Constituents of ophiuroidea. 1. Isolation and structure of three ganglioside molecular species from the brittle star Ophiocoma scolopendrina.

Three ganglioside molecular species, OSG-0 (1), OSG-1 (2), and OSG-2 (3) have been obtained from the polar lipid fraction of the chloroform/methanol extract of the brittle star Ophiocoma scolopendrina. The structures of these gangliosides have been determined on the basis of chemical and spectroscopic evidence as 1-O-[(N-glycolyl-alpha-D-neuraminosyl)-(2-->6)-beta-D-glucopyranosyl]-ceramide (1), 1-O-[8-O-sulfo-(N-acetyl-alpha-D-neuraminosyl)-(2-->6)-beta-D-glucopyranosyll-ceramide (2) and 1-O-[(N-glycolyl-alpha-D-neuraminosyl)-(2-->8)-(N-acetyl- and N-glycolyl-alpha-D-neuraminosyl)-(2-->6)-beta-D-glucopyranosyl]-ceramide (3). The ceramide moieties were composed of heterogeneous unsubstituted fatty acid, 2-hydroxy fatty acid and phytosphingosine units. Compounds 2 and 3 represent new ganglioside molecular species.     

ESR study of Mn2+ in GeTe and GeTeSi glasses

The electron spin resonance spectra of Mn²⁺ ions have been studied in Ge_xTe_100?x with x = 15, 17.5 and 20, and Ge_20?xTe₈₀Si_x with 0 ?x? 20. All samples are found to exhibit six hyperfine lines centered at g = 4.3 with hyperfine interaction constant A = 56 × 10^?4cm^?1. The g = 4.3 line is interpreted as being caused by Mn²⁺ ions incorporated in the amorphous network and surrounded by four Te atoms in an arrangement of orthorhombic symmetry. Some of the samples of GeTe show a g = 2.0 line. This line also appears after heat treatment in air at temperatures above the glass transition temperature. It is concluded that the g = 2.0 line is caused by Mn²⁺ ions in phase separated microcrystalline or concentrated regions of MnO in the glass.     

Functionalized pyrolytic highly oriented graphite polymer film for surface‐assisted laser desorption/ionization mass spectrometry in environmental analysis

The pyrolytic highly oriented graphite polymer film (PGS) was first employed to analyze low‐mass analytes in environmental analysis by surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS). PGS is a synthetic uniform and highly oriented graphite polymer film with high thermal anisotropic conductivity. We have found that negative ion mode SALDI‐MS using oxidized PGS (PGS‐SALDI‐MS) can be used to detect [M–H]^? ions from perfluorooctanoic acid (PFOA) and other perfluoroalkylcarboxylic acids when the PGS surface is modified with the cationic polymer polyethyleneimine (PEI). The signal intensity of PFOA when employing the PEI modification showed a ten‐fold increase over that obtained from desorption/ionization on porous silicon (DIOS). PFOA was quantified using PGS‐SALDI‐MS and the calibration curve showed a wide linear dynamic range of response (20–1000 ppb). The combination of atmospheric pressure ionization and PGS (AP‐PGS‐SALDI) showed greater signal intensity than vacuum PGS‐SALDI for deprotonated PFOA. Several other environmentally important chemicals, including perfluoroalkylsulfonic acid, pentachlorophenol, bisphenol A, 4‐hydroxy‐2‐chlorobiphenyl, and benzo[a]pyrene, were also successfully used to evaluate PGS‐SALDI‐MS. In addition, we found that nonafluoro‐1‐butanesulfonic acid was able to produce protonated peptides in positive ion PGS‐SALDI‐MS, but that perfluoropentanoic acid and trifluoroacetic acid were not. It is suggested that perfluoroalkylsulfonic acids are better protonating agents than perfluoroalkylcarboxylic acids in SALDI‐MS. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface structures and osteoblast response of hydrothermally produced CaTiO3 thin film on Ti-13Nb-13Zr alloy

This study investigated the surface characteristics and in vitro biocompatibility of a titanium (Ti) oxide layer incorporating calcium ions (Ca) obtained by hydrothermal treatment with or without post heat-treatment in the Ti-13Nb-13Zr alloy. The surface characteristics were evaluated by scanning electron microscopy, thin-film X-ray diffractometry, X-ray photoelectron spectroscopy, atomic force microscopy and contact angle measurements. In vitro biocompatibility of the Ca-containing surfaces was assessed in comparison with untreated surfaces using a pre-osteoblast cell line. Hydrothermal treatment produced a crystalline CaTiO₃ layer. Post heat-treatment at 400 °C for 2 h in air significantly decreased water contact angles in the CaTiO₃ layer (p < 0.001). The Ca-incorporated alloy surfaces displayed markedly increased cell viability and ALP activity compared with untreated surfaces (p < 0.001), and also an upregulated expression of various integrin genes (α1, α2, α5, αv, β1 and β3) at an early incubation time-point. Post heat-treatment further increased attachment and ALP activity in cells grown on Ca-incorporated Ti-13Nb-13Zr alloy surfaces. The results indicate that the Ca-incorporated oxide layer produced by hydrothermal treatment and a simple post heat-treatment may be effective in improving bone healing in Ti-13Nb-13Zr alloy implants by enhancing the viability and differentiation of osteoblastic cells.     

Equiaffine immersions of general codimension and its transversal volume element map

With an equiaffine immersion of codimension 1 into the affine space with the natural equiaffine structure, the conormal map is associated. In this paper, for an equiaffine immersion of general codimension into the space, we shall define the map corresponding to the conormal map, which is called the transversal volume element map. And we shall investigate if, an equiaffine immersion of general codimension into the space is determined by its affine fundamental form and its transversal volume element map.     

Automated phosphoproteome analysis for cultured cancer cells by two-dimensional nanoLC-MS using a calcined titania/C18 biphasic column.

We have developed an on-line automated system for phosphoproteome analysis using titania-based phosphopeptide enrichment followed by nanoLC-MS/MS. Titania beads were prepared by calcination of commercial chromatographic titania beads at 800 degrees C to convert the crystalline structure. The obtained rutile-form titania exhibited higher selectivity in phosphopeptide enrichment than commercial titania, even in the absence of a competitive chelating reagent for non-phosphopeptides. For phosphoproteome analysis of human cervical cancer HeLa cells, tryptic digests of the cell extracts were directly injected into this on-line system, and 696 non-redundant phosphopeptides with 671 unambiguously determined phosphorylation sites, derived from 512 phosphoproteins, were successfully identified. This is the first successful application of an on-line automated phosphoproteome analysis system to complex biological samples.     

Nonlinear resonances and self-excited oscillations of a rotor caused by radial clearance and collision

This paper investigates oscillations in a flexible rotor system with radial clearance between an outer ring of the bearing and a casing by experiments and numerical simulations. The mathematical model considers the collisions of the bearing with the casing. The following phenomena are found: (1) Nonlinear resonances of subharmonic, super-subharmonic and combination oscillation occur. (2) Self-excited oscillation of a forward whirling mode occurs in a wide range above the major critical speed. (3) Entrainment phenomena from self-excited oscillation to nonlinear forced oscillation occur at these nonlinear resonance ranges. Moreover, this study analyzes periodic solutions of the mathematical model by the Harmonic Balance Method (HBM). As the results, the nonlinear resonances of subharmonic oscillation and its entrainment phenomenon can be explained theoretically by investigating the stability of the periodic solutions. The influence of the static force and the bearing damping on these oscillation are also clarified.     

Synthesis of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates using acylative intramolecular cyclization of sulfonium salts

A simple and efficient synthesis of 4,5-dihydro-4-oxo-3-furancarboxylates using an acylative intramolecular cyclization of sulfonium salts is described. The reaction involved the efficient formation of a mixed anhydride between a linear carboxylic acid and trifluoroacetic anhydride in the presence of N-methylimidazole, followed by the sequential conversion into a highly reactive acylammonium species in situ. This procedure is easily handled, uses readily available inexpensive reagents, and provides a variety of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates.