Charged ultrafiltration membrane for permeation of proteins

Polyacrylonitrile-g-poly(N,N-dimethylaminoethyl methacrylate) was synthesized photochemically and quaternized. The positively charged membranes made from the quaternized graftcopolymer showed high ultrafiltration rate for water by adding poly(vinyl alcohol) to casting solution and washing it out after the casting. In buffered saline solution, the permeability of the membranes was very small at pH below isoelectric point of albumin but increased markedly at higher pH. On the other hand, the permeability for γ-globulin was very small and did not show any pH dependence.     

Positive-temperature-coefficient effect of electrical resistivity below melting point of poly(vinylidene fluoride) (PVDF) in Ni particle-dispersed PVDF composites

This paper discusses the positive-temperature-coefficient effects of resistivity in Ni particle-dispersed poly(vinylidene fluoride) (PVDF) composites based on experiment results from SEM, DSC, and pressure-volume-temperature (PVT) measurements. The melting points of composites with Ni content of 20, 30, 40, and 50vol.% were equal to that of pure PVDF. The PTC effects in composites with Ni content of 40 and 50vol.% occurred at temperatures near the melting point of the PVDF matrix, whereas those in composites with Ni content of 20 and 30vol.% occurred at temperatures below the melting point of the PVDF matrix. We found that the PTC effect occurs even without melting of the matrix polymer. Moreover, we determined that a slight increase in specific volume at temperatures below the melting point of the matrix polymer acts fully as a driving force for forming a gap between fillers. This suggestion was backed up by theoretical analyses using percolation theory and a thermal-fluctuation-induced tunneling model.     

Single-step synthesis and characterization of single-walled carbon nanohorns hybridized with Pd nanoparticles using N2 gas-injected arc-in-water method

Single-walled carbon nanohorns (SWCNHs) hybridized with palladium (Pd) nanoparticles were synthesized by a single-step gas-injected arc-in-water method (GI-AIW) with a Pd wire inserted inside the anode hole. In the arc zone, carbon and Pd were vaporized simultaneously, leading to the formation of hybrid material of SWCNHs and Pd nanoparticles due to effective quenching. Based on TEM and CO chemisorption analyses, Pd nanoparticles were found to be embedded inside SWCNH aggregates. The size of Pd nanoparticles, determined by X-ray diffraction, was in the range of 3–6 nm when Pd wires with diameters of 0.1 and 0.3 mm were used. Using a Pd wire with a diameter larger than 0.5 mm results in larger Pd nanoparticles which tend to be exposed to the outer surface of the hybrid material. According to thermogravimetric analyses, the weight fraction of Pd nanoparticles is increased by increasing the Pd wire diameter although the yield of Pd nanoparticles decreased. SWCNHs hybridized with dispersed Pd nanoparticles, synthesized with 0.1 mm Pd wire, exhibited strong anti-oxidation resistance with a highly graphitic structure.     

Distance measurement between Tyr10 and Met35 in amyloid beta by site-directed spin-labeling ESR spectroscopy: implications for the stronger neurotoxicity of Abeta42 than Abeta40

The neurotoxicity of the 42-mer and 40-mer amyloid beta peptides (Abeta42 and Abeta40) is closely related to the radicalization at both Tyr10 and Met35. Abeta42 is more neurotoxic than Abeta40. Our previous structural analyses of Abeta42 suggested that Tyr10 and Met35 are brought closer together by the turn at positions 22 and 23, and the S-oxidized radical cation at position 35, which is the ultimate toxic radical species, can be produced effectively through oxidation by the phenoxy radical at position 10. To verify this idea, their separation was measured by site-directed spin labeling (MTSSL) by using ESR spectroscopy. Among the three kinds of Abeta42 derivatives, which are doubly or singly spin-labeled at position 10 and 35, only 10,35-MTSSL-Abeta42 showed a clear dipole coupling in continuous-wave ESR; this suggests that the intramolecular spin labels at position 10 and 35 in Abeta42 are located within approximately 15 A. In contrast, 10,35-MTSSL-Abeta40 did not give such signals. The distance between Tyr10 and Met35 in 10,35-MTSSL-Abeta40, which was successfully measured by pulsed ESR spectroscopy was 30 A long. The difference in the distance between Abeta42 and Abeta40 could explain in part the stronger neurotoxicity of Abeta42 compared to Abeta40.     

Properties of novel diallyl phthalate resin modified with sulfur‐containing allyl ester compounds

Sulfur‐containing allyl ester, which reacts with diallyl phthalate (DAP) resin to have allyl groups, was synthesized by the reaction of allyl phthalic acid with bisphenol having sulfur atoms. The sulfur‐containing allyl ester compound was blended with DAP resin to improve the adhesive properties to copper. By modification with sulfur‐containing allyl ester compound, the T‐peel adhesive strength and the lap shear adhesive strength to copper was improved. In particular, the adhesive strength was greatly improved when the resin was modified with the allyl ester compound having a disulfide bond (?S?S?) (DADS). It is concluded that this result is due to the improvement of the interfacial adhesive strength because the sulfur atom was found to be located in the surface of the copper by Fourier transform infrared (FTIR) analysis. The glass transition temperature (T_g) and the thermal decomposition temperature (T_d) of the cured DAP resin modified with DADS slightly decreased with increasing concentration of DADS. The lowering of T_g is because the crosslinking density of the DAP resin modified with DADS is smaller than that of DAP resin. Moreover, from thermogravimetric analysis, the lowering of Td of the DAP resin modified with DADS is because DADS is likely to pyrolyze. © 2013 Society of Chemical Industry     

Early Fixation of Cobalt-Chromium Based Alloy Surgical Implants to Bone Using a Tissue-engineering Approach

To establish the methods of demonstrating early fixation of metal implants to bone, one side of a Cobalt-Chromium (CoCr) based alloy implant surface was seeded with rabbit marrow mesenchymal cells and the other side was left unseeded. The mesenchymal cells were further cultured in the presence of ascorbic acid, β-glycerophosphate and dexamethasone, resulting in the appearance of osteoblasts and bone matrix on the implant surface. Thus, we succeeded in generating tissue-engineered bone on one side of the CoCr implant. The CoCr implants were then implanted in rabbit bone defects. Three weeks after the implantation, evaluations of mechanical test, undecalcified histological section and electron microscope analysis were performed. Histological and electron microscope images of the tissue engineered surface exhibited abundant new bone formation. However, newly formed bone tissue was difficult to detect on the side without cell seeding. In the mechanical test, the mean values of pull-out forces were 77.15 N and 44.94 N for the tissue-engineered and non-cell-seeded surfaces, respectively. These findings indicate early bone fixation of the tissue-engineered CoCr surface just three weeks after implantation.     

An IR study on ion-specific and solvent-specific swelling of poly(N-vinyl-2-pyrrolidone) gel

Swelling degrees of poly(N-vinyl-2-pyrrolidone) (PVP) gel were measured in aqueous salt solutions and in water/organic solvent mixtures to find marked ion- and solvent-specificities. In order to investigate any correlation of those specificities with hydration or solvation of PVP, IR spectra band of the CO group was monitored by means of ATR method both for PVP gel and the relevant solution systems. Dependence of the peak frequency on the swelling ratio suggested that hydration of PVP carbonyl group in deswollen gel systems is different from that in the corresponding solution systems. In the solution systems, PVP carbonyl band showed a high-wavenumber shift for deswollen systems, which can be well correlated with changes in water proton charge through ionic hydration and with Gutmann's acceptor number of organic solvents. In the deswollen gel systems, the CO band showed a low-wavenumber shift, suggesting a strong hydration or doubly hydrated state. This unexpected behavior was interpreted by assuming an intermolecular hydrogen bond of two carbonyl groups intermediated by water molecules.     

Novel organic-inorganic hybrids prepared from polybenzoxazine and titania using sol-gel process

Novel organic-inorganic hybrids were prepared from polybenzoxazine and titania using sol-gel process by blending titanium isopropoxide as a precursor for titania with a typical benzoxazine monomer, bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane (Ba). Deep red brown and transparent hybrid materials were obtained after thermal cure at 200 °C. DSC indicated that, in the presence of titania precursor, the onset and maximum temperature of the exothermic peak due to the ring opening polymerization of Ba decreased by ca. 30 and 70 °C, respectively. Viscoelastic analyses revealed that the glass transition temperatures (T_g) of the polybenzoxazine-titania hybrids shifted to higher temperature than the neat polybenzoxazine. The storage moduli below T_g for the hybrids increased with the increase of the titania content, and the storage moduli were maintained constant up to higher temperature than the neat resin. TGA results confirmed that the thermal stability and char yield of polybenzoxazine increased by hybridization with titania.     

Reduction of irreversible capacities of amorphous carbon materials for lithium ion battery anodes by Li2CO3 addition

Amorphous carbon materials for lithium ion battery anodes which contain a small amount of Li₂CO₃ were prepared by three methods. The obtained materials were characterized using X-ray diffraction (XRD) analysis, Raman spectroscopy and CO₂ adsorption experiments. Although the XRD profiles and Raman spectra of these materials were similar to those of carbon materials synthesized with no addition, the amount of CO₂ adsorbed was largely decreased by Li₂CO₃ addition. These results suggest that the micropores in these materials were plugged and/or filled with Li₂ CO₃. Galvanostatic lithium charging and discharging experiments showed that the irreversible capacity of the material can be significantly decreased by Li₂CO₃ addition, which is thought to be due to the plugging of the pore inlets by Li₂CO₃. Moreover, it was also found that the reversible capacities of the materials can be increased by adjusting both the amount of Li₂CO₃ addition and carbonization temperature.