Properties of composite solid polymer electrolyte using hyperbranched polymer with ether-linkage

The cross-linked composite solid polymer electrolytes composed of poly(ethylene oxide), lithium salt (LiN(SO₂CF₃)₂), and a hyperbranched polymer whose repeating units were connected by ether-linkage (hyperbranched polymer (HBP)-2) were prepared, and their ionic conductivity, thermal properties, electrochemical stability, mechanical property, and chemical stability were investigated in comparison with the non-cross-linked or cross-linked composite solid polymer electrolytes using hyperbranched polymers whose repeating units were connected by ester-linkage (HBP-1a, 1b). The cross-linked composite solid polymer electrolyte using HBP-2 exhibited higher ionic conductivity than the non-cross-linked and cross-linked composite solid polymer electrolytes using HBP-1a and HBP-1b, respectively. The structure of the hyperbranched polymer did not have a significant effect on the thermal properties and electrochemical stability of the composite solid polymer electrolytes. The tensile strength of the cross-linked composite solid polymer electrolyte using HBP-2 was lower than that of the cross-linked composite solid polymer electrolyte using HBP-1b, but higher than that of the non-cross-linked composite solid polymer electrolyte using HBP-1a. The HBP-2 with ether-linkage showed higher chemical stability against alkaline hydrolysis compared with HBP-1a with ester-linkage.     

Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

High-throughput and high-resolution two dimensional mapping of pI and m/z using a microchip in a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer

We have developed a high-throughput, two-dimensional-mapping (isoelectric point [pI], mass-to-charge ratio [m/z]) method by combining a capillary isoelectric focusing chip sealed with removable resin tape and a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer. Sample proteins are separated in a meandering channel on the chip and immediately frozen. The tape is then removed and the proteins are freeze-dried. The freeze-drying maintains the separation state of the proteins and prevents movement of the sample solution, which can reduce pI resolution. A matrix solution is then applied and mass spectrometry is carried out by laser irradiation. The whole process takes less than 70 min, more than 10 times faster than with two-dimensional, polyacrylamide gel electrophoresis.     

Cationic starch derivatives as dynamic coating additives for protein analysis in capillary electrophoresis

Positively charged starch derivatives were used to modify the inner surface of fused-silica capillaries by addition to running buffer, which were subsequently employed in capillary electrophoresis (CE). Capillaries coated with the cationic starch derivatives were shown to generate a stable, reversed electroosmotic flow (EOF) in the investigated pH range of 3-9. The presented coating procedure was fast, based on a simple rinsing protocol where the polymer created a physically adsorbed, cationic polymer layer. Among the additives studied, a quaternary ammonium starch derivative showed a fast EOF mobility and effectively suppressed the adsorption of proteins. The intra- and inter-day reproducibility of the coating referring to the EOF mobility were satisfactory with relative standard deviation (RSD) of 0.27 and 1.67%, respectively. The coating enabled separation of some protein mixtures including basic proteins within l3 min with efficiencies up to 280,000 plates/m. In addition, this cationic starch derivative possessed a good solubility (about 100mg/mL), and it does not significantly contribute to the background adsorption in the UV region of 190-400 nm.     

A novel biosurfactant, 2-acyloxyethylphosphonate, isolated from waterblooms of Aphanizomenon flos-aquae

A novel biosurfactant, 2-acyloxyethylphosphonate, was isolated from waterblooms of Aphanizomenon flos-aquae. Its structure was elucidated by chemical degradation and HRFABMS, GC/EI-MS and 1D- and 2D-NMR spectral analyses. The surfactant contained one mole of 2-hydroxyethylphosphonate and one mole of fatty acid, with hexadecanoic acid accounting for 84.1% of the total fatty acid content. The structure was confirmed by synthesis of 2-oleoyloxyethylphosphonate from ethylene oxide, phosphorus acid and oleic acid chloride. Considering the isolated surfactant molecule as hexadecanoyloxyethylphosphonic acid (mw. 364), the critical micelle concentration (CMC) was about 22 mM.     

Perfectly straight nanowires of fullerenes bearing long alkyl chains on graphite

Fullerene derivatives bearing long alkyl chains epitaxially adsorb on the basal plane of graphite forming well-ordered one-dimensional lamellae. Within the lamellae, the C60 moieties are organized in a zigzag-type fashion. The ordering is mainly governed by the substitution pattern and chain length of the alkyl chains. The electrochemical activity of the C60 groups is fully maintained in the surface-confined assemblies.     

Utilization of the pleiotropy of a peptidic aptamer to fabricate heterogeneous nanodot-containing multilayer nanostructures

Peptide aptamers (=binders) against inorganic materials often show a capacity for mineralization of their target atoms; thus they are able to function both as binding molecules and as mediators for mineralization. Although the mechanisms underlying these two properties of peptide aptamers are not yet fully understood, they have been used separately to fabricate various nanostructures. Here, we present a novel method of nanofabrication, in which binding and mineralization by a peptide aptamer are alternately utilized to assemble multilayered nanostructures comprised of metal loaded cage proteins ornamented with Ti-binding peptides.     

Expeditious syntheses of conjugated allenyl esters and oxazoles through a cascade reaction of alpha-alkynyl malonates under alkaline conditions

Diethyl alpha-alkynyl-alpha-methoxymalonates (2a--e) were smoothly hydrolyzed and then decarboxylated under alkaline conditions employing 1 N KOH in EtOH to give conjugated allenyl esters (6a--e) in high yields, and similar alkaline treatment of diethyl alpha-alkynyl-alpha-acetylaminomalonates (5a, b, d, e) furnished unexpectedly the oxazoles (7a, b, d, e) having three substituent groups in excellent yields.     

Stereo structure-controlled and electronic structure-controlled estrogen-like chemicals to design and develop non-estrogenic bisphenol A analogs based on chemical hardness concept

The aim of this study was to elucidate the structure-activity relationship of bisphenol A (BPA) analogs using absolute hardness (eta) and absolute electronegativity (chi) (chemical hardness) and to design a non-estrogen active BPA. To determine the structure-activity relationships of BPA analogs, we investigated MCF-7 cell proliferation stimulated by BPA analogs and an eta-chi diagram based on the electronic structure of the BPA analogs. The results show that the actions of the environmental hormones BPA analogs have two chemical properties; (i) 'stereo structure-controlled' and (ii) 'electronic structure-controlled' estrogen-like chemical activities. Therefore, we designed and synthesized BPA analogs which do not possess these 2 characteristics, ((i) and (ii)), and demonstrate the non-estrogen activity of the analog.