Bimetallic Co–Pd alloy nanoparticles as magnetically recoverable catalysts for the aerobic oxidation of alcohols in water

Co–Pd bimetallic alloy nanoparticle catalysts were prepared from CoCl₂, Pd(OAc)₂ and several capping agents with Li(C₂H₅)₃BH. The nanoparticle catalysts were applied to the aerobic oxidation of a variety of alcohols in water to give the corresponding carbonyl products. The catalyst was magnetically recovered and reused for further oxidation. The nanoparticle catalysts were characterized with TEM, ICP, and XPS analyses.     

Multiple Ca(2+) environments in silicate glasses by high-resolution (43)Ca MQMAS NMR technique at high and ultra-high (21.8 T) magnetic fields

We here show the (43)Ca 5QMAS NMR spectra at high field (16.4 T) and the first 7QMAS spectrum at ultra-high field (21.8 T) for geologically important Ca-containing glasses. The high-resolution MQMAS spectra present a clear evidence of multiple Ca sites in the amorphous structures that have never been identified by other analytical methods. The present study suggests that the Ca(2+) ions are mainly in 7- and 8-fold coordination sites. This will offer valuable insights for dynamic properties of magmatic liquids. The MQMAS NMR technique at high magnetic field is a unique tool to understand the detailed structural information on a specific element in solids including organic and inorganic compounds.     

Effect of dopant structure on refractive index and glass transition temperature of polymeric fiber‐optic materials

Graded‐index plastic optical fibers, composed of doped polymers, have advantages over conventional glass optical fibers, but need to be developed further for practical application. Here, a variety of aromatic sulfide dopants were synthesized, and their effects on the refractive indexes and glass transition temperatures (T_g) of poly(methyl methacrylate) and methyl 2‐chloroacrylate/2,2,2‐trichloroethyl methacrylate copolymers were studied. While polymers containing large dopants exhibited relatively high refractive indices, their T_g values were low, making these materials unsuitable for graded‐index plastic optical fiber applications. Six dopants yielded polymers that exhibited higher T_g values than the conventionally used (diphenyl sulfide)‐doped polymer. The dopant dibenzothiophene, in particular, yielded polymers with the highest refractive indexes and T_g values, and polymers containing (phenylthio)benzene dopants also performed well. Copyright © 2013 John Wiley & Sons, Ltd.     

Folding of Synthetic Homogeneous Glycoproteins in the Presence of a Glycoprotein Folding Sensor Enzyme

UDP‐glucose:glycoprotein glucosyltransferase (UGGT) plays a key role in recognizing folded and misfolded glycoproteins in the glycoprotein quality control system of the endoplasmic reticulum. UGGT detects misfolded glycoproteins and re‐glucosylates them as a tag for misfolded glycoproteins. A flexible model to reproduce in vitro folding of a glycoprotein in the presence of UGGT in a mixture containing correctly folded, folding intermediates, and misfolded glycoproteins is described. The data demonstrates that UGGT can re‐glucosylate all intermediates in the in vitro folding experiments, thus indicating that UGGT inspects not only final folded products, but also the glycoprotein folding intermediates.     

Molecularly Designed Nanoparticles by Dispersion of Self‐Assembled Organosiloxane‐Based Mesophases

The design of siloxane‐based nanoparticles is important for many applications. Here we show a novel approach to form core–shell silica nanoparticles of a few nanometers in size through the principle of “dispersion of ordered mesostructures into single nanocomponents”. Self‐assembled siloxane–organic hybrids derived from amphiphilic alkyl‐oligosiloxanes were postsynthetically dispersed in organic solvent to yield uniform nanoparticles consisting of dense lipophilic shells and hydrophilic siloxane cores. In situ encapsulation of fluorescent dyes into the nanoparticles demonstrated their ability to function as nanocarriers.     

(Quasi‐)Racemic X‐ray Structures of Glycosylated and Non‐Glycosylated Forms of the Chemokine Ser‐CCL1 Prepared by Total Chemical Synthesis

Our goal was to obtain the X‐ray crystal structure of the glycosylated chemokine Ser‐CCL1. Glycoproteins can be hard to crystallize because of the heterogeneity of the oligosaccharide (glycan) moiety. We used glycosylated Ser‐CCL1 that had been prepared by total chemical synthesis as a homogeneous compound containing an N‐linked asialo biantennary nonasaccharide glycan moiety of defined covalent structure. Facile crystal formation occurred from a quasi‐racemic mixture consisting of glycosylated L ‐protein and non‐glycosylated‐D ‐protein, while no crystals were obtained from the glycosylated L ‐protein alone. The structure was solved at a resolution of 2.6–2.1 Å. However, the glycan moiety was disordered: only the N‐linked GlcNAc sugar was well‐defined in the electron density map. A racemic mixture of the protein enantiomers L ‐Ser‐CCL1 and D ‐Ser‐CCL1 was also crystallized, and the structure of the true racemate was solved at a resolution of 2.7–2.15 Å. Superimposition of the structures of the protein moieties of L ‐Ser‐CCL1 and glycosylated‐L ‐Ser‐CCL1 revealed there was no significant alteration of the protein structure by N‐glycosylation.     

Superelastic Organic Crystals

Superelastic materials (crystal‐to‐crystal transformation pseudo elasticity) that consist of organic components have not been observed since superelasticity was discovered in a Au‐Cd alloy in 1932. Superelastic materials have been exclusively developed in metallic or inorganic covalent solids, as represented by Ti‐Ni alloys. Organosuperelasticity is now revealed in a pure organic crystal of terephthalamide, which precisely produces a large motion with high repetition and high energy storage efficiency. This process is driven by a small shear stress owing to the low density of strain energy related to the low lattice energy.     

Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques

There is limited information on the mechanism for platinum oxidation and dissolution in Pt/C cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) under the operating conditions though these issues should be uncovered for the development of next‐generation PEFCs. Pt species in Pt/C cathode catalyst layers are mapped by a XAFS (X‐ray absorption fine structure) method and by a quick‐XAFS(QXAFS) method. Information on the site‐preferential oxidation and leaching of Pt cathode nanoparticles around the cathode boundary and the micro‐crack in degraded PEFCs is provided, which is relevant to the origin and mechanism of PEFC degradation.