Hydrogen-bonding abilities for phenols assessed by quantitative analyses of their partition coefficients derived from different partitioning systems

We recently proposed a new hydrogen-accepting scale, S(HA), on the basis of the heat of formation calculated by the conductor-like screening model (COSMO) method. In this work, the same approach was applied to a series of compounds with a common hydrogen-donor group. Thus the S(HA) values for monosubstituted phenols were calculated and used for correlating their log P(oct) values (P(oct): 1-octanol/water partition coefficient) with log P(CL) (P(CL): chloroform/water partition coefficient) and log P(E) (P(E): butyl ether/water partition coefficient). It was demonstrated that the S(HA) parameter works effectively, providing excellent correlations whose physicochemical meanings are well rationalized in terms of hydrogen-bonding characteristics of the substituents.     

Surface cleaning of germanium nanodot ionization substrate for surface‐assisted laser desorption/ionization mass spectrometry

In surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS), a chemical background signal, arising from organic contaminants such as plasticizers, is frequently observed mainly under m/z ca. 600, which impairs the advantages of the matrix‐free approach. Silver salts, which are used for the cationization of aromatic compounds, are also difficult to remove completely after the measurements. In this study, surface cleaning techniques used in semiconductor processing were used to clean our developed silicon‐based SALDI substrate on which self‐assembled germanium nanodots (GeNDs) had been deposited (termed a GeND chip). An immersion cleaning method using acetone with sonication, and a sulfuric‐peroxide mixture (SPM) cleaning method using a mixture of H₂SO₄/H₂O₂/deionized water, were examined for their effectiveness in removing organic compounds and residual silver salts. Removal of both types of contaminants was successfully performed by SPM cleaning. The limit of detection for glutathione was improved from ca. 5 pmol without cleaning to ca. 50 fmol after the SPM cleaning. Since GeND chips can tolerate acidic cleaning and sonication due to their chemical inertness and rigid nanodot structures, they appear to be an ideal reusable SALDI substrate. Copyright © 2009 John Wiley & Sons, Ltd.     

Segmental orientations and deformation mechanism of a poly(ether‐block‐amide) film

Simultaneous measurements of microscopic infrared dichroism, mesoscale deformation, and macroscopic stress have been made for a microphase‐separated film of poly(ether‐block‐amide) 4033 during uniaxial stretching at temperatures between 30 and 91 °C, well below the melting point of the hard polyamide‐12 (PA) domains. Before the onset of dramatic microstructural alterations, the true stress–strain relationship on the mesoscale can be described with an interpenetrating network model, and poly(tetramethylene oxide) (PTMO) soft segments undergo affine deformation. Beyond a threshold strain at which stress from the soft network becomes larger than that from the hard network, plastic deformation occurs in the hard PA domains, and this is accompanied by the downward derivations of the true stress and molecular orientation of PTMO blocks from the model predictions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1161–1167, 2005     

Preferential Alignment of Hydroxyapatite Crystallites in Nanocomposites with Chemically Disintegrated Silk Fibroin

Hydroxyapatite (HAp) nanocrystals were prepared at room temperature by a coprecipitation method from Ca(OH)₂ and H₃PO₄, in the presence of chemically disintegrated silk fibroin (SF). Adsorbed amounts of cations on SF and crystallinity of HAp in the composite were increased by the chemical disintegration of SF higher order structure. Preferential alignment of c-axis of HAp crystallites along the longitudinal direction of ca. 150nm SF fibril was observed. These changes due to disintegration of SF were discussed in terms of the chemical interaction between HAp and SF. The resulted composite with preferential alignment of HAp nanocrystals is a good candidate as a starting material for bone substitutes.     

Deformation and molecular orientation in films of metallocene polypropylene,ethylene–butylene rubber,and their 80/20 (w/w) blend revealed by the simultaneous kinetic measurement of microscopic infrared dichroism,macroscopic stress,and mesoscale strain

Simultaneous kinetic measurement of microscopic infrared dichroism, macroscopic stress, and mesoscale strain was used to study the deformation mechanisms of metallocene polypropylene (MPP), ethylene–butylene rubber (EBR), and their blend (MPP/EBR = 80/20 w/w). As with pure MPP, the molecular orientation in the blend is dominated by the necking of the isotactic polypropylene matrix. During the necking passage through the mesoscale sampling area, the molecular orientation of the polypropylene matrix in the blend is smaller than that in the pure polypropylene film at the same level of mesoscale strain. However, the orientation of the EBR dispersed phase in the blend is larger than that in the pure EBR film. This may result from the partial miscibility of the two ingredients in the amorphous phases and their resultant strong interfacial interaction. The large stress supported by the MPP matrix extends to the island of the EBR domain and leads to its large deformation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1520–1531, 2005     

Chemical synthesis and application of C-terminally 5-carboxyfluorescein-labelled thymopentin as a fluorescent probe for thymopoietin receptor.

Thymopentin (TP5) is a synthetic pentapeptide fragment, which corresponds to position 32 - 36 of thymic polypeptide thymopoietin. Thymopoietin and TP5 display a variety of biological functions, including phenotypic differentiation of T cells and the regulation of immune systems. Previous chemical modification experiments suggested that there was an absolute requirement for N-terminal amino acids to maintain the biological activity of TP5. On the basis of this structure-activity relationship, we designed and synthesized the C-terminally 5-carboxyfluorescein-coupled TP5 (TP5-FAM) as a fluorescent probe for thymopoietin receptor. TP5-FAM could bind to the membrane of human lymphoid cell lines, MOLT-4 cells, in which the thymopoietin receptor is expressed. The binding is specific and saturable (K(d) = 33 microM). TP5 and human splenopentin are nearly equipotent inhibitors of TP5-FAM binding to the thymopoietin receptor, but porcine secretin did not show any significant inhibition of TP5-FAM binding to MOLT-4 cells. Thus, TP5-FAM is suggested to be a potent and biologically active ligand that would be useful for studying the binding and functional characteristics of the human thymopoietin receptor.