Low temperature crystal structures of two rhodanine derivatives, 3-amino rhodanine and 3-methyl rhodanine: geometry of the rhodanine ring

Rhodanines (2-thio-4-oxothiazolidines) are synthetic small molecular weight organic molecules with diverse applications in biochemistry, medicinal chemistry, photochemistry, coordination chemistry and industry. The X-ray crystal structure determination of two rhodanine derivatives, namely (I), 3-aminorhodanine [3-amino-2-thio-4-oxothiazolidine], C3H4N2OS2, and (II) 3-methylrhodanine [3-methyl-2-thio-4-oxothiazolidine], C4H5NOS2, have been conducted at 100 K. I crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 9.662(2), b = 9.234(2), c = 13.384(2) angstrom, beta = 105.425(3)degrees, V = 1151.1(3) angstrom(3), Z = 8 (2 independent molecules per asymmetric unit), density (calculated) = 1.710 mg/m(3), absorption coefficient = 0.815 mm(-1). II crystallizes in the orthorhombic space group Iba2 with unit cell a = 20.117(4), b = 23.449(5), c = 7.852(2) angstrom, V = 3703.9(12) angstrom(3), Z = 24 (three independent molecules per asymmetric unit), density (calculated) = 1.584 mg/m(3), absorption coefficient 0.755 mm(-1). For I in the final refinement cycle the data/restraints/parameter ratios were 2639/0/161, goodness-of-fit on F-2 = 0.934, final R indices [I > 2sigma(I)] were R1 = 0.0299, wR2 = 0.0545 and R indices (all data) R1 = 0.0399, wR2 = 0.0568. The largest difference peak and hole were 0.402 and -0.259 e angstrom(-3). For II in the final refinement cycle the data/restraints/parameter ratios were 3372/1/221, goodness-of-fit on F(2) = 0.950, final R indices [I > 2sigma(I)] were R1 = 0.0407, wR2 = 0.1048 and R indices (all data) R1 = 0.0450, wR2 = 0.1088. The absolute structure parameter = 0.19(9) and largest difference peak and hole 0.934 and -0.301 e angstrom(-3). Details of the geometry of the five molecules (two for I and three for II) and the crystal structures are fully discussed. Corresponding features of the molecular geometry are highly consistent and firmly establish the geometry of the rhodanine

Phytoplankton carbon fixation chlorophyll-biomass and diagnostic pigments in the Atlantic Ocean

We have made daily measurements of phytoplankton pigments, size-fractionated (<2 and >2-μm) carbon fixation and chlorophyll-a concentration during four Atlantic Meridional Transect (AMT) cruises in 2003–04. Surface rates of carbon fixation ranged from <0.2-mmol C m−3 d−1 in the subtropical gyres to 0.2–0.5-mmol C m−3 d−1 in the tropical equatorial Atlantic. Significant intercruise variability was restricted to the subtropical gyres, with higher chlorophyll-a concentrations and carbon fixation in the subsurface chlorophyll maximum during spring in either hemisphere. In surface waters, although picoplankton (<2-μm) represented the dominant fraction in terms of both carbon fixation (50–70%) and chlorophyll-a (80–90%), nanoplankton (>2-μm) contributions to total carbon fixation (30–50%) were higher than to total chlorophyll-a (10–20%). However, in the subsurface chlorophyll maximum picoplankton dominated both carbon fixation (70–90%) and chlorophyll-a (70–90%). Thus, in surface waters chlorophyll-normalised carbon fixation was 2–3 times higher for nanoplankton and differences in picoplankton and nanoplankton carbon to chlorophyll-a ratios may lead to either higher or similar growth rates. These low chlorophyll-normalised carbon fixation rates for picoplankton may also reflect losses of fixed carbon (cell leakage or respiration), decreases in photosynthetic efficiency, grazing losses during the incubations, or some combination of all these. Comparison of nitrate concentrations in the subsurface chlorophyll maximum with estimates of those required to support the observed rates of carbon fixation (assuming Redfield stoichiometry) indicate that primary production in the chlorophyll maximum may be light rather than nutrient limited.

Structure of Ionic Liquid-Benzene Mixtures

Neutron diffraction has been used to investigate the structure of liquid mixtures of 1,3-dimethylimidazolium hexafluorophosphate with benzene. Two concentrations of benzene were investigated, namely, 33 mol % and 67 mol %, and show similar structures in each case. The presence of benzene significantly alters the ionic liquid structure, in particular, in the cation-cation interactions, in agreement with the single-crystal structure described recently (Holbrey, J. D.; Reichert, W. M.; Nieuwenhuyzen, M.; Sheppard, O.; Hardacre, C.; Rogers, R. D. Chem. Commun. 2003, 476). In each case, the data was analyzed using an empirical potential structure refinement process.

Influence of plasticizer type and storage conditions on properties of poly(methyl vinyl ether-co-maleic anhydride) bioadhesive films

Poly(methyl vinyl ether-co-maleic anhydride) formed films from aqueous formulations with characteristics that are ideal as a basis for producing a drug-containing bioadhesive delivery system when plasticized with a monohydroxyl functionalized plasticizer. Hence, films containing a novel plasticizer, tripropylene glycol methyl ether (TPME), maintained their adhesive strength and tensile properties when packaged in aluminized foil for extended periods of time. Films plasticized with commonly used polyhydric alcohols, such as the glycerol in this study, underwent an esterification reaction that led to polymer crosslinking, as shown in NMR studies. These revealed the presence of peaks in the ester/carbonyl region, suggesting that glyceride residue formation had been initiated. Given the polyfunctional nature of glycerol, progressive esterification would result in a polyester network and an accompanying profound alteration in the physical characteristics. Indeed, films became brittle over time with a loss of both the aqueous solubility and bioadhesion to porcine skin. In addition, a swelling index was measurable after 7 days, a property not seen with those films containing TPME. This change in bioadhesive strength and pliability was independent of the packaging conditions, rendering the films that contain glycerol as unsuitable as a basis for topical bioadhesive delivery of drug substances. Consequently, films containing TPME have potential as an alternative formulation strategy.

University students with disabilities in Universities. A study of their inclusion

Access to higher education has increased among students with disabilities, and universities are adopting different alternatives which must be assessed. The purpose of this study was to identify the situation of a sample of students with disabilities (n=91) who attend a university in Spain, through the design and validation of the “CUNIDIS-d” scale, with satisfactory psychometric properties. The results show the importance of making reasoned curriculum adaptations, adapting teacher training, improving accessibility and involving all the university community. Different proposals were provided which support the social dimension of the EHEA.

WASP-3b: a strongly irradiated transiting gas-giant planet

We report the discovery of WASP-3b, the third transiting exoplanet to be discovered by the WASP and SOPHIE collaboration. WASP-3b transits its host star USNO-B1.01256-0285133 every 1.846834 +/- 0.000002 d. Our high-precision radial velocity measurements present a variation with amplitude characteristic of a planetary-mass companion and in phase with the light curve. Adaptive optics imaging shows no evidence for nearby stellar companions, and line-bisector analysis excludes faint, unresolved binarity and stellar activity as the cause of the radial velocity variations. We make a preliminary spectroscopic analysis of the host star and find it to have Teff = 6400 +/- 100K and log g = 4.25 +/- 0.05 which suggests it is most likely an unevolved main-sequence star of spectral type F7-8V. Our simultaneous modelling of the transit photometry and reflex motion of the host leads us to derive a mass of 1.76+0.08-0.14 MJ and radius 1.31+0.07-0.14 RJ for WASP-3b. The proximity and relative temperature of the host star suggests that WASP-3b is one of the hottest exoplanets known, and thus has the potential to place stringent constraints on exoplanet atmospheric models.

Electrochemical studies of gold and chloride in ionic liquids

For the first time, the electrochemistry of gold has been studied in detail in a 'second-generation', non-haloaluminate, ionic liquid. In particular, the electrochemical behaviour of Na[AuCl4] has been investigated in 1-butyl-3-methylimidazolium bis{(tifluoromethyl)sulfonyl} imide, [C(4)mim][NTf2], over gold, platinum and glassy carbon working electrodes. The reduction of [AuCl4](-) initially forms [AuCl2](-) before deposition on the electrode as Au(0). To enable stripping of deposited gold or electrodissolution of bulk gold, the presence of chloride, trichloride or chlorine is required. Specifically trichloride and chlorine have been identified as the active species which preferentially form Au(I) and Au(III), respectively.

The temperature dependence of the adsorption of NO on Pt{211}: A RAIRS and DFT investigation

RAIRS experiments have been performed to investigate the adsorption of NO on Pt{211}. Results show that adsorption is complex and strongly temperature dependent. At 307 K, three bands are seen at saturation with frequencies of 1801, 1609, and 1576 cm(-1). However, at 120 K only two bands, at 1688 and 1620 cm(-1), are observed. To help with the assignment of these vibrational bands, DFT calculations were also performed. The calculations show that a bridged NO species, bonded to the step edge, is the most stable species on the surface and gives rise to the band observed at 1610-1620 cm(-1). The calculations also suggest that the temperature dependence of NO adsorption on Ptf{211} can be assigned to NO dissociation which occurs at room temperature but not at 120 K. In particular, the RAIRS band observed at 1801 cm(-1), which is observed on adsorption at 307 K but not at 120 K, is tentatively assigned to the formation of an O-NO complex. This species forms when a NO molecule bonds on top of an O atom, which results from the dissociation of NO on the Pt{211} surface at room temperature.

Notas sobre el "primum cognitum" en Cayetano y su vínculo con la metafísica

Cayetano tuvo un papel protagónico en los debates intelectuales de su época (s. XVI), destacándose como un auténtico adalid del tomismo; inclusive muchas de sus tesis pasaron a formar parte de tal doctrina, las cuales –a veces matizadas y otras no tanto– perviven hasta nuestros días. Entre los diversos temas que afrontó se destaca su particular noción de primum cognitum. Aquí, partimos del hecho de que la tradición tomista no ha visto mayores inconvenientes en equiparar lo que entienden Cayetano y el Aquinate por el ens primo cadit; empero nosotros estamos en condiciones de afirmar que tal equiparación al menos es problemática. En este sentido, nos ocuparemos de realizar un primer acercamiento al tema del ente primer conocido cayetaniano para intentar mostrar su real significado. Asimismo, procuraremos ver, ayudados por los aportes de algunos estudiosos contemporáneos –en especial el de Lawrence Dewan–, hasta qué punto tal noción se corresponde o no con los desarrollos teóricos de Tomás de Aquino, sobre todo con el vínculo entre el primer conocido y el ente como objeto de la metafísica.

Bis(trifluoromethyl)mercury(II) complexes with purine and 3,5-dimethyl-4 '-amino-triazole as ligands, [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2)

Colourless single crystals of [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2) were obtained from aqueous and etheric solutions of the respective components Purine, (imidazo[4,5-d]pyrimidine, Pur), 3,5-dimethyl-4 '-amino-triazole (Dat) and bis(trifluoromethyl)mercury(II), Hg(CF3)(2). [Hg(CF3)(2)(Pur)](4) crystallizes with the tetragonal system (P-4, Z = 8, a = 1486.8(2), c = 1026.2(l) pm, R-all = 0.0657) with tetrameric molecules consisting of four purine molecules bridged by slightly bent Hg(CF3)2 molecules forming a cage with the CF3 ligands surrounding this cage. The two modifications of [Hg(Dat)(CF3)2]2 (1: 170 K, triclinic, P-1, Z = 2, a 814.9(2), b = 845.4(2), c = 968.4(3) pm, alpha = 106.55(2)degrees, beta= 103.41(2)degrees, gamma = 110.79(2)degrees, R-all = 0.1189; II: monoclinic, P2(1)/c, Z = 8, a = 879.8(2), b = 1731.0(3), c = 1593.9(3) pm, beta = 106.89(2)degrees, R-all = 0.1199) both contain dimeric molecules that are stacked parallel to one crystal axis to strands which are arranged in a parallel fashion in I and rotated against each other in 11 by 110 degrees. In both, the tetrameric [Hg(CF3)(2)(Pur)](4) and the dimeric [Hg(CF3)(2)(Dat)](2) the Hg(CF3)(2) molecules are slightly bent (around 167 and 170 degrees) and rather weakly attached to the N-donor ligands Pur and Dat with Hg-N distances around 272 pm, although in both cases the Hg atoms bridge between two ligand molecules.