Structural effects and hydrogen bonds on N,N `-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, studied by experimental and theoretical methods

Pure N,N`-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, is quantitatively prepared by the hydrolysis reaction of CH(3)OC(O)SNCO and characterized by (1)H NMR, GC-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH(3)OC(O)SNH](2)CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P2(1)2(1)2 space group with a = 9.524(2), b = 12.003(1), c = 4.481 (1) angstrom, and Z = 2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C(2)) parallel to c and shows the anti-anti conformation (S-N single bonds antiperiplanar with respect to the opposite C-N single bonds in sulfenyl-urea-sic group). Neighboring molecules are arranged in a chain motif that extends along the C(2)-axis and is held by bifurcated NH center dot center dot center dot O center dot center dot center dot HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central -SN(H)C(O)N(H)S- skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N-H center dot center dot center dot O=C hydrogen bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis and Structural Analysis of New Palladium(II) Thiosaccharinates with Triphenylphosphane or Diphosphanes

A series of palladium(II) thiosaccharinates with triphenylphosphane (PPh(3)), bis(diphenylphosphanyl)methane (dppm), and bis(diphenylphosphanyl)ethane (dppe) have been prepared and characterized. From mixtures of thiosaccharin, Htsac, and palladium(II) acetylacetonate, Pd(acac)(2), the palladium(II) thiosaccharinate, Pd(tsac)(2) (tsac: thiosaccharinate anion) (1) was prepared. The reaction of I with PPh(3), dppm, and dppe leads to the mononuclear species Pd(tsac)(2)(PPh(3))(2)center dot MeCN (2), [Pd(tsac)(2)(dppm)] (3), Pd(tsac)(2)(dppm)(2) (4), and [Pd(tsac)(2)(dppe)]center dot MeCN (5). Compounds 2, 4, and 5 have been prepared also by the reaction of Pd(acac)(2) with the corresponding phosphane and Htsac. All the new complexes have been characterized by chemical analysis, UV/Vis, IR, and Raman spectroscopy. Some of them have been also characterized by NMR spectroscopy. The crystalline structures of complexes 3, and 5 have been studied by X-ray diffraction techniques. Complex 3 crystallizes in the monoclinic space group P2(1)/n with a = 16.3537(2), b = 13.3981(3), c = 35.2277(7) angstrom, beta = 91.284(1)degrees, and Z = 8 molecules per unit cell, and complex 5 in P2(1)/n with a = 10.6445(8), b = 26.412(3), c = 15.781(2) angstrom, beta = 107.996(7)degrees, and Z = 4. In compounds 3 and 5, the palladium ions are in a distorted square planar environment. They are closely related, having two sulfur atoms of two thiosaccharinate anions, and two phosphorus atoms of one molecule of dppm or dppe, respectively, bonded to the Pd(II) atom. The molecular structure of complex 3 is the first reported for a mononuclear Pd(II)-dppm-thionate system.

Structural and spectroscopic characterization of 2,2 `-methylenedi-8-quinolinol dihydrochloride dihydrate

The crystal structure of the title compound, a promising ligand for chelatoterapies in the treatment of Alzheimer`s disease, has been determined by single crystal X-ray diffractometry. The compound crystallized in the monoclinic space group C2/c with Z = 4. The dimeric 8-quinolinol molecule is sited on a crystallographic twofold axis passing through the CH(2) carbon atom that links the symmetry related molecular halves, giving rise to a two-bladed propeller-like conformation. The (1)H and (13)C NMR as well as the IFT-IR and Raman spectra of the compound were also recorded and are briefly discussed. Some comparisons with spectra of related species are made. (C) 2008 Elsevier B.V. All rights reserved.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

Tetrachlorocarbonyliridates: Water-Soluble Carbon Monoxide Releasing Molecules Rate-Modulated by the Sixth Ligand

A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR. NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 mu M min(-1) in a 10 mu M solution of myoglobin and 10 mu M of the complexes.

Cyclocreatine, an anticancer and neuroprotective agent. Spectroscopic, structural and theoretical study

The structural, spectroscopic and theoretical study of cyclocreatine (1-carboxymethyl-2-iminoimidazolidine, CyCre) has been performed prompted by the biological relevance of the molecule and its potential role as a ligand in biometalic compounds. The crystal structure of CyCre has been determined by X-ray diffraction methods. The compound crystallizes as a zwitterion in the monoclinic system, space group P2(1)/c. The crystal is further stabilized by a network of N-H center dot center dot center dot O bonds. Infrared and Raman spectra of the solid, electronic spectra of aqueous solutions at different pH values and (1)H and (13)C NMR spectra have been recorded and analyzed. Band assignments were accomplished with the help of theoretical calculations. Optimized molecular geometries, harmonic vibrational frequencies and molecular electrostatic potentials were calculated using methods based on the density functional theory. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, molecular structure and physicochemical properties of bis(3 `-azido-3 `-deoxythymidin-5 `-yl) carbonate

3`-Azido-3`-deoxythymidine (zidovudine, AZT), a synthetic analog of natural nucleoside thymidine, has been used extensively in AIDS treatments. We report here the synthesis. X-ray crystal and molecular structure, NMR, IR and Raman spectra and the thermal behavior of a novel carbonate of AZT [(AZT-O)(2)C=O], prepared by the reaction of zidovudine with carbonyldiimidazole. The carbonate compound, C(21)H(24)N(10)O(9), crystallizes in the tetragonal space group P4(1)2(1)2 with a = b = 15.284(1), c = 21.695(1) angstrom, and Z = 8 molecules per unit cell. It consists of two AZT moieties of closely related conformations which are bridged by a carbonyl group to adopt a folded Z-like shape. (C) 2010 Elsevier B.V. All rights reserved.

Fano resonance in heavily doped porous silicon

Unexpectedly, the Fano resonance caused by the interference of continuum electron excitations with the longitudinal optical (LO) phonons was observed in random porous Si by Raman scattering. The analysis of the experimental data shows that the electron states trapped at the Si-SiO(2) interface dominate in the observed Raman scattering. The gap energy associated with the interface states was determined. Copyright (C) 2011 John Wiley & Sons, Ltd.

High T/P evolution and metamorphic ages of the migmatitic basement of northern Sierras Pampeanas, Argentina: Characterization of a mid-crustal segment of the Famatinian belt

New petrologic, thermobarometric and U-Pb monazite geochronologic information allowed to resolve the metamorphic evolution of a high temperature mid-crustal segment of an ancient subduction-related orogen. The EI Portezuelo Metamorphic-Igneous Complex, in the northern Sierras Pampeanas, is mainly composed of migmatites that evolved from amphibolite to granulite metamorphic facies, reaching thermal peak conditions of 670-820 degrees C and 4.5-5.3 kbar. The petrographic study combined with conventional and pseudosection thermobarometry led to deducing a short prograde metamorphic evolution within migmatite blocks. The garnet-absent migmatites represent amphibolite-facies rocks, whereas the cordierite-garnet-K-feldspar-sillimanite migmatites represent higher metamorphic grade rocks. U-Pb geochronology on monazite grains within leucosome record the time of migmatization between approximate to 477 and 470 Ma. Thus, the El Portezuelo Metamorphic-Igneous Complex is an example of exhumed Early Ordovician anatectic middle crust of the Famatinian mobile belt. Homogeneous exposure of similar paleo-depths throughout the Famatinian back-arc and isobaric cooling paths suggest slow exhumation and consequent longstanding crustal residence at high temperatures. High thermal gradients uniformly distributed in the Famatinian back-arc can be explained by shallow convection of a low-viscosity asthenosphere promoted by subducting-slab dehydration. (C) 2011 Elsevier Ltd. All rights reserved.

Tectonothermal evolution and exhumation history of the Paleozoic Proto-Andean Gondwana margin crust: The Famatinian Belt in NW Argentina

We studied the P-T-t evolution of a mid-crustal igneous-metamorphic segment of the Famatinian Belt in the eastern sector of the Sierra de Velasco during its exhumation to the upper crust. Thermobarometric and geochronological methods combined with field observations permit us to distinguish three tectonic levels. The deepest Level I is represented by metasedimentary xenoliths and characterized by prograde isobaric heating at 20-25 km depth. Early/Middle Ordovician granites that contain xenoliths of Level I intruded in the shallower Level II. The latter is characterized by migmatization coeval with granitic intrusions and a retrograde isobaric cooling P-T path at 14-18 km depth. Level II was exhumed to the shallowest supracrustal Level III, where it was intruded by cordierite-bearing granites during the Middle/Late Ordovician and its host-rock was locally affected by high temperature-low pressure HT/LP metamorphism at 8-10 km depth. Level III was eventually intruded by Early Carboniferous granites after long-term slow exhumation to 6-7 km depth. Early/Middle Ordovician exhumation of Level II to Level III (Exhumation Period I,0.25-0.78 mm/yr) was faster than exhumation of Level III from the Middle/Late Ordovician to the Lower Carboniferous (Exhumation Period II, 0.01-0.09 mm/yr). Slow exhumation rates and the lack of regional evidence of tectonic exhumation suggest that erosion was the main exhumation mechanism of the Famatinian Belt. Widespread slow exhumation associated with crustal thickening under a HT regime suggests that the Famatinian Belt represents the middle crust of an ancient Altiplano-Puna-like orogen. This thermally weakened over-thickened Famatinian crust was slowly exhumed mainly by erosion during similar to 180 Myr. (C) 2010 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Evaluation of petrogenetic models for intermediate and silicic plutonic rocks from the Sierra de Valle Fertil-La Huerta, Argentina: Petrologic constraints on the origin of igneous rocks in the Ordovician Famatinian-Puna paleoarc

The whole Valle Fertil-La Huerta section appears as a calc-alkaline plutonic suite typical of a destructive plate margin. New Sr and Nd isotopic whole-rock data and published whole-rock geochemistry suggest that the less-evolved intermediate (dioritic) rocks can be derived by magmatic differentiation, mainly by hornblende + plagioclase +/- Fe-Ti oxide fractional crystallization, from mafic (gabbroic) igneous precursors. Closed-system differentiation, however, cannot produce the typical intermediate (tonalitic) and silicic (granodioritic) plutonic rocks, which requires a preponderant contribution of crustal components. Intermediate and silicic plutonic rocks from Valle Fertil-La Huerta section have formed in a plate subduction setting where the thermal and material input of mantle-derived magmas promoted fusion of fertile metasedimentary rocks and favored mixing of gabbroic or dioritic magmas with crustal granitic melts. Magma mixing is observable in the field and evident in variations of chemical elemental parameters and isotopic ratios, revealing that hybridization coupled with fractionation of magmas took place in the crust. Consideration of the whole-rock geochemical and isotopic data in the context of the Famatinian-Puna magmatic belt as a whole demonstrates that the petrologic model postulated for the Sierra Valle Fertil-La Huerta section has the potential to explain the generation of plutonic and volcanic rocks across the Early Ordovician paleoarc from central and northwestern Argentina. As the petrologic model does not require the intervention of old Precambrian continental crust, the nature of the basement on which thick accretionary turbiditic sequences were deposited remains a puzzling aspect. Discussion in this paper provides insights into the nature of magmatic source rocks and mechanisms of magma generation in Cordilleran-type volcano-plutonic arcs of destructive plate margins. (C) 2010 Elsevier Ltd. All rights reserved.

Challenges and opportunities for knowledge organization at the intersection with information technologies

In this paper we study the intersection of Knowledge Organization with Information Technologies and the challenges and opportunities for Knowledge Organization experts that, in our view, are important to be studied and for them to be aware of. We start by giving some definitions necessary for providing the context for our work. Then we review the history of the Web, beginning with the Internet and continuing with the World Wide Web, the Semantic Web, problems of Artificial Intelligence, Web 2.0, and Linked Data. Finally, we conclude our paper with IT applications for Knowledge Organization in libraries, such as FRBR, BIBFRAME, and several OCLC initiatives, as well as with some of the challenges and opportunities in which Knowledge Organization experts and researchers might play a key role in relation to the Semantic Web.

Iheringichthys syi (Siluriformes: Pimelodidae), a new pimelodid species from upper Paraná basin, Brazil

We describe a new species of pimelodid catfish of the genus Iheringichthys from the upper Paraná basin, Brazil. Iheringichthys syi n. sp. is distinguished by the comparatively fine serration along the anterior margin of the pectoral-fin spine, an adpressed dorsal-fin remote from the adipose-fin origin, a large eye (23.2-31.2% of head length), narrow interorbital (16.2-23.0% of head length), long snout (42.0-51.0% of head length), long postorbital length (30.6-34.0% of head length), low adipose fin (4.8-7.8% of standard length), eye diameter 97.0-140.0% of interorbital length, and body with numerous, small dots irregularly scattered on flanks, especially marked on anterior half of flank.

Nested central volcanism related to rift development and giant landsliding in oceanic islands

Centro Superior de Investigaciones Científicas, Museo Nacional de Ciencias Naturales, Estación Volcanológica de Canarias

El diseño y el imperativo ecológico

La degradación del medio ambiente surge en las sociedades desarrolladas en un contexto de plena industrialización; en los países no desarrollados, sin embargo, aparece en un contexto de incipiente o nula industrialización. Dado que a inicios de los '70 se esperaba que los países no desarrollados entraran en un proceso acelerado de crecimiento, los problemas ambientales derivados de la falta de desarrollo fueron relegados dentro del debate mundial. El diseño no escapó a esta tendencia, adoptando como propios problemas de otras sociedades. En el presente trabajo se hace una revisión de la problemática ambiental implícita en el concepto de Ecodiseño al tiempo que se brindan nuevos elementos de análisis para una interpretación desde el diseño en la periferia.