Quinone-recognition by Four-point Hydrogen Bonding in Porphyrin System Having Urea Moiety

5,15- cis -bis(Ureidophenyl)porphyrins have significant recognizing ability for p -benzoquinones through four-point hydrogen bonding. Although an unusual temperature-dependence of the complexation is observed with bis( N '-phenylureidophenyl) porphyrin, bis( N '-ethylureidophenyl)porphyrin shows a satisfactorily linear van't Hoff plot and recognizes an electron-rich p -benzoquinone such as tetramethyl- p -benzoquinone more effectively, which is ascribed to the large enthalpy change in the complex.     

Mannose‐Binding Geometry of Pradimicin A

Pradimicins (PRMs) and benanomicins are the only family of non‐peptidic natural products with lectin‐like properties, that is, they recognize D ‐mannopyranoside (Man) in the presence of Ca²⁺ ions. Coupled with their unique Man binding ability, they exhibit antifungal and anti‐HIV activities through binding to Man‐containing glycans of pathogens. Notwithstanding the great potential of PRMs as the lectin mimics and therapeutic leads, their molecular basis of Man recognition has yet to be established. Their aggregate‐forming propensity has impeded conventional interaction analysis in solution, and the analytical difficulty is exacerbated by the existence of two Man binding sites in PRMs. In this work, we investigated the geometry of the primary Man binding of PRM‐A, an original member of PRMs, by the recently developed analytical strategy using the solid aggregate composed of the 1:1 complex of PRM‐A and Man. Evaluation of intermolecular distances by solid‐state NMR spectroscopy revealed that the C2–C4 region of Man is in close contact with the primary binding site of PRM‐A, while the C1 and C6 positions of Man are relatively distant. The binding geometry was further validated by co‐precipitation experiments using deoxy‐Man derivatives, leading to the proposal that PRM‐A binds not only to terminal Man residues at the non‐reducing end of glycans, but also to internal 6‐substituted Man residues. The present study provides new insights into the molecular basis of Man recognition and glycan specificity of PRM‐A.     

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.     

Preparation of Molecule‐Responsive Microsized Hydrogels via Photopolymerization for Smart Microchannel Microvalves

Microdevices designed for practical environmental pollution monitoring need to detect specific pollutants such as dioxins. Bisphenol A (BPA) has been widely used as a monomer for the synthesis of polycarbonate and epoxy resins. However, the recent discovery of its high potential ability to disrupt human endocrine systems has made the development of smart systems and microdevices for its detection and removal necessary. Molecule‐responsive microsized hydrogels with β‐cycrodextrin (β‐CD) as ligands are prepared by photopolymerization using a fluorescence microscope. The molecule‐responsive micro‐hydrogels show ultra‐quick shrinkage in response to target BPA. Furthermore, the flow rate of a microchannel is autonomously regulated by the molecule‐responsive shrinking of their hydrogels as smart microvalves.

     

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.