The photo-block-graft-copolymerization method using an iniferter, benzyl N,N-diethyldithiocarbamate,
was utilized to design a biomedically functional surface for fabricated devices. Ultraviolet light irradiation
under sequential charge of vinyl monomers, such as acrylic acid (AA), n-butyl methacrylate (BMA), N,N-dimethylacrylamide (DMAAm), N-[3-(dimethylamino)propyl]acrylamide (DMAPAAm), or styrene (ST),
produced block-grafted surfaces, in which different polymer blocks were sequentially formed on polyST
(PST) partially derivatized with N,N-diethyldithiocarbamate groups. Examination of a cross-sectional
view under a transmission electron microscope (TEM) revealed a bilayered structure of the PST-b-PDMAAm
block-graft copolymer. Three different AB-type block-graft-copolymerized surfaces were prepared for
biomedical applications, where block A was the bottom layer and block B the top layer: (1) For heparin
immobilization, a polyPDMAPAAm (PDMAPAAm) (A)−polyDMAAm (PDMAAm) (B) block-graft-copolymerized surface was prepared, where the block A layer contained ionically immobilized heparin and
the block B layer functioned as a protective layer to suppress protein adsorption and cell adhesion. (2) For
protein immobilization, a PDMAAm (A)-polyAA (PAA) (B) block-graft-copolymerized surface was prepared,
where the block B layer covalently fixed the protein and the block A layer functioned as a protective layer
to prevent contact of the protein with the substrate. (3) For a drug-releasing surface, a PDMAAm (A)-polyBMA (PBMA) (B) block-graft-copolymerized surface was prepared, where the block A layer contained
the drug and the block B layer functioned as a barrier to regulate drug release. These macromolecularly
designed surfaces were characterized by X-ray photoelectron spectroscopy, and the immobilization of
heparin and protein was visualized by light microscopy, after staining with toluidine blue (for heparin),
and fluorescence microscopy (for protein).