Preparation of Porous Protein-Based Hydogel for Highly Sensitive Protein Chips

Summary: Protein chips are important tools for high-throughput analysis of biological events. We have developed a novel method to prepare a protein-based hydrogel, that is, a “Three-Dimensional Nano-structured Protein Hydrogel” (3-D NPH), which is composed of protein and polymer nano-particles. The 3-D NPH could be easily prepared by dispensing a protein and polymer mixture on a substrate. Surprisingly, gold particles conjugated with protein A diffused into the 3-D NPH which was made of mouse IgG through the pores. We have shown that the protein chips made with our 3-D NPH method has tremendously improved sensitivity in detecting protein-protein interactions compared with that of direct protein immobilization methods.     

A 57 Fe Mössbauer study on the FeSe and Fe(Se,Te) superconductors: discontinuities in the hyperfine parameters at T c

Polycrystalline samples of FeSe_0.82 and FeSe_0.5Te_0.5 were synthesized using a solid-state reaction route. Bulk superconductivity was confirmed using SQUID magnetometry. The onset of T _c was at 8.0 K for FeSe_0.82 and 12.5 K for FeSe_0.5Te_0.5. Paramagnetic ⁵⁷Fe Mössbauer spectra were recorded at temperatures between 5.4 and 320 K in transmission geometry. All spectra exhibited simple quadrupole splitting. For FeSe_0.5Te_0.5 a small drop in the quadrupole splitting was observed about T _c upon cooling. Additionally, for both samples the isomer shift and the total absorption started to drop around T _c , indicating a softening of the lattice. The drop is estimated to correspond to at least 60 K from the original Debye temperatures.     

Ruthenium-catalyzed hydrophosphinylative cyclization of 1,6-diynes. Stereoselective synthesis of exocyclic 1,3-dienylphosphine oxides

The first catalytic synthesis of exocyclic 1,3-dienylphosphine oxides was achieved by the ruthenium-catalyzed selective hydrophosphinylative cyclization of 1,6-diynes. A plausible mechanism involving a ruthenacyclopentatriene intermediate is proposed on the basis of the DFT calculations of model ruthenium complexes.     

Application of high‐resolution ESI and MALDI mass spectrometry to metabolite profiling of small interfering RNA duplex

We investigated the application of a high‐resolution Orbitrap mass spectrometer equipped with an electrospray ionization (ESI) source and a matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) mass spectrometer to the metabolite profiling of a model small interfering RNA (siRNA) duplex TSR#34 and compared their functions and capabilities. TSR#34 duplex was incubated in human serum in vitro, and the duplex and its metabolites were then purified by ion exchange chromatography in order to remove the biological matrices. The fraction containing the siRNA duplex and its metabolites was collected and desalted and then subjected to high‐performance liquid chromatography (HPLC) equipped with a reversed phase column. The siRNA and its metabolites were separated into single strands by elevated chromatographic temperature and analyzed using the ESI‐Orbitrap or the MALDI‐TOF mass spectrometer. Using this method, the 5' and/or 3' truncated metabolites of each strand were detected in the human serum samples. The ESI‐Orbitrap mass spectrometer enabled differentiation between two possible RNA‐based sequences, a monoisotopic molecular mass difference which was less than 2 Da, with an intrinsic mass resolving power. In‐source decay (ISD) analysis using a MALDI‐TOF mass spectrometer allowed the sequencing of the RNA metabolite with characteristic fragment ions, using 2,4‐dihydroxyacetophenone (2,4‐DHAP) as a matrix. The ESI‐Orbitrap mass spectrometer provided the highest mass accuracy and the benefit of on‐line coupling with HPLC for metabolite profiling. Meanwhile, the MALDI‐TOF mass spectrometer, in combination with 2,4‐DHAP, has the potential for the sequencing of RNA by ISD analysis. The combined use of these methods will be beneficial to characterize the metabolites of therapeutic siRNA compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

Nash equilibrium based fairness

There are several approaches of sharing resources among users. There is a noncooperative approach wherein each user strives to maximize its own utility. The most common optimality notion is then the Nash equilibrium. Nash equilibria are generally Pareto inefficient. On the other hand, we consider a Nash equilibrium to be fair as it is defined in a context of fair competition without coalitions (such as cartels and syndicates). We show a general framework of systems wherein there exists a Pareto optimal allocation that is Pareto superior to an inefficient Nash equilibrium. We consider this Pareto optimum to be ??Nash equilibrium based fair.?? We further define a ??Nash proportionately fair?? Pareto optimum. We then provide conditions for the existence of a Pareto-optimal allocation that is, truly or most closely, proportional to a Nash equilibrium. As examples that fit in the above framework, we consider noncooperative flow-control problems in communication networks, for which we show the conditions on the existence of Nash-proportionately fair Pareto optimal allocations.     

Stochastic switching of subphthalocyanine arrays triggered by scanning tunneling microscopy

Single-molecular switching phenomena in monolayer arrays of subphthalocyanine adsorbed on Cu(1 0 0) surface were investigated by scanning tunneling microscopy (STM) under ultrahigh vacuum. The molecules evaporated on the surface arranged in a square lattice taking the Cu(1 0 0)SubPc(5 × 5) epitaxy. During continuous STM imaging at fixed tunneling conditions the topography of the individual molecules spontaneously changed between the high and low states. This topographic change was attributed to orientational switching between the upward and downward adsorption of the axial Cl atom of the molecule on the Cu surface. Molecular energy calculations and statistical thermodynamic evaluation concluded that the tip-triggered disturbance in the close-packed molecular array induced the molecular rearrangement accompanied with the stochastic orientational switching.     

Flow characteristics and spinnability of sols prepared from silicon alkoxide solution

Structural evolution of the solution of tetraethoxysilane hydrolyzed with [H₂O]/[Si(OC₂H₅)₄] = 2 under acidic condition has been investigated by rheological measurements. It was found that the solution behaves as a Newtonian liquid up to a highly viscous state and shows spinnability before gelation when the evaporation of the solvent is allowed during gelation reaction. On the other hand, the solution behaved as a non-Newtonian liquid in the viscous state, showing no spinnability when the evaporation of the solvent was not allowed during the reaction. It was indicated from the Casson plots that the spinnable solution prepared in the open system has no yield stress up to highly viscous states, whereas the non-spinnable solution prepared in the closed system has a yield stress at viscous states. It was proposed that the increase in viscosity of the open system solution is attributable to the concentration of the sol particles whereas that of the closed system solution is attributable to the formation of the three dimensional network in the solution.     

On the convergence of partial differential equations of parabolic type with rapidly oscillating coefficients to stochastic partial differential equations

In this paper we consider the convergence of the solutions to a sequence of partial differential equations of parabolic type with rapidly oscillating coefficients to the solutions of a stochastic partial differential equation. We use the martingale method and the characteristic functional to prove that the martingale problem has a unique solution. Our emphasis is in treating strongly mixing noises.This research was partially supported by Stifting Volkswagenwerk through Forschungszentrum BiBoS Universität Bielefeld and Grant-in-Aid for General Scientific Research (C) 61540162, the Ministry of Education, Science and Culture (Japan). Presented at the International Workshop on Diffusion Approximations and Related Topics, IISA, Laxenburg, Austria, 29 June to 3 July 1987.     

Synthesis of soluble quinacridones

The synthesis of 4,11-dialkylthioquinacridones and 5,12-dialkyl-4,11-dialkylthioquinacridone from o-alkylthioanilines and diethyl 2,5-dioxo-1,4-cyclohexanedicarboxylate is described. These compounds are easily soluble in organic solvents in contrast to unsubstituted quinacridone.