nuestra región a fin de delinear políticas sectoriales en el ámbito local