9 Environmentally Friendly Synthesis of Polymer-Grafted Nanoparticles
Inorganic nanoparticles such as silica, and titanium oxide, are widely used industrially as fillers and pigments for polymer materials, because inorganic nanoparticles have excellent properties such as chemical, heat and weather resistance, lightweight, thermal conductivity and low thermal expansion. On the other hand, nanocarbons, such as carbon black, nanodiamond, and carbon nanotube, are well known as one of the industrially important carbon materials. Carbon materials also have outstanding properties such as electro-conductivity, heat-resistance, biocompatibility, and chemical-resistance. Carbon nanotubes in particular have attracted attention as nanotechnology related materials. In general, dispersing inorganic nanoparticle and nanocarbons uniformly into a polymer or an organic solvent is very difficult because of aggregation. In addition, the mechanical properties of polymer composite from nanoparticles and nanocarbons are considered to depend on not only the mechanical properties of the polymer matrix but also on the properties of interfacial regions between surface of nanoparticles and matrix polymers. The chemical and physical modifications of inorganic nanoparticle and nanocarbon surfaces, therefore, have been extensively studied. The chemical modification of surfaces is permanent, but physical modification is temporary. We have pointed out that the dispersibility of silica nanoparticles and nanocarbons is extremely improved by surface grafting of polymers, namely, chemical binding of polymers, onto nanoparticle and nanocarbon surfaces (Tsubokawa, 1999; Tsubokawa, 2002; Tsubokawa, 2007). In addition grafting of polymers onto these surfaces interests us for designing new functional composite materials which have the excellent properties both of nanoparticles as mentioned above and of grafted polymers, such as photosensitivity, biorepellent activity, antibacterial activity, and pharmacological activity (Tsubokawa, 2007). We have succeeded in the grafting of various polymers such as vinyl polymer (Tsubokawa et al., 1988a; Tsubokawa et al., 1990; Fujiki et al., 1990; Tsubokawa et al., 1992a), polyester (Tsubokawa et al., 1982; Tsubokawa et al., 1983), polyether (Tsubokawa et al., 1986; Tsubokawa et al., 1988b), poly(organophosphazene) (Tsubokawa et al., 1992b), and poly(dimethysiloxane) (Tsubokawa et al., 1992c) onto silica nanoparticle and carbon black surfaces using surface functional groups as grafting sites. Furthermore, many experimental attempts by other researchers also have been made to graft polymers onto silica nanoparticle and carbon black surfaces.
Introduction of peroxide groups onto carbon black surface by radical trapping and radical graft polymerization of vinyl monomers initiated by the surface peroxide groups
The introduction of peroxide groups onto carbon black surface was achieved through the trapping of the peroxide radicals formed by the decomposition of polymeric peroxide, such as poly(tetraethylene glycol peroxyadipate) (ATPPO), and bis-peroxide, such as 1,1′-bis (t-butyldioxy)cyclohexane (Perhexa-C), by the surface: the amount of peroxide groups introduced onto carbon black surface by the treatment with ATPPO and Perhexa-C were determined to be 0.07 mmol/g and 0.12 mmol/g, respectively. The polymerization of vinyl monomers with positive e-value, such as methyl methacrylate and 2-hydroxyethy methacrylate, was successfully initiated by the peroxide groups introduced onto carbon black surface. During the polymerization, the corresponding polymers were effectively grafted onto the surface as a result of the propagation of polymer from the surface radicals formed by decomposition of the peroxide groups. The polymerization of vinyl monomers with negative e-value, such as styrene and vinyl acetate, however, was scarcely initiated by the peroxide groups on carbon black. This may be due to the fact that surface active radicals, which were formed by the hydrogen abstraction from carbon black by fragment radicals, inhibit the polymerization of vinyl monomers with negative e-value. © 1996 John Wiley & Sons, Inc.
Stereoselective interaction between the R enantiomer of warfarin and cimetidine.
The stereoselectivity of the pharmacokinetic interaction between warfarin and cimetidine was investigated in eight healthy volunteers. The warfarin enantiomers were given separately as single doses (15 mg) alone and during chronic administration of cimetidine (1 g day-1). Cimetidine did not interact with S warfarin but there was an interaction with the R enantiomer of warfarin. Cimetidine caused a significant increase in the mean plasma half-life of R warfarin (from 47.8 h to 57.8 h) and a significant decrease in its mean plasma clearance (from 2.3 to 1.7 ml h-1 kg-1) (P less than 0.02). Administration of a pharmacological dose of vitamin K1 together with the enantiomers of warfarin was necessary clinically and resulted in elevation of vitamin K1 2,3-epoxide concentrations, which were similar in each case.