Preparation and Characterization of Branched β-Cyclodextrins Having Manno-Oligosaccharide Side Chains Derived from Yeast Mannan and Study of Their Functions

Branched -cyclodextrins (-CDs) having manno-oligosaccharide side chains were investigated. Three kinds of monobranched -CDs and five kinds of dibranched -CDs were chemically synthesized using the trichloroacetimidate method. Their structures were analyzed by HPLC, MS, and NMR spectroscopies. The specific interaction between those compounds and mannose-binding lectins (Concanavalin A and Pisum sativum agglutinin) was investigated by inhibition tests of hemagglutinating activity and by using an optical biosensor of the IAsys apparatus with a resonant mirror detector. The results showed that all branched -CDs interactedwith lectins. The binding affinity was 6¹,6⁴-(Man₃)₂- 6¹,6⁴-(Man₂)₂- > 6¹,6⁴-(Man₄)₂--CD when the derivatives were compared on the basis of side chain length and 6¹,6³- 6¹,6⁴- > 6¹,6²-(Man₂)₂--CD when compared on the basis of side chain position.     

Planarity of acetamides,thioacetamides, and selenoacetamides: Crystal structure of N,N‐dimethylselenoacetamide

The planarity of acetamides 1a–3a , thioacetamides 4a–6a , and selenoacetamides 7a–9a , R¹R²NC(=E)CH₃ where E = O, S, Se, and R¹, R² = H or CH₃, was investigated using theoretical calculations at the density functional theory (DFT) level. The calculations showed that the methyl substitution on nitrogen and the change from the amide moiety (NCO) to NCS or NCSe group increased the double bond character of the N C bond. In other words, the planarity of these compounds ( 1a–9a ) increases in the order NH₂ < NHCH₃ < N(CH₃)₂ and O < S < Se. The calculations of bending energy suggest that the planar geometry represents the lowest energy conformation for all compounds investigated in this work. N,N‐Dimethyl‐selenoacetamide ( 9a ), (CH₃)₂NC(Se) CH₃, has the largest bending energy of 10.37 kcal/mol, which suggests that it possesses the greatest planarity among the compounds 1a–9a . However, the solid phase molecular structure of 9a was found to be slightly nonplanar by X‐ray crystallography. The slight nonplanarity observed experimentally is very likely the consequence of intermolecular interactions arising within the crystal packing. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:380–386, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10056     

Preparation and Characterization of 61,6n-DI-O-(α-D-Galactopyranosyl)Cyclomaltooctaoses

ABSTRACT

Four positional isomers of 6¹,6ⁿ-di-O-(D-galactopyranosyl)cyclomaltooctaoses (cG₈s, γ-cyclodextrins) (n = 2?5) were chemically synthesized using the trichloroacetimidate method. The desired compounds having two α-(1→6)-linkages were isolated from a mixture of configurational isomers by HPLC, and their structures were confirmed by ¹³C NMR spectroscopy and FAB-high resolution mass spectra (HRMS). The elution behavior of their four positional isomers on an ODS column by HPLC is discussed.     

TiO2-based superhydrophobic-superhydrophilic patterns: Fabrication via an ink-jet technique and application in offset printing

A superhydrophobic-superhydrophilic pattern was prepared on an anodized Al plate by a new fabrication process. The process consists of five key steps: (1) TiO₂ coating of the plate, (2) surface modification with self-assembled monolayers (SAMs), (3) formation of aqueous UV light-resistant ink patterns by an ink-jet technique, (4) photocatalytic decomposition of SAMs and surface conversion to the superhydrophilic state and (5) removal of the aqueous ink patterns by water washing. It is particularly noteworthy that the wettability pattern can be quickly formed on the plate, without the use of a photomask. The fabricated superhydrophobic-superhydrophilic pattern is shown to be applicable to offset printing.     

Degradation of fenitrothion by ultrasound/ferrioxalate/UV system

The sonochemical photodegradation of fenitrothion, which is one of phosphorothiate insecticides, was carried out in the presence of Fe(III) and oxalate. The degradation rate was strongly influenced by initial concentrations of Fe(III) and oxalate. An initial fenitrothion concentration of 10 mg L⁻¹ was completely degraded after 30 min at pH 6 under the optimum conditions. Therefore, the photo-Fenton reaction combined with sonication in the presence of oxalate was available around neutral pH. The decrease of TOC as a result of mineralization of fenitrothion was observed during ultrasound (US)/ferrioxalate/UV process. In addition, the formations of nitrite and sulfate ions as end-products were observed during this degradation system. The decomposition of fenitrothion gave two kinds of intermediate products. The degradation mechanism of fenitrothion was proposed on the base of the evidence of the identified intermediates. Based on these results, US/ferrioxalate/UV system could be useful technology for the treatment of wastewater containing fenitrothion.     

Crystallization behavior of bisphenol A polycarbonate with a simple vacuum process

The crystallization behavior of an amorphous polymer, bisphenol A polycarbonate (BAPC), was evaluated. BAPC was crystallized by exposure to diphenylpropane, a component of BAPC, by vapor transportation methods. Furthermore, the surface of BAPC was also crystallized by this method. Crystallized BAPC was employed as a novel simple storage medium, and bit patterns were recorded on its surface by laser irradiation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2307–2313, 2005     

Orientation of Rod-Shape Molecule, 2,2′-Bis[4-(Trifluoromethyl)Phenyl]-5,5′-Bithiazole in Films Deposited in a Vacuum on Oriented α-Sexithiophene Films

We demonstrated orientation control of n-type rod-shape, 2,2′-Bis[4-(trifluoromethyl)phenyl]-5,5′-bithiazole (BTMPB) molecules when deposited on the in-plane oriented polythiophene (PT) and α-sexithiophene (6T)/PT films in vacuum. The results showed that the π-π stacking direction of BTMPB molecules on the PT and 6T/PT films is perpendicular to the substrate plane. In addition, a molecular long axis of BTMPB oriented parallel to the friction direction of the PT. Moreover, in-plane orientation of BTMPB was more enhanced by in-plane oriented 6T molecules than in-plane oriented PT underneath. On the other hand, the molecular long axis of BTMPB deposited on the substrates stood on the substrates.     

Study of multipole contributions to the structure of water around ions in solution using the soft sticky dipole-quadrupole-octupole (SSDQO) model of water

The solvation of ions in the soft sticky dipole-quadrupole-octupole (SSDQO) model for liquid water is presented here. This new potential energy function for liquid water describes water-water interactions by a Lennard-Jones term plus a sticky potential consisting of an approximate moment expansion with point dipole, quadrupole, and octupole moments. The SSDQO potential energy function using the moments from extended simple point charge (SPC/E), TIP3P, or TIP5P reproduces the pair potential energy functions and radial distribution functions of the respective multipoint model but it is much faster than even the three-point models. Here, the solvation of ions in SSDQO water is studied using ion-water potential energy functions consisting of moment expansions up to the charge-quadrupole term, up to the charge-octupole term, and up to an approximate charge-hexadecapole term using the moments of SPC/E water. The radial distributions from Monte Carlo simulations show the best agreement with the results for ions in SPC/E water for the expansion up to the charge-hexadecapole term. Thus, the best results are obtained when the water-water and ion-water potentials are exact up to the 1r(4) term and also contain an approximate 1r(5) term. Overall, the simplicity, efficiency, and accuracy of the SSDQO potential make it potentially very useful for computer simulations of aqueous solvation.     

Reaction of ethyl 3-ethoxymethylene-2,4-dioxovalerate with monosubstituted hydrazines

Reactions of ethyl 3-ethoxymethylene-2,4-dioxovalerate (1) with phenyl- and methylhydrazines are described. While the reaction of 1 with phenylhydrazine gave a mixture of ethyl 4-acetyl-1-phenylpyrazole-5-carboxylate (4) and ethyl 5-methyl-1-phenylpyrazole-4-glyoxylate (5), 1 reacted with methylhydrazine to give ethyl 4-acetyl-1-methylpyrazole-3-carboxylate (14) as the sole product.