Inclusion and Release of Hinokitiol into/from MCT-β-CD Fixed on Japanese Washi Paper

The potential for surface modification of paper by modified cyclodextrins was demonstrated by the model system of Japanese washi paper and monochlorotriazinyl-β-cyclodextrin (MCT-β-CD). MCT-β-CD was covalently bonded to the paper. The optimal bonded reaction conditions were found to be 10 min at 150 °C with a moisture content of less than 2.5 (g water/g dry paper). The bounded MCT-β-CD on the paper was able to include and release hinokitiol representing the group of antibacterial agents. The maximum molar inclusion ratio of hinokitiol in the immobilized MCT-β-CD was around 0.8. The release rates of hinokitiol, included in the fixed MCT-β-CD, were monitored at 50 °C for different relative humidities. The release rate was strongly influenced by the relative humidity. These results demonstrate that the antibacterial agent can be included and released from MCT-β-CD fixed on the paper. The antibacterial activity of the fixed hinokitiol against airborne microorganisms was demonstrated.     

Synthesis and radical polymerization behavior of bifunctional vinyl monomer derived from N‐vinylacetamide and p‐chloromethylstyrene

The radical polymerization of N‐(p‐vinylbenzyl)‐N‐vinylacetamide ( 1 ) prepared by the reaction of N‐vinylacetamide with p‐chloromethylstyrene was carried out by using radical initiators such as AIBN or BPO in benzene, chlorobenzene, or bulk. As a result, poly 1 was successfully isolated by dialysis (yield, 10–36%). The crosslinking reaction of poly 1 was carried out at 60–100 °C for 8 h. By using a radical initiator such as AIBN or BPO (3 mol %), the crosslinking reaction proceeded (yield, 63–79%). Moreover, the crosslinking reaction of poly 1 proceeded at 100 °C without a radical initiator in 50% yield. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2714–2723, 2006     

Estimation of secondary electron effect in the J-PARC rapid cycling synchrotron after first study

The J-PARC 3 GeV rapid-cycling synchrotron (RCS) is required to provide 1 MW pulsed protons to the spallation neutron target and the 50 GeV main ring. Since the RCS finally accelerates very high intensity beam such as 8.3 × 10¹³ ppp, the secondary electron cloud may affect the accelerator performance. We measured the secondary electron emission from the TiN coating surface and the ferrite sample. By using these measurement results, we estimated the effect of the electron cloud made by the emitted secondary electron at present beam parameters.     

Grafting of polymers onto and/or from silica surface during the polymerization of vinyl monomers in the presence of γ‐ray‐irradiated silica

The effects of radicals on silica surface, which were formed by γ‐ray irradiation, on the polymerization of vinyl monomers were investigated. It was found that the polymerization of styrene was remarkably retarded in the presence of γ‐ray‐irradiated silica above 60 °C, at which thermal polymerization of styrene is readily initiated. During the polymerization, a part of polystyrene formed was grafted onto the silica surface but percentage of grafting was very small. On the other hand, no retardation of the polymerization of styrene was observed in the presence of γ‐ray‐irradiated silica below 50 °C; the polymerization tends to accelerate and polystyrene was grafted onto the silica surface. Poly(vinyl acetate) and poly(methyl methacrylate) (MMA) were also grafted onto the surface during the polymerization in the presence of γ‐ray‐irradiated silica. The grafting of polymers onto the silica surface was confirmed by thermal decomposition GC‐MS. It was considered that at lower temperature, the grafting based on the propagation of polystyrene from surface radical (“grafting from” mechanism) preferentially proceeded. On the contrary, at higher temperature, the coupling reaction of propagating polymer radicals with surface radicals (“grafting onto” mechanism) proceeded to give relatively higher molecular weight polymer‐grafted silica. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2972–2979, 2006     

Simultaneous determination of mass-dependent isotopic fractionation and radiogenic isotope variation of strontium in geochemical samples by multiple collector-ICP-mass spectrometry.

We present a method to determine (88)Sr/(86)Sr and (87)Sr/(86)Sr simultaneously. The former variation reflects the mass-dependent isotopic fractionation through the physico-chemical processes, and the latter originates from beta(-)-decay of the parent nuclide (87)Rb as well as the mass-dependent isotopic fractionation. In order to determine the mass-dependent isotopic fractionation, the mass-discrimination effect on (88)Sr/(86)Sr was externally corrected by an exponential law using Zr. For the radiogenic growth of (87)Sr/(86)Sr, the mass-dependent isotopic fractionation effect on (87)Sr/(86)Sr was corrected by a conventional correction technique using the (88)Sr/(86)Sr ratio. The reproducibility of the (88)Sr/(86)Sr and (87)Sr/(86)Sr measurements for a high-purity Sr chemical reagent was 0.06 per thousand (2SD, n = 20) and 0.07 per thousand (2SD, n = 20), respectively. Strontium isotopic ratios ((88)Sr/(86)Sr and (87)Sr/(86)Sr) were measured on six geochemical reference materials (igneous rock: JB-1a and JA-2; carbonate mineral: JLs-1, JDo-1, JCp-1 and JCt-1) and one seawater sample. The resulting (87)Sr/(86)Sr ratios obtained here were consistent with previously published data within the analytical uncertainties. The resulting (88)Sr/(86)Sr ratios for igneous rock samples did not vary significantly within the samples, whereas the carbonate samples showed enrichments of the lighter Sr isotopes over the seawater sample. The (88)Sr/(86)Sr ratio of geochemical samples could reflect the physico-chemical processes for the sample formation. Also, a combined discussion of (88)Sr/(86)Sr and (87)Sr/(86)Sr of samples will render multi-dimensional information on geochemical processes.     

Precise control of microstructure of functionalized polypropylene synthesized by the ansa‐zirconocene/ MAO catalysts

We inclusively investigated polymerization behavior and structure of copolymer in the copolymerization of propylene and alkylaluminum‐protected polar allyl monomers. The control of the arrangement of polar group in the copolymer was discussed. It was proved that the location of polar group could be controlled by zirconocene catalyst and a kind of polar monomer. The indenyl or the 2‐methylindenyl ligands of zirconocene were favored to produce end‐functionalized polymers. It was also found that the trimethylaluminum‐protected allylamine and triisobutylaluminum‐protected allylmercaptan had superior ability in the synthesis of end‐functionalized polypropylene. On the other hand, the 2‐methyl‐4‐phenylindenyl ligand produced the copolymers containing both the end‐polar unit and inner‐polar unit at the polymer chains. Terpolymerization of propylene, polar allyl monomer, and 5‐hexen‐1‐ol was also conducted. The NMR study of the terpolymer revealed that both the 5‐hexen‐1‐ol and the polar allyl monomer were incorporated into the polymer chain. It has also become apparent that the polar allyl monomer units predominantly occupied the chain end, while the 5‐hexen‐1‐ol units were located at the inner of main chain. Consequently, we have achieved the synthesis of functionalized polypropylene in which the arrangement of polar group was precisely controlled. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1738–1748, 2008     

Anionic alternating copolymerization of a bifunctional six‐membered lactone and glycidyl phenyl ether: Selective synthesis of a linear polyester having lactone moiety

An imidazole‐initiated copolymerization of an aromatic bislactone, 10‐methyl‐2H,8H‐benzo[1,2‐b:5,4‐b′]bipyran‐2,8‐dione ( 1 ), and glycidyl phenyl ether (GPE) was investigated. In spite of the bifunctional nature of 1 that would potentially permit formation of networked and thus insoluble polymers upon its copolymerization, only one of the two lactone moieties of 1 exclusively underwent the copolymerization to give a linear polyester. Spectroscopic analysis of the polyester and its reductive scission into the corresponding fragment revealed that the polyester was formed by a 1:1 alternating copolymerization of GPE and the lactone moiety of 1 . The other lactone in 1 that did not participate in the copolymerization was quantitatively incorporated into the side chain of the polyester as a reactive site, of which ring‐opening reactions by amine and alcohol as nucleophilic reagents allowed chemoselective polymer reactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1661–1672, 2009