Dissolution and wet spinning of silk fibroin using phosphoric acid/formic acid mixture solvent system

Regenerated silk fibroin (SF) filaments could be prepared by wet spinning in common solvent/coagulation system. SF was directly dissolved in mixture solvent of phosphoric acid and formic acid (20/80–30/70 ratio) and coagulated in methanol bath. The concentration and stability of SF dope solution have been studied by varying the mixture ratios of these solvents in accordance with elucidating the role of formic acid in the mixture solvent system. Morphological structure as well as crystalline structure of the regenerated filament was examined using SEM and XRD analyses. As a result of tensile test, the regenerated SF filament, which was made by one‐step dissolution and coagulation process, had good mechanical properties, 2.3 gf/d tenacity and 18% breaking strain. In this study, a simple wet spinning method which enables to apply to practical production has been reported for the preparation of the regenerated SF filament. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly(N‐isopropylacrylamide) gel‐based macroporous monolith for continuous‐flow recovery of palladium(II) ions

Macroporous monoliths, composed of thermoresponsive, tertiary‐aminated, and crosslinking monomers, were prepared for continuous‐flow separation of palladium(II) ions. N ‐Isopropylacrylamide was required to form the porous structure in the monoliths, indicating that the mechanism of porous structure formation involved polymerization‐induced phase separation of the poly(N ‐isopropylacrylamide) gel. Tertiary‐aminated monoliths showed adsorption selectivity for palladium(II) ions in hydrochloric media, compared with copper(II) ions. The maximum capacities of the monoliths with tertiary amine contents of 10, 20, 30, and 70 mol % for palladium(II) ions were 0.6, 1.1, 1.3, and 2.3 mmol/g, respectively. Darcy's permeabilities of water through the macroporous monolith were 10^?14 to 10^?13 m², and those were comparable to that through a commercially available membrane filter with a pore size of several micrometers. In the continuous‐flow process, the macroporous monolith with tertiary amine selectively adsorbed palladium(II) ions in the coexistence of copper(II) ions with 10 times higher concentration than the palladium(II) ions. The palladium(II) ions were eluted from the macroporous monolith, and the concentration of palladium(II) ions in the eluate was up to 45 times of that in the feed solution. The average enrichment factor and total recovery percentage of palladium(II) ions were 8.7 times and 95%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44385.     

Measurement of carbon sputtering yield by N ion beam and lifetime dependence of resulting foils on thickness

Carbon stripper foils with a higher nitrogen content were made by ion beam sputtering with reactive nitrogen gas. Such foils seem to be very useful as strippers for high-intensity heavy ion accelerators. To know further characteristics of the lifetime of such carbon foils, we have measured the sputtering yield of the carbon source material at a sputtering voltage of 4–15 kV and the lifetime dependence of such foils on thickness. Lifetime measurement was performed with a 3.2 MeV Ne⁺ ion beam. The sputtering yield on average showed 0.75 atoms/ion at over 9 kV sputtering voltage. The lifetime of the foils noticeably depends on the foil thickness, and the thickness range as practical stripper foil is to be around 15 to 33 μg/cm². Two foils made at 13 kV showed extremely long lifetimes of 6800 and 6000 mC/cm² at maximum and the foils made above 10 kV lived longer than about 900 mC/cm², which correspond to about 270 and 40 times longer than commercially available best foils. We measured the thickness ratio of nitrogen to carbon in each foil made at the different sputtering voltages and at the different irradiation stages (mC/cm²) by RBS method. We also inspected the structure of a nitrided carbon foil by transmission electron microscopy.     

Lifetime improvement of slackened thin cluster carbon stripper foils by suppression of carbon buildup

We control the amount of carbon buildup on slackened thin cluster carbon stripper foils (less than 3.5 μg/cm²) by heating with a high-power infrared lamp during beam bombardment. Foil lifetime measurements were performed using 2.0±0.5 μA beams of 3.2 MeV Ne⁺ ions and quantified as the total charge/area before breakage. Lifetimes were obtained up to 1286 mC/cm² at maximum and 1139 mC/cm² on the average; these values are, respectively, approximately 51 times at maximum and 46 times on average greater than the best commercially available foils, when used unheated and unslackened.     

Experiment study on fracture fixation with low rigidity titanium alloy

In order to investigate bone tissue reaction to the low rigidity titanium alloy of TNTZ in bone plate fixation, animal experiment with rabbit was performed with X-ray follow-up and histological observation. Experimental fractures were made in rabbit tibiae, and fixed by different bone plates of SUS316L, Ti–6Al–4V and TNTZ. Although there was no significant difference in fracture healing, bone atrophy was observed in cortical bone especially under the bone plate, which was different in time course among three materials. The bone atrophy under the bone plate was confirmed as porous or poor bone tissue in histological observation. In addition, the diameter of the tibia bone was increased in TNTZ as the result of bone remodeling with a new cortical bone. It is confirmed that the elastic modulus of the bone plate will naturally influence bone tissue reaction to the bone plate fixation according to the Wolff’s law of functional restoration.     

Theoretical study of the adsorption of Cs,Cs+, I,I−, and CsI on C60 fullerene

Theoretical investigation for the adsorption of the cesium atom (Cs), the cesium iodide molecule (CsI), the iodine atom (I), the cesium cation (Cs⁺), and the iodide anion (I^?) onto the surface of a single fullerene molecule (C₆₀) are reported. A hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) is employed. The adsorption energies, i.e., the opposite of enthalpy change through adsorption, are calculated to be 143, 12, 9, 46, and 49 kJ mol^?1 for Cs, CsI, I, Cs⁺, and I^?, respectively. The equilibrium constant for Cs is calculated to be 7×10³ atm^?1 at the temperature of 1000 K and is seven orders of magnitude higher than that for CsI, indicating that the C₆₀ molecule adsorb the Cs atom highly selectively against the CsI molecule.     

Site-specific functionalization of proteins by organopalladium reactions

A new carbon-carbon bond has been regioselectively introduced into a target position (position 32 or 174) of the Ras protein by two types of organopalladium reactions (Mizoroki-Heck and Sonogashira reactions). Reaction conditions were screened by using a model peptide, and the stability of the Ras protein under the reaction conditions was examined by using the wild-type Ras protein. Finally, the iF-Ras proteins containing a 4-iodo-L-phenylalanine residue were subjected to organopalladium reactions with vinylated or propargylated biotin. Site-specific biotinylations of the Ras protein were confirmed by Western blot and LC-MS/MS.     

Dehydration of d-glucose in high temperature water at pressures up to 80 MPa

Reaction of d-glucose in water to yield 5-hydroxymethylfurfural (5-HMF), 1,2,4-benzenetriol (BTO) and furfural was studied at high temperatures (up to 400 °C) and high pressures (up to 80 MPa) using a continuous flow reactor. Maximum temperature and pressure conditions gave maximum furfural yield. Increasing pressure from 40 to 70 and 80 MPa enhanced dehydration reactions to 5-HMF, but also enhanced hydrolysis of 5-HMF leading to the production of BTO and thus lead to lower yields of 5-HMF (below 10%). Remarkably, the dehydration reaction to 5-HMF and the hydrolysis of 5-HMF were both enhanced by the increase in water density at 400 °C.     

Soft materials with graphitic nanostructures

This review article focuses on our recent studies on novel soft materials consisting of carbon nanotubes. Single-walled carbon nanotubes, when suspended in imidazolium ion-based ionic liquids and ground in an agate mortar, form physical gels (bucky gels), where heavily entangled bundles of carbon nanotubes are exfoliated to give highly dispersed, much finer bundles. By using bucky gels, the first printable actuators that operate in air for a long time without any external electrolyte are developed. Furthermore, the use of polymerizable ionic liquids as the gelling media results in the formation of electroconductive polymer/nanotube composites with enhanced mechanical properties. The article also highlights a new family of nanotubular graphite, via self-assembly of amphiphilic hexabenzocoronene (HBC) derivatives. The nanotubes consist of a graphitic wall composed of a great number of pi-stacked HBC units and are electroconductive upon oxidation. The use of amphiphilic HBCs with functional groups results in the formation of nanotubes with various interesting properties.     

Detection of influenza virus hemagglutinin with randomly immobilized anti-hemagglutinin antibody on a carbon nanotube sensor

Carbon nanotube sensors were capable of detecting hemagglutinin binding to anti-hemagglutinin antibody immobilized on the sensor. The carbon nanotube sensors were fabricated by chemical vapor deposition method and it showed field effect transistor property. Anti-hemagglutinin antibody was immobilized by cross-linking on the reverse surface of the carbon nanotube sensor. The current between the source and the drain was measured after incubation of various concentration of hemagglutinin antigen with immobilized anti-hemagglutinin antibody. I-Vgate curve was obtained by plotting the current as a function of the potential applied to the back gate. The I-Vgate curve showed a positive shift in a manner dependent on the hemagglutinin antigen concentration after immobilization of anti-hemagglutinin while no shift was observed without immobilization of anti-hemagglutinin antibody on the surface. The sensitivity of the CNT sensor was higher than that of the QCM method even without controlling the orientation of the anti-hemagglutinin antibody. This method constitutes a new tool to analyze interactions among biomolecules on a substrate.