Carboxymethylbetaine copolymer layer covalently fixed to a glass substrate.

A random copolymer of zwitterionic monomer, carboxymethylbetaine (CMB), and 3-methacryloyloxypropyl trimethoxysilane was prepared in ethanol using 2,2'-azobisisobutyronitrile as initiator. The incubation of ethanol solution of the copolymer with a glass plate gave a layer of the copolymer with a thickness of about 2-3 nm. The copolymer-modified glass substrate became highly hydrophilic upon immersion in water, and showed a resistance against non-specific adsorption of proteins, and the degree of resistance increased with the content of CMB residues in the copolymer and leveled off.

Silica particles coated with zwitterionic polymer brush: formation of colloidal crystals and anti-biofouling properties in aqueous medium.

Silica particles (SiP) were modified with 2-bromoisobutyryl group-carrying silane coupling reagent, and a polymer brush of carboxymethylbetaine, poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), was introduced onto surface of the particles using surface-initiated atom transfer radical polymerization (ATRP). After purification by simple ultrafiltration, the layer of the PolyCMB brush-carrying silica particle (SiP-PolyCMB) in aqueous medium showed a clear iridescence at the bottom of a quartz cell upon a slow sedimentation, indicating the formation of colloidal crystals due to both electrostatic and steric repulsion between the particles. The peak of the reflection spectra gradually shifted to a smaller wavelength region due to the formation of more densely packed ordered structure of the SiP-PolyCMB.

Image printing on the surface of anti-biofouling zwitterionic polymer brushes by ion beam irradiation.

A CMB monomer was polymerized on a glass plate with a surface-confined ATRP initiator containing a 2-bromoisobutyryl group. The glass plate modified with a PCMB brush was highly hydrophilic and showed a strong resistance against non-specific adsorption of proteins and cell adhesion. Upon ion beam irradiation, furthermore, the PCMB brush was ablated and a hollow space with a designed shape could be made to which HEK293 cells (from human embryonic kidney) and Hep G2 (from human hepatoma) cells non-specifically adhered, while no adhesion of these cells to the non-treated area on the brush was observed.

Temperature-responsive polymer-brush constructed on a glass substrate by atom transfer radical polymerization.

A polymer brush of 2-(2-methoxyethoxy)ethyl methacrylate (MDM) was prepared by atom transfer radical polymerization (ATRP) using a 11-(2-bromoisobutyroyloxy)undecyl moiety-carrying initiator covalently fixed to a glass substrate. An aqueous solution of the MDM polymer (E-PMDM), which had been prepared for comparison, turned to be opaque above certain temperature (26.2 °C for E-PMDM (M(n,GPC)=1.

Molecular recognition at the exterior surface of a zwitterionic telomer brush.

3-Sulfo-N,N-dimethyl-N-(2'-methacryloyloxyethyl)propanaminium inner salt (SPB) was polymerized on a glass plate with a surface-confined initiator of atom transfer radical polymerization (ATRP) having a 2-bromoisobutyryl group. The glass plate modified with a brush of sulfobetaine telomer (PSPB) was highly hydrophilic and showed a strong resistance against nonspecific adsorption of proteins such as lysozyme and albumin. Through the polymerization from the free surface of PSPB chain by ATRP, furthermore, N-methacryloyloxysuccinimide (MAOSu) residues were introduced, and the incubation of the telomer (PSPB-b-PMAOSu)-modified glass chip with a lectin (concanavalin A, Con A) gave a glass chip covered with the Con-A-modified PSPB brush.

Anti-biofouling properties of a telomer brush with pendent glucosylurea groups.

A thiol-group-carrying telomer with pendent D-glucosylurea groups [poly(glucosylureaethyl methacrylate)-SH (PolyGUMA-SH)] was obtained by reversible addition-fragmentation chain-transfer (RAFT) polymerization of GUMA in the presence of 4,4'-azobis(4-cyanopentanoic acid) (initiator) and 4-cyanopentanoic acid dithiobenzoate (chain-transfer agent) and subsequent reduction with NaBH4. The thiol-carrying telomer was accumulated on both a gold electrode and a colloidal gold-immobilized glass substrate as proven by cyclic voltammetry using hydroquinone as a probe, and the increase in absorbance at 550 nm was ascribable to localized surface plasmon resonance (LSPR), respectively. The adsorption of various proteins to the surface of the telomer brush was examined by the LSPR method, too.