Block-graft Copolymers Research Articles

Synthesis of nanocylinders consisting of graft block copolymers by the photo‐induced ATRP technique

AbstractPhotoinduced atom transfer radical polymerizations (ATRP) of t‐butyl methacrylate (BMA) were carried out, initiated by model initiator benzyl N,N‐diethyldithiocarbamate (BDC) in the presence of CuCl/bipyridine (bpy) under UV irradiation. We performed the first‐order time‐conversion plots in this polymerization system, and the straight line in the semilogarithmic coordinates indicated a first‐order in the monomer. The molecular weight of poly(t‐butyl methacrylate) (PBMA) increased in direct proportion to monomer conversion. The molecular weight distribution (Mw/Mn) of PBMA was about 1.3. The initiator efficiency, f, was close to 1.0, which indicated that no side reactions occurred. A copper complex, CuCl/bpy, reversibly activated the dormant polymer chains via a N,N‐diethyldithiocarbamate (DC) transfer reaction such as Cu(DC)Cl/bpy, and it was dynamic equilibrium that was responsible for the controlled behavior of the polymerization of BMA. On the basis of this information, we established a preparation method of nanocylinders consisting of graft block copolymers by grafting from photoinduced ATRP of multifunctional polystyrene having DC pendant groups with vinyl monomers [first monomer, BMA; second monomer, styrene or methyl methcrylate (MMA)]. We have carried out the characterization of such nanocylinders in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 63–70, 2005

Graft polymerization of polysilsesquioxane containing chloromethylphenyl groups by atom transfer radical polymerization

AbstractPolysilsesquioxane with phenyl and chloromethylphenyl groups (PCPSQ) was prepared readily from phenyltrimethoxysilane and [2‐(chloromethylphenyl)ethyl]trimethoxysilane under acidic conditions. Polymerization with chloromethylphenyl groups on PCPSQ with methyl methacrylate (MMA) was conducted in the presence of a catalytic amount of copper(I) bromide and (−)‐sparteine. Atom transfer radical polymerization yielded a graft polymer (PCPSQ‐g‐MMA) efficiently, and no gelation was observed. The process was also applied to the preparation of graft block copolymers on PCPSQ with several methacrylate monomers. An advantage of the graft hybrid polymers was shown in improved thermal behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4212–4221, 2004

Synthesis of Well-Defined High-Density Branched Polymers Carrying Two Branch Chains in Each Repeating Unit by Coupling Reaction of Benzyl Bromide-Functionalized Polystyrenes with Polymer Anions Comprised of Two Polymer Segments

A series of high-density branched polymers have been synthesized by the coupling reaction of poly(4-(3-(4-bromomethylphenyl)propyl)styrene with polymer anion comprised of two same or different polymer chains, prepared from polystyryllithium and either polystyrene or polyisoprene with 1,1-diphenylethylene chain-end functionalization. Under certain conditions, the reaction proceeded essentially quantitatively to afford the requisite extremely high-density branched polymers carrying two branch chains in each repeating unit and having Mw values of up to 3 × 106. Furthermore, quite new graft-block copolymers with similar high-density branched architectures could also be successfully synthesized. The resulting polymers are well-defined in branched architecture and precisely controlled in chain lengths of both backbone and branch segments. It was however observed that the reaction efficiency was significantly affected by several variables such as degrees of polymerization of the backbone polymer and polymer anion and branched and chemical structures of the polymer anion. The structures of the resulting high-density branched polymers were investigated by intrinsic viscosity measurement. These polymers may possibly adopt starlike structures in toluene as evidenced by their g‘ values.

Synthesis of styrene-methyl methacrylate graft and block-graft copolymers via combination of atom transfer radical polymerization and stable free radical polymerization

Styrene (St)-methyl methacrylate (MMA) graft and block-graft copolymers were prepared by combination of atom transfer radical polymerization (ATRP) and stable free radical polymerization (SFRP). In the first step, MMA and comonomer 2-phenyl-2-[(2,2,6,6-tetramethylpiperidino)oxy]ethyl methacrylate were polymerized in the presence of ethyl-2-bromo isobutyrate by ATRP in order to give suitable macroinitiator for the following SFRP step of St. Alternatively, first SFRP of St was carried out by using a dual initiator, 2-phenyl-2-[(2,2,6,6-tetramethylpiperidino)oxy]ethyl 2-bromopropanoate, yielding macroinitiator to be used in ATRP of MMA and the comonomer. The corresponding block copolymer was used as a polyfunctional macroinitiator in SFRP of St to yield final block-graft copolymer. The obtained graft and block-graft copolymers were characterized by 1H-NMR, UV-Vis and GPC measurements.

New methodology for synthesizing polyolefinic graft block copolymers and their morphological features

AbstractThis paper describes a new synthetic route for polyolefinic graft block copolymers by adopting coupling reaction between terminally hydroxylated polyolefins and maleic anhydride grafted polyolefins. Terminally hydroxylated polypropylene (PP‐OH) was coupled with maleic anhydride modified polyethylene (PE‐g‐MAH) and such ethylene‐propylene random copolymer (EPR‐g‐MAH) to give polyolefinic graft block copolymers (PE‐g‐PP and EPR‐g‐PP, respectively). The formation of PE‐g‐PP was confirmed by enhancement on molecular weight and it brought about distinctive decrease in size of dispersed domain in its phase separation morphology. Occurrence of coupling reaction to give EPR‐g‐PP was indicated by extreme decrease in its solubility to n‐decane and it led to unique morphology demonstrating lamella microstructure that had never been reported for a comparable polyolefin composite.

Formation and Morphology of Methacrylic Polymers and Block Copolymers Tethered on Polymer Microspheres

We report the use of atom transfer radical polymerization (ATRP) to graft off polymeric microspheres. Residual vinyl groups on nonswellable poly(divinylbenzene-80) microspheres were converted into ATRP initiators by hydroboration/oxidation followed by esterification. Subsequent grafting by ATRP of poly(hydroxylethyl methacrylate) (poly(HEMA)) and poly((dimethylamino)ethyl methacrylate) (poly(DMAEMA)) led to hydrophilically modified microspheres. The surface properties of these microspheres, FT-IR spectra, and potentiometric titration confirm the successful modification. In addition, swellable, lightly cross-linked poly(DVB-co-HEMA) microspheres were modified in a similar manner by grafting, i.e., methyl methacrylate (MMA) and glycidyl methacrylate (GMA), to form graft block copolymers including poly(MMA-b-DMAEMA), poly(MMA-b-trimethylammonium ethylmethacrylate (TMAEMA)), and poly(MMA-b-GMA). Microphase separation of the grafted amphiphilic block copolymers was studied by scanning electron microscopy. The microspheres modified with poly(MMA-b-DMAEMA) and poly(MMA-b-TMAEMA) show polyelectrolyte properties.

Synthesis of Polyethylene Graft Block Copolymers from Styrene, Butyl Acrylate, and Butadiene

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTSynthesis of Polyethylene Graft Block Copolymers from Styrene, Butyl Acrylate, and ButadieneNed B. Bowden, Michaela Dankova, Willy Wiyatno, Craig J. Hawker, and Robert M. WaymouthView Author Information Center for Polymer Interfaces and Macromolecular Assemblies, Departments of Chemistry and Chemical Engineering, Stanford University, IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099 Cite this: Macromolecules 2002, 35, 25, 9246–9248Publication Date (Web):November 8, 2002Publication History Received5 April 2002Published online8 November 2002Published inissue 3 December 2002https://doi.org/10.1021/ma020544gCopyright © 2002 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views787Altmetric-Citations33LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (54 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Copolymerization,Copolymers,Graft polymerization,Homopolymers,Polymers Get e-Alerts

Grafting of Poly(alkyl (meth)acrylates) from Swellable Poly(DVB80-co-HEMA) Microspheres by Atom Transfer Radical Polymerization

We report the graft polymerization of methyl acrylate (MA), methyl methacrylate (MMA), hydroxyethyl methacrylate (HEMA), and 2-(dimethylamino)ethyl methacrylate (DMAEMA) by atom transfer radical polymerization (ATRP) from lightly cross-linked poly(DVB80-co-HEMA) microspheres. These poly(DVB80-co-HEMA) microspheres were prepared by precipitation copolymerization and subsequently modified by reaction with 2-bromopropionyl bromide to serve as ATRP macroinitiators. MMA, MA, and HEMA were then grafted from these initiator microspheres at room temperature using CuBr/Me4cyclam as catalyst. The graft sites, and hence the grafted polymers, are distributed throughout the initiator microspheres. Addition of a second monomer formed grafted block copolymers, indicating that a significant portion of the first grafts could be reactivated. The final particles represent novel, high-capacity polymer supports comprised of swellable core particles carrying 5.09 and 5.18 mmol/g of grafted poly(DMAEMA) and poly(MMA-b-DMAEMA), respectively. The grafted particles were characterized using ESEM, FTIR, Coulter particle sizing, and potentiometric titration.

Design and formulation of polyplexes based on pluronic-polyethyleneimine conjugates for gene transfer.

Previously, we reported the evaluation of several polyplex-based gene delivery systems with respect to their effectiveness, toxicity, and cell type dependence in vitro. One system, P123-g-PEI(2K), a cationic graft block copolymer, is of particular interest as it has been demonstrated to successfully deliver genetic material to murine liver following systemic delivery [Nguyen, H. K., Lemieux, P., Vinogradov, S. V., Gebhart, C. L., Guerin, N., Paradis, G., Bronich, T. K., Alakhov, V. Y., and Kabanov, A. V. (2000) Evaluation of Polyether-Polyethyleneimine Graft Copolymers as Gene Transfer Agents. Gene Ther. 7, 126-138 (1)]. The P123-g-PEI(2K) system requires nonmodified Pluronic P123 as an excipient to stabilize the dispersion. The purpose of the current work was to more closely characterize this system, to assess the role of each component of the system to the overall transfection process. We evaluated particle size, stability, and resistance to nuclease degradation. In addition, cellular uptake and localization of plasmid, as well as transgene expression, were evaluated following in vitro transfection of prostate cancer cells (PC-3) with various individual components of the system. Nonmodified Pluronic alone did not significantly enhance DNA uptake, transgene expression, or DNase protection. Therefore, we conclude that nonmodified Pluronic acted primarily by optimizing the size of the polyplex. Furthermore, though this system displays several characteristics thought desirable of a nonviral gene delivery system, these studies did discriminate a potential limitation of this system for in vivo applications, namely, the insufficient level of protection of plasmid DNA from nuclease degradation. This may limit the effective dose delivered, as well as limiting the effective circulation time. These studies provide vital information that will guide modification of this system to enhance the current in vivo profile.

Synthesis of amphiphilic block–graft copolymers [poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)‐g‐poly(acrylic acid)] and their aggregation in water

AbstractNovel block–graft copolymers [poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)‐g‐poly(tert‐butyl acrylate)] were synthesized by the atom transfer radical polymerization (ATRP) of tert‐butyl acrylate (tBA) with chloromethylated poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) as a macromolecular initiator. The copolymers were composed of triblock SEBS as the backbone and tBA as grafts attached to the polystyrene end blocks. The macromolecular initiator (chloromethylated SEBS) was prepared by successive hydrogenation and chloromethylation of SEBS. The degree of chloromethylation, ranging from 1.6 to 36.5 mol % according to the styrene units in SEBS, was attained with adjustments in the amount of SnCl4 and the reaction time with a slight effect on the monodispersity of the starting material (SEBS). The ATRP mechanism of the copolymerization was supported by the kinetic data and the linear increase in the molecular weights of the products with conversion. The graft density was controlled with changes in the functionality of the chloromethylated SEBS. The average length of the graft chain, ranging from a few repeat units to about two hundred, was adjusted with changes in the reaction time and alterations in the initiator/catalyst/ligand molar ratio. Incomplete initiation was detected at a low conversion; moreover, for initiators with low functionality, sluggish initiation was overcome with suitable reaction conditions. The block–graft copolymers were hydrolyzed into amphiphilic ones containing poly(acrylic acid) grafts. The aggregation behavior of the amphiphilic copolymers was studied with dynamic light scattering and transmission electron microscopy, and the aggregates showed a variety of morphologies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1253–1266, 2002

日本膜学会膜学研究奨励賞（２００２年）受賞論文 多成分系高分子膜の構造と有機液体混合液の透過分離特性に関する研究

This paper describes the relationship between structures of multicomponent polymer membranes and their permselectivity for organic liquid mixtures in pervaporation. The morphology of microphase separation in the multicomponent polymer membranes containing poly (dimethylsiloxane) (PDMS) was quite different between block copolymer membranes and graft copolymer ones. The annealing of the block copolymer membranes resulted in dramatic changes in the morphology of their microphase separation, but that of the graft copolymer membranes did not. Their morphology strongly influenced the membrane permselectivity for organic liquid mixtures in pervaporation. This paper also focuses on simple surface modifications of membranes by polymer additives. Surface characteristics of polymer membranes were controlled by adding hydrophilic and hydrophobic copolymer additives. The permselectivity of the surface-modified membranes was improved without lowering their permeability by the simple surface modification. The addition of calixarene to microphase-separated membranes improved the permselectivity for volatile organic compounds in dilute aqueous solutions. Our results suggest a novel concept for designing the structure of multicomponent polymer membranes, that is, a method for controlling the permselectivity of pervaporation membranes.

Architecture of nanostructured polymers by segregated domain crosslinking of block‐graft copolymer micelles

Polystyrene-block-polyisoprene (PS-block-PI; high 3,4-structure) diblock copolymer was prepared by living anionic polymerization. For transfer into a reactive intermediate, the hydroxylation of the double bonds of PI block was achieved by hydroboration, followed by oxidation. Esterification of the hydroxy-derivative with stearoyl chloride or decanoyl chloride resulted in block-graft copolymers composed of PS (flexible chain)-grafted long alkane (stretched chains). After partial chloromethylation of PS block copolymer, photofunctional N,N-diethyldithiocarbamate (DC) groups were introduced into such pendant sites by reaction with the corresponding sodium salt. We studied the self-assemblies of photofunctional block-graft copolymers in a selective solvent, such as heptane, and constructed nanostructured polymers by crosslinking PS cores under UV irradiation. © 2001 Society of Chemical Industry

Synthesis of Block Graft Copolymer with Syndiospecific Living Polymerization of Styrene Derivatives by (Trimethyl)pentamethylcyclopentadienyltitanium/Tris(pentafluorophenyl)borane/Trioctylaluminium Catalytic System

Two kinds of syndiotactic AB type block copolymers were prepared, which were (1) poly(4-methylstyrene)-block-polystyrene {Poly(4MS-b-S), (A: poly(4MS), B: polystyrene (S))}, (2) poly(4-methylstyrene)-block-poly(styrene-co-3-methylstyrene) {poly[4MS-b-(S-co-3MS)] (A: poly(4MS), B: styrene/3-methylstyrene (3MS) copolymer)}. For the syntheses of these diblock copolymers, the living polymerization catalytic system composed of (trimethyl)pentamethylcyclopentadienyltitanium (Cp*TiMe3) premixed with trioctylaluminium (AlOct3), and tris(pentafluorophenyl)borane (B(C6F5)3) was used at –25°C. Chlorination of the methyl groups of poly[4MS-b-(S-co-3MS)] was conducted by aqueous sodium hypochlorite (NaOCl) and phase-transfer catalyst such as tetrabutylammonium hydrogensulfate (TBAHS). The novel tapered densely grafted diblock copolymer was synthesized with by coupling reaction of living poly(2-vinyl pyridine)lithium (Poly(2VP)Li) with the partly chloromethylated poly[4MS-b-(S-co-3MS)].

Evaluation of polyplexes as gene transfer agents

Non-viral transfection systems based on the complexes of DNA and polycations (‘polyplexes’) were evaluated with respect to their effectiveness, toxicity and cell type dependence in a variety of in vitro models. The panel of polycations examined included branched and linear polyethyleneimines, poly[ N-ethyl-4-vinyl pyridinium bromide], polyamidoamine dendrimer (Superfect™), poly(propyleneimine) dendrimer (Astramol™) and a conjugate of Pluronic ® P123 and polyethyleneimine (P123-g-PEI(2K)), having a graft-block copolymer architecture. Using a panel of cell lines the linear polyethyleneimine ExGen™ 500, Superfect™, branched polyethyleneimine 25 kDa, and P123-g-PEI(2K) were determined as systems displaying highest transfection activity while exhibiting relatively low cytotoxicity. These systems had activity higher than or comparable to lipid transfection reagents (Lipofectin ®, LipofectAMINE™, CeLLFECTIN ® and DMRIE-C) but did not reveal serum dependence and were less toxic than the lipids. Overall, this study demonstrates good potential of structurally diverse polyplex systems as transfection reagents with relatively low cytotoxicity.

Preparation of AB-type diblock copolymers containing poly-(2,6-dimethyl-1,4-phenylene oxide) and methyl methacrylate or styrene blocks

High molecular weight poly-(2,6-dimethyl-1,4-phenylene oxide) (PPO) is obtained from 2,6-dimethylphenol (DMP) by oxidative coupling polymerization. The polymerization is accomplished by passing oxygen through a solution of DMP, a catalytic amount of copper(I) salt, and amine in an organic solvent. High molecular weight PPO is a useful material for engineering thermoplastic applications because of its outstanding physical and chemical properties. However, the use of neat poly-PPO is insignificant as a commercial product because of its high melt viscosity. The commercially available products are generally blends of PPO with high-impact polystyrene. Recently, low molecular weight PPO has attracted considerable interest as starting materials for the preparation of block copolymers, graft copolymers, macromonomers, and star-type polymers of well-defined architectures. Low molecular weight PPO with a narrow molecular weight distribution can be prepared by the precipitation polymerization of DMP in the solvent/nonsolvent mixture under the action of Cu(I) Cl/amine-catalyst and oxygen or by the redistribution of PPO with functional phenols. Tingerthal et al. carried out the synthesis of an ABA-type triblock copolymer containing PPO (A) and polysulfone (B) blocks. Servens et al. studied the preparation of a diblock copolymer with PPO and 1,4polyisoprene segments. More recently, VanAert et al. prepared diblock copolymers by the reaction of phenolterminated polystyrene with PPO. The controlled/“living” radical polymerization such as copper-catalyst-mediated atom transfer radical polymerizations (ATRP) has been utilized for the synthesis of well-defined polymers with narrow molecular weight distributions. ATRP involves the activation and deactivation of a propagating chain end as a result of the reversible atom transfer reaction between a metal salt and alkyl halides. A wide variety of monomers such as styrenes, acrylates, and acrylonitrile have been used for ATRP. To the best of our knowledge, this is the first report on the synthesis and characterization of AB-type block copolymers with well-defined PPO and methyl methacrylate (MMA) blocks. Also, a sample of block copolymer containing PPO and styrene (St) segments was achieved. The PPO oligomers with activated halogen end groups were used as macroinitiators for ATRP.

T-Junction Grain Boundaries in Block Copolymer−Homopolymer Blends

T-junction grain boundaries were studied in a blend of polyisoprene homopolymer and a single graft block copolymer I2S with two equal length blocks of polyisoprene and one arm of polystyrene linked at a common junction point. The overall polyisoprene volume fraction in the blend was 0.52, and its equilibrium morphology was lamellar. While T-junctions were previously observed to be quite rare compared to other tilt grain boundary morphologies such as chevrons and omegas, they were found in abundance in the blend used in the current study. The T-junctions in the blend show a number of distinctive characteristics including enlarged semicylindrical end caps terminating polystyrene lamella and an increase in the spacing of the lamella as they near their termination at the T-junction. Simple free energy calculations show that the homopolymer present in the blend stabilizes the cylindrical curvature of the end caps, rendering the T-junction morphology more stable in blends than in neat block copolymers. This agr...

Nanostructures from POSS-Grafted Block Copolymer Precursors

ABSTRACTA new method to prepare novel nanocomposites has been studied in which a polyhedral oligomeric silsesquioxane (POSS) monomer is grafted to a polyisoprene-block-polystyrene copolymer to yield an inorganic-organic hybrid copolymer (POSS-g-PI-block-PS). PS-block-PI copolymers (SI) were synthesized via anionic polymerization in tetrahydrofuran (THF) as solvent. The polyisoprene block of the SI diblock copolymers in this study featured a very high vinyl group fraction (65 mole % of 3,4- addition and 35 mole % of 1,2-addition) available to react with hydride-substituted POSS (isobutyldimethyl silane-POSS) to form a grafted block copolymer. Due to the immiscibility between POSS-grafted PI block and PS block, the grafted block copolymer developed a microdomain structure. The volume fraction of PS block in the grafted block copolymer was varied in the range of 0.45 to 0.37 in order to yield cylindrical PS microdomains in the matrix of POSS-grafted PI. After exposure to an oxygen plasma, it is expected that preferential erosion of the grafted block copolymer will occur for the organic potion (PS microdomains) thus leaving a well-defined nanoporous surface structure for nonlithographic functionalization of coated substrates.

“Living” Free Radical Photopolymerization Initiated from Surface-Grafted Iniferter Monolayers

A method for chemically modifying a surface with grafted monolayers of initiator groups, which can be used for a “living” free radical photopolymerization, is described. By using “living” free radical polymerizations, we were able to control the length of the grafted polymer chains and therefore the layer thickness up to ∼100 nm. Also, single-layer grafted block copolymers were obtained by subsequent polymerizations of styrene and methyl methacrylate monomers. The surface-grafted polymer and block copolymer layers were evidenced by direct imaging methods (transmission and scanning electron microscopy) and by indirect surface characterization methods (contact angle measurements, SFM, XPS, and IR). The ability to control the thickness of the grafted polymer as well as the synthesis of a grafted block copolymer layer in a well-defined manner affirms the “living” character of the surface-initiated free radical photopolymerization.

Synthesis and characterization of block-graft copolymers composed of poly(styrene-b-ethylene-co-propylene) and poly(ethyl methylacrylate) by atom transfer radical polymerization

Synthesis and characterization of block-graft copolymers composed of poly(styrene-b-ethylene-co-propylene) and poly(ethyl methylacrylate) by atom transfer radical polymerization

Surface Macromolecular Microarchitecture Design: Biocompatible Surfaces via Photo-Block-Graft-Copolymerization Using N,N-Diethyldithiocarbamate

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).