Morphology of composite polymer emulsion particles consisting of two kinds of polymers between which ionic bonding intermolecular interaction operates

The morphology of particles (I) produced by seeded emulsion copolymerization of styrene (S) and sodium p-styrene sulfonate (NaSS) with butyl acrylate (BA)-methacryloyloxyethyl-trimethylammonium chloride (QDM) copolymer particles as seed was examined in comparison with poly(butyl acrylate) (PBA)-polystyrene (PS) composite polymer emulsion particles (II). In an electron microscopic observation, it was observed that II particles had an anomalous shape and the electron densities at different points in the particle were heterogeneous, whereas I particles had an almost spherical shape and the electron densities were homogeneous. The maximum tensile strength and toughnes were much larger in II than I. The dynamic mechanical studies indicate that II film had a macroheterogeneous structure consisting of PS-rich and PBA-rich phases, whereas I film had a microheterogeneous structure. These ressults suggest that there is an effect of intermolecular interaction between polymers of different kinds on the formation of heterogeneous structure in particles consisting of two kinds of polymers.     

Detection of six single-nucleotide polymorphisms associated with rheumatoid arthritis by a loop-mediated isothermal amplification method and an electrochemical DNA chip

An electrochemical DNA chip using an electrochemically active intercalator and DNA probe immobilized on a gold electrode has been developed for genetic analysis. In this study, the six polymorphisms associated with rheumatoid arthritis (RA), N-acetyltransferase2 (NAT2) gene polymorphisms T341C, G590A, and G857A, methylenetetrahydrofolate reductase (MTHFR) gene polymorphisms C677T and A1298C, and serum amyloid A1 (SAA1) gene promoter polymorphism C-13T were simultaneously detected by the electrochemical DNA chip and the loop-mediated isothermal amplification (LAMP) method, which is a novel technique for DNA amplification. Human genomic DNAs were extracted from blood, and the targets containing the six polymorphisms were amplified by the LAMP method. A sample containing the six LAMP products was reacted with the electrochemical DNA chip using a DNA detection system that controls hybridization reaction, washing, electrochemical detection, and data analysis automatically. A total of 31 samples were genotyped by this method, and the results were completely consistent with those determined by the polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) analysis or the PCR direct sequence analysis. The time required for this method was only 2 h, and operations were very simple. Therefore, this method is expected to contribute to personalized medicine based on genotype.     

Surface grafting of polymers onto glass plate: Polymerization of vinyl monomers initiated by initiating groups introduced onto the surface

The surface grafting of polymers onto a glass plate surface was achieved by the polymerization of vinyl monomers initiated by initiating groups introduced onto the surface. Azo groups were introduced onto the glass plate surface by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with isocyanate groups, which were introduced by the treatment with tolylene-2,4-diisocyanate. The radical polymerization of various vinyl monomers was initiated by azo groups introduced onto the glass plate surface and the corresponding polymers were grafted from the surface: The surface grafting of polymers was confirmed by IR spectra, and the contact angle of surface, with water. The contact angle of the glass plate increased by the grafting of hydrophobic polymers, but decreased by the grafting of hydrophilic polymers. The radical postpolymerization was successfully initiated by the pendant peroxycarbonate groups of grafted polymer on the surface to give branched polymer-grafted glass plate. The cationic polymerization of vinyl monomers was also successfully initiated by benzylium perchlorate groups introduced onto the glass plate surface and the corresponding polymers were grafted onto the surface. The contact angle of the glass plate surface obtained from the cationic polymerization of styrene was larger than that obtained from the radical polymerization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2165–2172, 1997     

Novel poly-gamma-glutamate-processing enzyme catalyzing gamma-glutamyl DD-amidohydrolysis

The pgdS gene product of Bacillus subtilis, PgdS, cleaves poly-gamma-glutamate (PGA) in an endo-peptidase-like fashion. However, its catalytic property remains obscure. In this study, a simple assay for the PgdS enzyme using 1-fluoro-2,4-dinitrobenzene was developed, and some characteristics of PgdS, such as optimal pH, were examined. The enzyme was strongly inhibited by a thiol-modifying reagent, suggesting that it possesses essential cysteine residue(s) in catalysis. PgdS exhibited a high affinity to PGA that consisted mainly of D-glutamate residues, but no affinity to PGA composed only of L-glutamate residues (L-PGA). The enzyme processed DL-copolymer-type PGA (DL-PGA) with an average molecular mass of 1,000 kDa to a high-molecular-mass L-glutamate-rich fragment (average 200 kDa), the L-rich PGA fragment, and low-molecular-mass fragment composed mostly of D-glutamate residues (average 5 kDa), D-fragment. To deepen our understanding of the catalytic property of the PgdS enzyme, we analyzed the structures of the N- and C-terminal regions and found that D-glutamyl residues successively lie even at both ends of the L-rich PGA fragment. Our observations indicate that PgdS is a novel endo-peptidase that specifically cleaves the gamma-amide linkage between two D-glutamate residues in PGA, i.e., gamma-glutamyl DD-amidohydrolase. The enzyme is possibly useful in the biochemical processing of B. subtilis DL-PGA.     

Metal ion assembly in macromolecules

Self-assembled organic-inorganic hybrid nano-materials have recently received much attention due to their novel and original functions, including new electronic, optical, magnetic, and catalytic properties. Especially, reactions in organic-metallic hybrid materials are closely related to biological reactions, such as the reactions in metal-containing protein, and the controlled metal ions assembly into organic polymers becomes very important. In the first part of this review, recent progresses in two types of organic-inorganic hybrid nano-materials (Organic compounds [character: see text] inorganic mesoporous materials and Metal ions [character: see text] organic polymer) are summarized. In the latter parts, dendrimer-metal complexes, examples of nature-mimetic materials, are introduced, and their controlled metal assembly in dendrimer and their application are reviewed.     

FTIR studies of adsorption and photocatalytic decomposition under UV irradiation of dimethyl sulfide on calcium hydroxyapatite

The adsorption and photocatalytic decomposition under UV irradiation of dimethyl sulfide ((CH₃)₂S: DMS) on synthetic colloidal calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂: Hap) particles were examined by in vacuo IR measurements. The adsorption isotherms of DMS on Hap exhibited the Langmuir type. The saturated adsorbed amount of DMS was increased with increasing the outgassing temperature of Hap, showing a maximum of 2.4 molecules/nm² at 250 °C. Similar tendency could be observed for change in area intensity of surface P-OH bands of Hap estimated from in vacuo IR measurements against outgassing temperature. By adsorption of DMS, the surface P-OH bands of Hap weakened while the CH bands due to DMS appeared. These results revealed that the DMS was adsorbed on surface P-OH groups of Hap. When the UV light was irradiated to the DMS-adsorbed Hap, the surface P-OH bands revived and the CH bands weakened. This fact strongly indicated the photocatalytic decomposition of DMS took place on surface P-OH groups of Hap, which was thought to be due to the formation of surface P-OH radicals by UV irradiation.     

Fabrication of conductive porous alumina (CPA) structurally modified with carbon nanotubes (CNT)

A novel binary porous composite nano-carbon networks (NCNs)/alumina, which is denoted as electrically conductive porous alumina (CPA), was structurally modified by carbon nanotubes (CNT) pre-treated with mixed concentrated acids at 60 °C for 6 h in this study. This conductive ceramics (CCs) was fabricated by combination of gelcasting and high temperature reductive sintering (HTRS) in novel atmosphere. CNT pre-treatment leading to the increased hydrophilicity makes it possible to make uniformly dispersed CNT/alumina slurry. And by HTRS in Ar at 1700 °C for 2 h, well-gelled polymer net-paths in green body prepared by gelcasting technology were totally converted to nano-carbon networks (NCNs) without destruction of CNT. NCN with graphitic crystal structure was evaluated by Raman spectroscopy in sintered ceramic body. Moreover, comparing with as-received CNT, the decreased surface defect of detected composite also supported the further graphitization of CNT via HTRS in Ar instead of burning out. With the aid of field-emission scanning electronic microscopy (FE-SEM) observation, the increased alumina grains in sintered ceramic body CNT/NCN/alumina was valid. Moreover, it was demonstrated that there were three components in this composite, which is carbon filler with two different forms (CNT and NCN) and alumina matrix. And these three components CNT covered with Al₂O₃ particles (Al₂O₃/CNT), NCN and alumina grains (alumina) co-exist in four different situations as follows: (a) Al₂O₃/CNT–alumina co-junction, (b) Al₂O₃/CNT–NCN co-junction, (c) Al₂O₃/CNT–alumina–NCN and (d) Al₂O₃/CNT mesh between alumina boundaries. Furthermore, by comparing with binary composite NCN/alumina (CPA), the increased flexural strength of ternary composite CNT/NCN/alumina (CNT/CPA) up to 38 MPa was attributed to the reinforcement CNT acting as elastic bridge in composite.     

Infinite multiplication factor of low-enriched UO2–concrete system

The possibility of criticality of fuel debris in a form of uranium dioxide (UO₂)–concrete mixture is evaluated by calculating the infinite multiplication factor (k _∞) for a study of criticality control on the fuel debris generated through the molten core concrete interaction in a severe accident of a light water reactor. The infinite multiplication factor can be greater than unity, which means that handling of the mixture is subject to criticality control. This paper shows that concrete provides efficient neutron moderation and points out the necessity of further investigations on the criticality of UO₂–concrete system for actual handling of fuel debris.     

ESR study of silica‐filled SBR with different rubber/filler interactions

Silica‐filled styrene–butadiene rubber (SBR) unvulcanizates and their vulcanizates with different rubber/filler interactions were prepared by using several kinds of coupling agents. Tensile tests and electron spin resonance (ESR) measurements were carried out for both unvulcanized and vulcanized samples to get information on the effects of filler/rubber interactions on the breakdown of carbon–carbon (C? C) linkages in SBR and carbon–sulfur (C? S? C, C? S? S? C) linkages at the crosslinked points between rubber and sulfur by a tensile force. The combination of ESR results and stress–strain data suggested that with increasing the mechanical energy applied to the samples by the stretching, the carbon–sulfur linkages around silica particles were broken first, followed by the breakdown of carbon–sulfur and C? C linkages in the rubber matrix. The assignment of ESR spectrum was also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of substrate bias voltage on the properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

Diamond-like carbon (DLC) thin films were deposited on silicon and ITO substrates with applying different negative bias voltage by microwave surface wave plasma chemical vapor deposition (MW SWP-CVD) system. The influence of negative bias voltage on optical and structural properties of the DLC film were investigated using X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Optical band gap of the films decreased from 2.4 to 1.7 with increasing negative bias voltage (0 to − 200 V). The absorption peaks of sp³ CH and sp² CH bonding structure were observed in FT-IR spectra, showing that the sp²/sp³ ration increases with increasing negative bias voltage. The analysis of Raman spectra corresponds that the films were DLC in nature.