Mamiko Narita

Diblock copolymer of bacterial cellulose and poly(methyl methacrylate) initiated by chain-end-type radicals produced by mechanical scission of glycosidic linkages of bacterial cellulose.

Bacterial cellulose (BC) was mechanically fractured in vacuum at 77 K; this resulted in the scission of the β-1,4 glycosidic linkages of BC. The chain-end-type radicals (mechanoradicals) generated from the scissions were assigned by electron spin resonance (ESR) spectral analyses. A diblock copolymer of BC and poly(methyl methacrylate) (BC-block-PMMA) was produced by the mechanical fracture of BC with MMA (methyl methacrylate) in vacuum at 77 K. Radical polymerization of MMA was initiated by the mechanoradicals located on the BC surface. The BC surface was fully covered with the PMMA chains of the BC-block-PMMA. Novel modification of the BC surface with the BC-block-PMMA was confirmed by spectral analyses of ESR, Fourier-transform infrared, (1)H NMR, and gel permeation chromatography.

Virus-templated photoimprint on the surface of an azobenzene-containing polymer.

A photoimprint-based immobilization process is presented for cylindrical viruses on the surface of an azobenzene-bearing acrylate polymer by using atomic force microscopy (AFM). Tobacco mosaic virus (TMV), 18 nm in diameter and ca. 300 nm in length, was employed as a model virus. First, a droplet of an aqueous solution containing TMV was placed on the acrylate polymer surface. After drying the droplet, the polymer surface was irradiated with light at a wavelength of 470 nm from blue-light-emitting diodes. Finally, the surface was washed by aqueous solution with detergents. The polymer surface was observed at each step by AFM. TMV was shown to embed itself gradually on the polymer surface during photoirradiation in a time scale of tens of minutes because of the formation of the surface groove complementary to the shape of TMV. Analysis of immobilization efficiency of TMV on the polymer surface by the immunological enzyme luminescence indicated that efficiency increased proportional to the photoirradiation time. In these experimental conditions, the absorption band of the azobenzene moiety remained constant before and after the photoirradiation. These results show that TMV is physically held on the complementary groove formed on the polymer surface by the photoirradiation.

Orientation Control of Photo‐Immobilized Antibodies on the Surface of Azobenzene‐Containing Polymers by the Introduction of Functional Groups

In our photo-induced immobilization technique for an antibody (IgG) using azopolymers, the introduction of COOH and NMe(2) into the azopolymers, which can introduce surface charges, strongly affected the immobilization properties such as the efficiency of immobilization and the activity of the immobilized IgG (i.e., the orientation of the immobilized IgG). The introduction of COOH promoted a more active orientation of the immobilized IgG. The orientation was determined during the adsorption process onto the azopolymer surface in solution before photo-immobilization, and was maintained during the photo-immobilization. The surface charge of the azopolymer appears to be an important factor for IgG orientation, which involves electrostatic interactions between its Fab and the azopolymer surface.

Surface-assisted unidirectional orientation of ZnO nanorods hybridized with nematic liquid crystals.

Inorganic semiconductor nanorods are regarded as the primary components of optical and electrical nanoscale devices. In this paper, we demonstrate the unidirectional alignment of monolayered and dispersed ZnO nanorods on a rubbed polyimide alignment layer, which was achieved by a conventional liquid crystal alignment technique. The outermost surfaces of the ZnO nanorods (average diameter 7 nm; length 50 nm) were modified by polymerization initiator moieties, and nematic liquid crystalline (LC) methacrylate polymers were grown by atom transfer radical polymerization. By regulating the densities of the polymerization initiator moieties, we successfully hybridized LC-polymer-grafted ZnO nanorods and small nematic LC molecules. The LC-polymer-modified ZnO nanorods were hierarchically aligned on the substrate via cooperative molecular interactions among the liquid crystal mesogens, which induced molecular orientation on the rubbed polyimide alignment layer.