AG codes from vector bundles

We discuss the properties of algebraic-geometric codes defined by a vector bundle on a curve X over a finite field. We investigate the correction capacities of the codes defined from vector bundles constructed by means of finite coverings of X.     

D abstraction by H at a D-saturated Ru(0 0 1) surface

D abstraction (ABS) by H at Ru(0 0 1) surfaces initially saturated with D adatoms has been investigated using in situ mass spectrometry. HD and D₂ desorption rates are measured at various surface temperatures T as a function of H exposure time. Yield of D₂ desorption increases with T, while that of HD is little affected. Analyzing the measured rate curves, HD and D₂ desorption orders are evaluated to be 1.7 ± 0.1 and 2.5 ± 0.1, respectively, with respect to D coverage θ_D. To pursue the origin of the derived non-integral reaction orders the rate curves are further analyzed with the rate equations constructed to involve several ABS channels. Consequently, we find that the HD desorption is mainly governed by a second-order rate law in θ_D rather than the conventional hot atom-mediated ABS reaction even when it is corrected to include an isotope effect on ABS. We argue that such second-order ABS kinetics becomes important when the H atoms in excited state of chemisorption have energetically relaxed to some extent, and thereby tend to reside at, e.g. hexagonal closed packed hollow sites, interacting with nearby adatoms. On the other hand, the D₂ rate curves can be fit with third-order kinetics, consistent with the Langmuir-Hinshelwood mechanism in a super-saturation state. The isotope effect plays an essential role in the ABS reaction of D abstraction by H which competes with H abstraction by H as D adatoms are replaced by H atoms.     

Fluorescent detection for cyclic and acyclic alcohol guests by naphthalene-appended amino-beta-cyclodextrins

Spectroscopic and thermodynamic investigations on complexation of naphthalene-appended amino-beta-cyclodextrins 1 and 2 with cyclic alcohols (cyclohexanol and cycloheptanol) and acyclic alcohols (1-pentanol, 2-pentanol, 1-hexanol, and 1-heptanol) have been carried out. Host 1 exhibits a drastic fluorescent enhanced-signal change in the presence of alcohol guests in aqueous solution. [structure: see text]     

Rupture and regeneration of colloidal crystals as studied by two-dimensional ultra-small-angle X-ray scattering

The structure of colloidal crystals of silica particles in water was studied by using the two-dimensional (2D) ultra-small-angle X-ray scattering (USAXS) technique. By violent shaking of the dispersion, large (body-centered cubic, bcc) crystals were broken into microcrystals while the lattice structure and lattice constant were preserved. The 2D-USAXS profiles revealed that the [111] direction of bcc microcrystals was parallel to the capillary axis and their orientational distribution with respect to the capillary axis was random. While a prepeak was observed in the one-dimensional USAXS measurements, no such peak was detected by the 2D-USAXS technique. The prepeak was concluded to be due to {110} being rotated by 54.7 degrees (the angle between [001] and [111]) from the capillary axis. The diffraction from the plane was out of the horizontal plane and was observed at a lower angle as a prepeak by detector scanning in the horizontal direction.     

Thermotropic Liquid Crystalline Polymers Having Five‐Membered Heterocycles as Mesogens, 7. Synthesis and Photoluminescent Properties of Semi‐Rigid Thermotropic Liquid Crystalline Polyesters Based on a Quaterphenyl Analog of 2,2′‐Bis(1,3,4‐thiadiazole)

New semi‐rigid thermotropic liquid crystalline (LC) polyesters composed of a quaterphenyl analogue of 2,2′‐bis(1,3,4‐thiadiazole) were synthesized by high‐temperature solution polycondensation of a dioxydiundecanol derivative of 5,5′‐diphenyl‐2,2′‐bis(1,3,4‐thiadiazole) with four diacyl chlorides, whose structures were characterized by FT‐IR and ¹³C NMR spectroscopy, as well as elemental analysis. Differential scanning calorimetry (DSC) measurements and texture observations using polarizing microscopy displayed that all the polyesters form stable enantiotropic smectic and/or nematic LC phases. Solution and solid state absorption and fluorescence spectra indicated that the polyesters show absorption maxima arising from the 2,2′‐bis(1,3,4‐thiadiazole) moiety and emit bluish green light, the Stokes shifts being 129 nm in solution and 60–64 nm in the solid state. Band gap energies of the polyesters calculated from the solid state absorption spectra were 2.67–2.82 eV.     

In situ ATR-IR investigation of L-lysine adsorption on montmorillonite

The adsorption behavior of lysine on montmorillonite in aqueous solution was investigated by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy. To distinguish the protonation states of α-amino group, side-chain amino group and carboxyl group in lysine structure using ATR-IR spectra (i.e., NH₂ versus and COO⁻ versus COOH), pH-induced spectral changes of dissolved lysine were firstly measured and correlated with the thermodynamically calculated dissociation states of lysine (di-cationic, cationic, zwitterionic and anionic states). The obtained result was applied to interpret the ATR-IR spectra of lysine adsorbed on montmorillonite. We found that the adsorbed lysine was dominantly present as cationic state over the whole range of tested pH (pH = 4.9–9.7). This indicates that the adsorption is mainly driven by electrostatic interaction between the negatively charged montmorillonite surface and positively charged cationic lysine. We also found that lysine interacts with montmorillonite surface through the protonated side-chain amino group. This result suggests that lysine has a preferred vertical orientation, with the side-chain amino group pointing toward the surface.     

Chiral Dinuclear EuIII,TbIII, and YIII Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)₄, was synthesized to prepare C₂ dinuclear M(hfa)₃ complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)₃ complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)₂, were also prepared, and comparison of their photophysical properties for the Eu^III complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)₃ units through intramolecular π-π stacking constraint in the dinuclear system.     

Circularly Polarized Luminescence and Circular Dichroism of Bichromophoric Difluoroboron-β-diketonates: Inversion and Enhanced Chirality Based on Spatial Arrangements and Self-Assembly

We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher g_abs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the g_lum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the g_lum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores.     

A temperature study on critical micellization concentration (CMC), solubility, and degree of counterion binding of α-sulfonatomyristic acid methyl ester in water by electroconductivity measurements

 For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, critical micellization concentration (CMC), solubility and degree of counterion binding (β) were determined by means of electrocon-ductivity measurements at different temperatures (at every 5 °C) ranging from 15 to 50 °C. The phase diagram of 14SFNa in pure water was constructed from the CMC- and solubility-temperature data, in which the Krafft temperature (critical solution temperature) was found around 0 °C. The changes in the Gibbs energy, ΔG ⁰ _m, enthalpy, ΔH ⁰ _m, and entropy, ΔS ⁰ _m, upon micelle formation as a function of temperature were evaluated taking βvalues into calculation. Received: 28 August 1996 Accepted: 5 November 1996     

Exploiting Transient Radical Cations as Brønsted Acids for Allylic C–H Heteroarylation of Enol Silyl Ethers

Intermediary radical cations, generated through single-electron oxidation of enol silyl ethers by excited Ir-based photocatalysts, can be exploited as Brønsted acids for the activation of heteroarylcyanides. This strategy enables the direct allylic C−H heteroarylation of enol silyl ethers under visible-light irradiation.