Keratanase II-catalyzed synthesis of keratan sulfate oligomers by using sugar oxazolines as transition-state analogue substrate monomers: a novel insight into the enzymatic catalysis mechanism

Keratan sulfate (KS) oligomers with well-defined structures were synthesized by keratanase II (KSase II)-catalyzed transglycosylation. N-Acetyllactosamine [Galbeta(1-->4)GlcNAc; LacNAc] oxazoline derivatives with sulfate groups at the C-6 (1 a) and both the C-6 and the C-6' (1 b) were prepared as transition-state analogue substrate monomers for KSase II. Monomer 1 a was effectively oligomerized by the enzyme under weak alkaline conditions, to give alternating 6-sulfated KS oligomers (2 a) in good yields, and with total control of regioselectivity and stereochemistry. KSase II also recognized 1 b, which provided fully 6-sulfated KS oligomers (2 b) in good yields under similar conditions. Nonsulfated LacNAc oxazoline was difficult to oligomerize enzymatically. These results imply that the catalysis mechanism of KSase II involves a sugar oxazolinium ion that requires the 6-sulfate group in the GlcNAc residue not only in hydrolysis of KS chains, but also in oligomerization of oxazoline monomers. This is the first report of KSase II-catalyzed transglycosylation to form beta(1-->3)-glycosidic bond through a substrate-assisted mechanism.     

Preparation of Pd-Ag thin films by the RF-sputtering method and its catalysis for oxidative dehydrogenation of allylic alcohols

Pd-Ag thin films were prepared by the RF sputtering method on a Pyrex glass substrate to give monophasic alloys. Oxidation of allylic alcohols using the films gave selectively , -unsaturated carbonyl compounds in the presence of O₂; highly dispersed Pd species on Ag, Pd₇Ag₉₃ showed 95% selectivity for acrolein from allyl alcohol at 473 K.     

Interfacial tension of demixed polymer solutions near the critical temperature: polystyrene + methylcyclohexane

Interfacial tension between demixed solutions of polystyrene + methylcyclohexane has been measured near the critical temperature as a function of temperature using polystyrenes with molecular weights 9000 ～ 1.26 × 10⁶. The critical exponent for the interfacial tension was determined to be about 1.30 for the lower molecular weight systems. However, for higher molecular weights the exponent could not be obtained because the system departed from critical behaviour. Magnitudes of the interfacial tension were proportional to about N^?0.44, where N is the polymerization index. Experimental results were compared with the recently-proposed theories and found to be in qualitative agreement. The tricritical theory of polymer solutions was also compared with the experimental results.     

DNA recognition by a {beta}-sheet

DNA recognition by a ß-sheet is discussed in the lightof crystal structures of the MetJ and Arc repressors. The DNAbinding geometry of a ß-sheet can be understood interms of (i) close fitting of the two surfaces and (ii) matchingof residue and base positions. A ß-sheet is not entirelyflat but has a curvature. A ß-sheet of the Met-Arcfamily faces the DNA major groove with its convex surface; thelocal DNA major groove is deepest at the centre. The ß-sheetfollows 6 bp; every two residues face the DNA and the firstand fifth residues, which are separated by 13.2 Å, bind,respectively, to the third and sixth bases, which are separatedby 13.5 Å, on the same DNA strand.     

Chemical analysis and acetylcholinesterase inhibitory effect of anthocyanin-rich red leaf tea (cv. Sunrouge)

BACKGROUND: The purpose of this study was to evaluate the effects of leaf order or crop season on anthocyanins and other chemicals in the anthocyanin‐rich tea cultivar ‘Sunrouge’ (Camellia sinensis x C. taliensis) by using high‐performance liquid chromatography, and to study the effect of ‘Sunrouge’ extract on acetylcholinesterase (AChE) activity in human neuroblastoma SK‐N‐SH cells. RESULTS: The total anthocyanin content was higher in the third (3.09 mg g^?1) than in the second (2.24 mg g^?1) or first crop season (1.79 mg g^?1). The amount of anthocyanins contained in the stem was high (1.61 mg g^?1). In the third crop season, the concentrations of delphinidin‐3‐O‐β‐D ‐(6‐(E)‐p‐coumaroyl)galactopyranoside (DCGa), cyanidin‐3‐O‐β‐D ‐(6‐(E)‐p‐coumaroyl)galactopyranoside, delphinidin‐3‐O‐β‐D ‐galactopyranoside, delphinidin‐3‐O‐β‐D ‐(6‐O‐(Z)‐p‐coumaroyl)galactopyranoside, cyanidin‐3‐O‐β‐D ‐galactoside, and delphinidin‐3‐O‐β‐D ‐glucoside were 1.57 mg g^?1, 0.52 mg g^?1, 0.40 mg g^?1, 0.22 mg g^?1, 0.14 mg g^?1, and 0.11 mg g^?1, respectively. DCGa accounted for about 50% of the anthocyanins present. The suppressive effect of ‘Sunrouge’ water extract on AChE activity in human neuroblastoma SK‐N‐SH cells was the strongest among the three tea cultivars (‘Sunrouge’, ‘Yabukita’ and ‘Benifuuki’). CONCLUSION: These results suggested that ‘Sunrouge’ might protect humans from humans from AChE‐related diseases by suppressing AChE activity. To obtain sufficient amounts of anthocyanins, catechins and/or caffeine for a functional food material, ‘Sunrouge’ from the third crop season should be used. Copyright © 2012 Society of Chemical Industry     

Safety evaluation of rechargeable cells with lithium metal anodes and amorphous V2O5 cathodes

Rechargeable cells with lithium metal anodes have a very large theoretical energy density and are a promising cell system. However, rechargeable lithium metal cells are not yet currently commercially available. One of the biggest problems with the cells is the poor safety aspect resulting from the high chemical reactivity of lithium. We have been studying a cell system consisting of an amorphous (a-)V2O5P2O5 (95:5 in molar ratio) cathode, a lithium (Li) metal anode and an organic electrolyte in fabricating an AA-size prototype. In this paper, we report recent progress on our rechargeable lithium metal cell focusing on its safety.     

Direct Observation of Internal Structure in Spray-Dried Alumina Granules

The internal structure of spray-dried alumina granules was characterized by optical microscopy by immersing them in a liquid having a refractive index close to that of alumina. This method provides a unique technique for the detailed analysis of the internal structure of spray-dried granules.     

Reaction and diffusion of reactive disperse dye in nylon 6

The diffusion of a reactive disperse dye with a vinylsulfonyl group accompanied by simultaneous reaction with the amino end groups in nylon 6 was examined by the method of cylindrical film roll at 70°C and pH 2.2–8.0. The experimental diffusion profiles of the active and fixed species of the dye in nylon 6 were confirmed to be described by the diffusion equation accompanied by the chemical reaction with substrate taking the limited amount of the end groups into account, where the active species of dye were assumed to react only with the free base of amino end groups. The completion of the reaction with the amino end groups was observed in the first layer from the surface at pH 6.0–8.0. The value of diffusion coefficient was constant (8.0 × 10^?10 cm²/s) at all the pH's. The product of the second-order rate constant, k₂, of reaction of the dye and the dissociation constant, K_a, of the amino end groups was constant (k₂K_a = 4.0 × 10^?9 s^?1) at pH 2.2–8.0. The k₂ values of the reaction with various substrates for vinylsulfonyl and monochlorotriazinyl-reactive dyes were compared and the practical dyeing conditions were discussed.     

Mechanical properties of DLC films prepared inside of micro-holes by pulse plasma CVD

Diamond-like carbon (DLC) films are metastable amorphous carbon materials with superior tribological characteristics. In order to improve wear resistance of micro-extrusion dies with numerous imperceptible holes, DLC films were deposited on the inner wall surface of model dies with holes of 2 and 0.9 mm in diameter, and 20 mm in depth by using pulse plasma CVD method. This paper will discuss how argon gas, deposition pressure and time affect the characteristics of films deposited on the inner wall surface of dies. This micro-coating method can be applied widely for inner wall surface treatment of components with thin holes.     

Glyme-based nonaqueous electrolytes for rechargeable lithium cells

Poly(ethylene glycol)dimethyl ethers [(CH₃O(CH₂CH₂O)_nCH₃, n = 1, 2, 3, and 4)] are generally known as “glymes”. This study examines the conductivity, lithium ion solvation state and charge-discharge cycling efficiency of lithium metal anodes in glyme-based electrolytes for rechargeable lithium cells. 1 M (M: mol l⁻¹) LiPF₆ was used as the solute. The properties of the glymes were investigated by using a ternary mixed solvent consisting of n-glyme, ethylene carbonate (EC) and methylethylcarbonate (MEC). This was because the solubility of LiPF₆ is far less than 1 M in an n-glyme single solvent. The glyme solutions exhibited higher conductivity and higher lithium cycling efficiency than EC/MEC. The conductivity tended to increase with decreases in ethylene oxide chain number (n) and solution viscosity. The decrease in the solution viscosity resulted from the change in the lithium ion solvation structure that occurred when a glyme was added to EC/MEC. The selective solvation of the glyme with respect to lithium ions was clearly demonstrated by -NMR measurements. The lithium cycling efficiency value depended on the charge-discharge current (I_ps). When n increased there was an increase in lithium cycling efficiency at a low I_ps and a decrease in the reduction potential of the glymes. When the conductivities including those at low temperature (below 0 °C), and charge-discharge cycling at a high current are taken into account, di- or tri-glyme is superior to the other glymes tested here.