The ice-vapor interface and the melting point of ice I(h) for the polarizable POL3 water model

We use molecular dynamics simulations to determine the melting point of ice I(h) for the polarizable POL3 water force field (Dang, L. X. J. Chem. Phys.1992, 97, 2659). Simulations are performed on a slab of ice I(h) with two free surfaces at several different temperatures. The analysis of the time evolution of the total energy in the course of the simulations at the set of temperatures yields the melting point of the POL3 model to be T(m) = 180 ± 10 K. Moreover, the results of the simulations show that the degree of hydrogen-bond disorder occurring in the bulk of POL3 ice is larger (at the corresponding degree of undercooling) than in ice modeled by nonpolarizable water models. These results demonstrate that the POL3 water force field is rather a poor model for studying ice and ice-liquid or ice-vapor interfaces. While a number of polarizable water models have been developed over the past years, little is known about their performance in simulations of supercooled water and ice. This study thus highlights the need for testing of the existing polarizable water models over a broad range of temperatures, pressures, and phases, and developing a new polarizable water force field, reliable over larger areas of the phase diagram.     

Tip- or electron beam-induced surface polymerization

Control on the formation of a two-dimensional polymer could be achieved in two different ways. Manipulation with the tip of a scanning tunneling microscope allowed for assigning the localization of the polymerization reaction. Additionally, electron irradiation could accelerate greatly the reaction kinetics.     

An easily accessible Re-based catalyst for the selective conversion of methanol: evidence for an unprecedented active site structure through combined operando techniques

Heterogeneous Re/SiO(2) catalysts prepared using a one pot sol-gel synthesis were found to display high activity in the direct, selective methanol conversion to methylal, which is correlated to an unprecedented rhenium oxide structure.     

Protonation of the oxygen axial ligand in galactose oxidase model compounds as seen with high resolution X-ray emission experiments and FEFF simulations

X-ray Emission Spectroscopy (XES) crossover peaks were shown to be sensitive to the protonation state of solvent molecules in the Zn protein carbonic anhydrase and its model compounds. Here we extend such studies to galactose oxidase models i.e. Cu(ii) open d-shell systems, illustrating that XES combined with FEFF8 simulations reflect changes in the protonation state of the phenolate ligand for the copper center.     

Chemical composition of the essential oil from Corsican Mentha aquatica--combined analysis by GC(RI), GC-MS and 13C NMR spectroscopy

The essential oil (EO) of M. aquatica L. growing wild in Corsica was isolated by dry vapor distillation and submitted to combined analysis by column chromatography over silica gel, GC(RI), GC-MS and 13C NMR spectroscopy. The composition was dominated byoxygenated monoterpenes and characterized by the occurrence of menthofuran (50.7%) as the major component. In parallel, seven laboratory-distilled oil samples isolated from individual plants collected in Corsica were analyzed by GC(RI) and 13C NMR spectroscopy. Onlyquantitative differences were observed between the samples. Beside the usual terpenes, various p-menthane lactones (mintlactone, isomintlactone, hydroxymintlactone, menthofurolactone and epimenthofurolactone) have been identified in all the oil samples.     

Approximation by Conic Splines

We show that the complexity of a parabolic or conic spline approximating a sufficiently smooth curve with non-vanishing curvature to within Hausdorff distance ɛ is c ₁ɛ^−1/4 + O(1), if the spline consists of parabolic arcs, and c ₂ɛ^−1/5 + O(1), if it is composed of general conic arcs of varying type. The constants c ₁ and c ₂ are expressed in the Euclidean and affine curvature of the curve. We also show that the Hausdorff distance between a curve and an optimal conic arc tangent at its endpoints is increasing with its arc length, provided the affine curvature along the arc is monotone. This property yields a simple bisection algorithm for the computation of an optimal parabolic or conic spline. The research of SG and GV was partially supported by grant 6413 of the European Commission to the IST-2002 FET-Open project Algorithms for Complex Shapes in the Sixth Framework Program.     

Feuilletages holomorphes locaux et analyticité partielle d'applications C ∞

 Let f : M → M′ be a smooth CR mapping between a generic real analytic submanifold M ⊂ ℂ ⁿ , n > 1, and a real analytic subset M′ ⊂ ℂ ^n′ . We prove that if M is minimal and if M′ does not contain any complex curves, then f is analytic on a dense open subset of M. More generally, we establish an upper estimate of the partial analyticity of f, which depends on the maximal dimension of local holomorphic foliations contained in M ^′ . Received: 7 August 2001 Mathematics Subject Classification (2000): 32V25, 32V40, 32H99     

Corniculoside,a New Biosidic Ester Secoiridoid from Halenia corniculata

Chemical screening of the secondary metabolites from Halenia corniculata L. (CORNAZ ), by LC/UV,LC/TSP-MS (thermospray), and LC/ES-MS (electrospray) was used for the targeted isolation of corniculoside ( 1 ), a new biosidic ester secoiridoid. The structure was established as 7-β-[(E)-4′-O-(β-D -glucopyranosyl)caffeoyloxy]-sweroside by 1D- and 2D-NMR, LC/UV, LC/MS, and FAB-MS data, in combination with chemical reactions.