In situ hydrogenation of terminal halogen in poly(methyl methacrylate) by ruthenium-catalyzed living radical polymerization: direct transformation of "polymerization catalyst" into "hydrogenation catalyst"

An in situ, selective, and quantitative hydrogenation of the terminal chlorine (alpha-haloester) in living PMMA-Cl into PMMA-H was achieved via direct transformation of a "polymerization catalyst" into a "hydrogenation catalyst" in the Ru(II)-catalyzed living radical polymerization, where the polymerization mixture of MMA was directly treated in situ with K2CO3 as a base and 2-propanol as a hydrogen donor. The reaction terminated the polymerization and, more importantly, the terminal chlorine was quantitatively hydrogenated, as confirmed by SEC, 1H NMR, and MALDI-TOF MS.     

A flow-based enzyme-linked immunosorbent assay on a polydimethylsiloxane microchip for the rapid determination of immunoglobulin A

A flow-based enzyme-linked immunosorbent assay (ELISA) on a polydimethylsiloxane (PDMS) microchip has been developed for the rapid determination of immunoglobulin A (IgA). The analytical principle of this integrated method is the same as the conventional sandwich-type ELISA. A primary antibody (anti-IgA) was adsorbed on the surface of a PDMS microchannel, and then an antigen (IgA) and a secondary antibody (anti-IgA HRP labeled) were reacted successively. The resulting antigen-antibody complex, fixed on the surface of the microchannel, was detected using Amplex^® Red and a fluorescent imaging system. The calibration curve of the IgA standard solution was linear in the range of 0-50 ng/mL at the flow rate of 10 μL/min. This flow rate corresponds to the reaction time of 4.8 s. Compared to the conventional assay on a 96-well microtiter plate, the present assay on the microchip dramatically shortened the reaction time necessary for the enzyme-substrate reaction from 30 min to 4.8 s, i.e., to 1/375. The amounts of the reagent and sample were also reduced to 1/100 compared to the 96-well microtiter plate.     

Chemical synthesis of homogeneous human glycosyl-interferon-β that exhibits potent antitumor activity in vivo

Chemical synthesis of homogeneous human glycoproteins exhibiting bioactivity in vivo has been a challenging task. In an effort to overcome this long-standing problem, we selected interferon-β and examined its synthesis. The 166 residue polypeptide chain of interferon-β was prepared by covalent condensation of two synthetic peptide segments and a glycosylated synthetic peptide bearing a complex-type glycan of biological origin. The peptides were covalently condensed by native chemical ligation. Selective desulfurization followed by deprotection of the two Cys(Acm) residues gave the target full-length polypeptide chain of interferon-β bearing either a complex-type sialyl biantennary oligosaccharide or its asialo form. Subsequent folding with concomitant formation of the native disulfide bond afforded correctly folded homogeneous glycosyl-interferon-β. The chemically synthesized sialyl interferon-β exhibited potent antitumor activity in vivo.     

Anthranilamide-protected vinylboronic acid: rational monomer design for improved polymerization/transformation ability providing access to conventionally inaccessible copolymers

We have studied several protecting groups for vinylboronic-acid derivatives as monomers in radical polymerizations with the objective to improve the polymerization ability and C–B bond-cleaving post-transformation performance. Anthranilamide (aam)-protected vinylboronic acid (VBaam) exhibited experimentally a relatively high polymerization activity, which was theoretically corroborated by density functional theory (DFT) calculations that revealed a peculiar effect of the interaction between the aam groups on the polymerization behavior. The VBaam units in the copolymers can subsequently be transformed into vinyl alcohols or into ethylene units through C–B-bond-cleaving side-chain replacement, which affords valuable copolymers such as poly(vinyl alcohol-co-styrene), poly(ethylene-co-styrene), and poly(ethylene-co-acrylate).

We designed a vinyl-boronic-acid protected by anthranilamide as a “transformable” monomer in radical polymerization to synthesize conventionally inaccessible copolymers, such as poly(vinyl alcohol-co-styrene) and poly(ethylene-co-acrylate).     

Second Harmonic Generation Measurements for Biomacromolecules: Celluloses

The molecular chain orientation of mercerized cellulose II was examined by optical second harmonic generation (SHG) measurements. The SHG intensities of several kinds of mercerized cellulose II were found to be much larger than those expected for a structural model with an antiparallel molecular chain orientation as proposed by X-ray studies. This result suggests that the orientation of mercerized cellulose II is parallel as suggested by molecular dynamics simulation. © 2004 The Optical Society of Japan     

Bayesian cooperative choice of strategies

This paper provides a formal framework within which to study cooperative behavior in the presence of incomplete information, and shows how far the known results in the static cooperative game theory can readily be applied to the proposed framework. The new concepts of Bayesian society, Bayesian strong equilibrium and Bayesian incentive compatible strong equilibrium are introduced and studied.     

Protic NNN and NCN Pincer‐Type Ruthenium Complexes Featuring (Trifluoromethyl)pyrazole Arms: Synthesis and Application to Catalytic Hydrogen Evolution from Formic Acid

NNN and NCN pincer‐type ruthenium(II) complexes featuring two protic pyrazol‐3‐yl arms with a trifluoromethyl (CF₃) group at the 5‐position were synthesized and structurally characterized to evaluate the impact of the substitution on the properties and catalysis. The increased Brønsted acidity by the highly electron‐withdrawing CF₃ pendants was demonstrated by protonation–deprotonation experiments. By contrast, the IR spectra of the carbonyl derivatives as well as the cyclic voltammogram indicated that the electron density of the ruthenium atom is negligibly influenced by the CF₃ group. Catalysis of these complexes in the decomposition of formic acid to dihydrogen and carbon dioxide was also examined. The NNN pincer‐type complex 1 a with the CF₃ group exhibited a higher catalytic activity than the tBu‐substituted analogue 1 b . In addition, the bis(CF₃‐pyrazolato) ammine derivative 4 catalyzed the reaction even in the absence of base additives.     

Saccharification and alcohol fermentation in starch solution of steam-exploded potato

Steam explosion pretreatment of potato for the efficient production of alcohol was experimentally studied. The amount of water-soluble starch increased with the increase of steam pressure, but the amounts of methanol-soluble material and Klason lignin remained insignificant, regardless of steam pressure. The potatoes exploded at high pressure were hydrolyzed into a low molecular liquid starch, and then easily converted into ethanol by simultaneous saccharification and fermentation using mixed microorganisms: an amylolytic microorganism,Aspergillus awamori, and a fermentation microorganism,Saccharomyces cerevisiae. The maximal ethanol concentration was 4.2 g/L in a batch culture at 15 g/L starch concentration, and 3.6 g/L in a continuous culture fed the same starch concentration. In the fed-batch culture, the maximal ethanol concentration increased more than twofold, compared to the batch culture.