Diethyl 2-[cyano(toluene-4-sulfinyl)methylene]propanedioate and its Diels–Alder adduct with cyclopentadiene

The thermal Diels–Alder cyclo­additon reaction of diethyl 2-­[cyano­(toluene-4-sulfinyl)­methyl­ene]­propane­dioate, C₁₆H₁₇­NO₅S, with cyclo­penta­diene gave the pure racemates of two of the four possible diastereomers, with a complete π-facial selectivity and a high (80:20) endo/exo-sulfinyl selectivity. X-ray diffraction studies of diethyl 2-[cyano­(toluene-4-sulfinyl)­methyl­ene]­propane­dioate and the major isomer of the cyclo­addition product, namely diethyl 3-cyano-3-(toluene-4-sulfinyl)­bi­cyclo­[2.2.1]­hepta-5-ene-2,2-di­carboxyl­ate, C₂₁H₂₃­NO₅S, reveal that the conformation of the substituents on the acrylo­nitrile moiety produces both steric and electronic effects, which affect the stereoselectivity of the reaction.     

Adsorptive Stripping Voltammetric Determination of 2,4-Dichlorophenol by Laponite Modified Carbon Paste Electrode

A laponite modified carbon paste electrode was prepared, characterized and applied for the 2,4-dichlorophenol (2,4-DCP) voltammetric determination. It takes advantage of the ability of laponite to adsorb phenols, as well as of its availability and very low cost. Kinetic and equilibrium data for 2,4-DCP adsorption by laponite in aqueous dispersions demonstrated that the adsorption process obeyed a pseudo first order kinetic model and was consistent with the formation of adsorbed multilayers on a surface with heterogeneous pore distribution. The composite paste electrode exhibited a heterogeneous surface with 65 % increased surface area and 27 % enhanced catalytic activity compared to the unmodified one. The adsorptive stripping voltammetric determination of 2,4-DCP at an electrode with an optimized graphite:laponite ratio of 55 : 15 w% using a 3 min accumulation time at pH 5.5 was found to be suitable for its quantification in the linear concentration range extended up to 50 μmol L⁻¹ with a sensitivity of 0.56 μA L μmol⁻¹ and a LOD of 0.2 μmol L⁻¹ (S/N=3).The 2,4-DCP electrochemical response was not affected by the presence of some structurally similar phenols, like catechol and p-nitrophenol, while resorcinol, 2-chlorophenol, and 4-chlorophenol presented interferences. The results were validated by 2,4-DCP determination in spiked tap water.     

Resolving Atomic-Scale Defects in Conjugated Polymers On-Surfaces

Atomic scale defects significantly affect the mechanical, electronic, and optical properties of π-conjugated polymers. Here, isolated atomic-scale defects are deliberately introduced into a prototypical anthracene-ethynylene π-conjugated polymer, and its local density of states is carefully examined on the atomic scale to show how individual defects modify the inherent electronic and magnetic properties of this one-dimensional systems. Scanning tunneling and atomic force microscopy experiments, supplemented with density functional theory calculations, reveal the existence of a sharp electronic resonance at the Fermi energy around certain defects, which is associated with the formation of a local magnetic moment accompanied by substantial mitigation of the mobility of charge carriers. While defects in traditionally synthesized polymers lead to arbitrary conformations, the presented results clearly reflect the preferential formation of low dimensional defects at specific polymer sites, which may introduce the possibility of engineering macroscopic defects in surface-synthesized conjugated polymers.     

Curvature and conjugate points in Lorentz symmetric spaces

We give some relations between conjugate points and curvature in a locally symmetric Lorentzian manifold. In the compact case, we show that the sectional curvature of timelike planes is non positive, and the lightlike sectional curvature of null planes is non negative. We also compute the lightlike conjugate loci of Cahen–Wallach manifolds, which are an important family of symmetric Lorentzian spaces.     

A first principle study of the structural,vibrational and electronic properties of tetrathiafulvalene adsorbed on Ag(110) and Au(110) surfaces

We have studied the adsorption properties of a charge donor organic molecule, tetrathiafulvalene (TTF), on the (110) surfaces of silver and gold by means of the generalized gradient approach of the density functional theory using periodic slab models. This molecule is the core building block of a host of molecular materials exhibiting extremely reach phase diagrams with a variety of ground states. The interfaces formed with metallic surfaces have received only limited attention, despite of their relevance. We have determined the stable adsorption sites for two unit cells representing high and low coverage, which are determinant for the adsorption properties of TTF on the surface. The preferential chemisorption is via the direct interaction of sulfur atoms with the Ag or Au atoms on top sites. All adsorbed TTF are more stable than gas phase TTF. The simulation of the vibrational spectra has permitted us to find the fingerprints of these structures to characterize them on this surface. The donor nature of TTF induces charge transfer to the metallic surfaces. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Leucoxol,a new diterpenoid from acacia leucophloea. X-ray structure determination

From $\text{Acacia leucophloea}$ (Roxb.) Willd. (Mimosaceae) the new diterpenoid 11α, 16-epoxy-1β, 15$\text{R}$-dihydroxy-isopimar-8(14)-ene (leucoxol) has been isolated. Its structure was determined by X-ray diffraction analysis.     

1H and 13C NMR spectral assignments and conformational analysis of 14 19-nor-neoclerodane diterpenoids

Unambiguous and complete assignments of 1H and 13C NMR chemical shifts for 14 19-nor-neoclerodane diterpenoids, nine of them isolated from natural sources and five other synthetic derivatives, are presented. The assignments are based on 2D shift-correlated (1H,1H-COSY, 1H,13C-gHSQC and 1H,13C-gHMBC) and NOE experiments. The conformations of rings A and B of these compounds are supported by the 3J(H,H) values and they agree with the low-energy conformations obtained by semi-empirical calculations. Moreover, the data obtained in this work for 2-acetoxyteucvidin and a semisynthetic 18-aldehyde derivative indicate that the configuration at C-2 of the former and at C-10 of the latter must be reversed with respect to those reported previously.     

Structural and spectral assignment by two-dimensional NMR of two new derivatives of the abietane diterpenoid taxodione

Two new abietane derivatives were obtained by treatment of the diterpene taxodione with diazomethane. Their structures were determined by mass spectrometry and NMR studies, including one- and two-dimensional experiments.     

A new intermediate intercalate in superconducting sodium-doped hafnium nitride chloride

A new phase has been observed during the sodium intercalation of hafnium nitride chloride as intermediate between the host beta-HfNCl and the already reported Na(0.29)HfNCl with Tc of 24 K; the new intermediate shows interlayer spacings ranging from 9.48 to 9.67 A, corresponds to a second stage intercalate of HfNCl and is superconducting with a critical temperature of 20 K.     

Synthesis and Characterization of Ethylene/Propylene Copolymers in the Whole Composition Range

Summary: The incorporation of comonomer molecules in the backbone of a homopolymer can influence the final properties of the material, decreasing its crystallinity and the melting and glass transition temperatures, and increasing its impact resistance and transparency. In the present work, ten ethylene/propylene copolymers have been synthesized using a supported metallocene catalytic system covering the whole composition range. Any desired composition was obtained by controlling the feed composition during the reaction. These synthesized copolymers have been characterized by different techniques in order to study the effect of the comonomer incorporation onto their final properties. When the comonomer content is low, the behaviour of the copolymer is similar to that of the corresponding homopolymer. Nevertheless, if the comonomer content increases, the copolymer becomes more amorphous (low crystallization temperature and soft XRD signals) and easily deformable, reaching a behaviour close to that corresponding to an elastomeric material. In order to corroborate these results the samples have been characterized by TREF and GPC-MALS. TREF analysis showed that copolymers containing less than 10% and more than 80% of ethylene are semicrystalline, with elution temperatures typical of this kind of polymers. Molecular weights are higher for homopolymers and they decrease as the comonomer concentration increases, whereas the polydispersity index keeps almost constant at the expected value for this kind of samples.