Synthesis of functional polymers bearing pendant mono-and oligo-saccharide residues

The present paper focuses on (i) a new synthetic methodology to prepare vinyl ether-based synthetic glycoconjugates (glycopolymers) with well-controlled structure, and on (ii) the application of glycopolymers bearing modified disaccharide residue as thermotropic liquid crystalline (LC) materials. Two vinyl ethers (VEs) having pendant glucose residues with their hydroxyl functions protected by acetyl and isopropylidene groups, respectively, were found to undergo living cationic polymerization initiated by a HI/ZnI2-initiating system. Deprotection of the resultant monodisperse polymers led to water-soluble polymers bearing a pendant glucose residue. Sequential living block copolymerization of glucose-containing VE and alkyl VE, and subsequent deprotection afforded an amphiphilic block copolymer of well-controlled structure. Transmission electron microscopic observation of its cast thin film revealed microphase-separated surface morphologies that varied with varying segment composition ratio. A VE substituted with a heptadecanoated cellobiose pendant was independently prepared, and was cationically polymerized to give a thermotropic LC polymer. From X-ray analysis, the mesophase was assigned to a discotic columnar in type, in which each main chain, extended due to the steric repulsion between the neighboring bulky pendants, was surrounded by three discotic columns.     

Conservative quantum computing

The Wigner-Araki-Yanase theorem shows that conservation laws limit the accuracy of measurement. Here, we generalize the argument to show that conservation laws limit the accuracy of quantum logic operations. A rigorous lower bound is obtained of the error probability of any physical realization of the controlled-NOT gate under the constraint that the computational basis is represented by a component of spin, and that physical implementations obey the angular momentum conservation law. The lower bound is shown to be inversely proportional to the number of ancilla qubits or the strength of the external control field.     

Conservation laws, uncertainty relations, and quantum limits of measurements

The uncertainty relation between the noise operator and the conserved quantity leads to a bound on the accuracy of general measurements. The bound extends the assertion by Wigner, Araki, and Yanase that conservation laws limit the accuracy of "repeatable," or "nondisturbing," measurements to general measurements, and improves the one previously obtained by Yanase for spin measurements. The bound represents an obstacle to making a small quantum computer.     

High-speed recovery of germanium in a convection-aided mode using functional porous hollow-fiber membranes

A porous hollow-fiber membrane capable of recovery of germanium from a liquid stream was prepared by radiation-induced graft polymerization of an epoxy-group-containing vinyl monomer, glycidyl methacrylate, and subsequent functionalization with 2,2'-iminodiethanol, di-2-propanolamine, N-methylglucamine, and 3-amino-1,2-propanediol. The functional group density was as high as 1.4 mol per kg of the resultant hollow fiber. The polymer chains containing functional groups surrounding the pores enabled a high-speed recovery of germanium during permeation of a germanium oxide (GeO2) solution through the pores of the hollow fiber. Because of a negligible diffusional mass-transfer resistance, germanium concentration changes with the effluent volume, i.e., breakthrough curves, overlapped irrespective of the residence time of the solution, which ranged from 0.37 to 3.7 s across the hollow fiber. After repeated use of adsorption and elution, the adsorption capacity did not deteriorate.     

Highly effective synthetic methods for substituted 2-arylbenzofurans using [3,3]-sigmatropic rearrangement: short syntheses of stemofuran a and eupomatenoid 6

A new and efficient synthesis of 2-arylbenzofurans has been achieved via a route involving acylation and subsequent [3,3]-sigmatropic rearrangement of oxime ethers. Its synthetic utility is demonstrated by a short synthesis of stemofuran A and eupomatenoid 6 in which no procedure for protection of the phenolic hydroxyl groups is needed. [reaction--see text]     

Palladium-indium iodide-mediated allylation and propargylation of glyoxylic oxime ether and hydrazone: the role of water in directing the diastereoselective allylation

Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl.     

Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides

1,2-Diphenyl-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene was used as an additive ligand in copper-catalysed amination reactions of halobenzenes with amines in the presence of base to afford the corresponding secondary or tertiary amines in good to excellent yields.