Nanoporous Gyroid-Structured Epoxy from Block Copolymer Templates for High Protein Adsorbability.

Nanoporous epoxy with gyroid texture is fabricated by using a nanoporous polymer with gyroid-forming nanochannels as a template for polymerization of epoxy. The nanoporous polymer template is obtained from the self-assembly of degradable block copolymer, polystyrene-b-poly(l-lactide) (PS-PLLA), followed by hydrolysis of PLLA blocks. Templated polymerization can be conducted under ambient conditions to create well-defined, bicontinuous epoxy networks in a PS matrix. By taking advantage of multistep curing of epoxy, well-ordered robust nanoporous epoxy can be obtained after removal of PS template, giving robust porous materials. The through-hole nanoporous epoxy in the film state can be used as a coated layer to enhance the adsorbability for both lysozyme and bovine serum albumin.

[1]  Jinho Oh,et al.  A homochiral metal–organic porous material for enantioselective separation and catalysis , 2000, Nature.

[2]  Hirokazu Hasegawa,et al.  Inorganic gyroid with exceptionally low refractive index from block copolymer templating. , 2010, Nano letters.

[3]  G. Fredrickson,et al.  Block Copolymers—Designer Soft Materials , 1999 .

[4]  A. Nguyen,et al.  Epoxy-Based Monoliths. A Novel Hydrophilic Separation Material for Liquid Chromatography of Biomolecules , 2006 .

[5]  J. Chen,et al.  Epoxy modified with triblock copolymers: morphology, mechanical properties and fracture mechanisms , 2012, Journal of Materials Science.

[6]  C. T. O'konski,et al.  The hydrodynamic properties of bovine serum albumin monomer and dimer. , 1968, Biochemistry.

[7]  Shinn-Gwo Hong,et al.  DSC and FTIR analysis of the curing behaviors of epoxy/DICY/solvent open systems , 1998 .

[8]  Y. Yamauchi,et al.  Fabrication of mesoporous silica KIT-6/polymer composite and its low thermal expansion property , 2011 .

[9]  Joy Cheng,et al.  Formation of a Cobalt Magnetic Dot Array via Block Copolymer Lithography , 2001 .

[10]  Bao-Tsan Ko,et al.  Solvent-induced microdomain orientation in polystyrene-b-poly(l-lactide) diblock copolymer thin films for nanopatterning , 2005 .

[11]  R. Ho,et al.  Tubular Nanostructures from Degradable Core–Shell Cylinder Microstructures in Chiral Diblock Copolymers , 2006 .

[12]  Lan-sun Zheng,et al.  MOF-Derived Porous Co/C Nanocomposites with Excellent Electromagnetic Wave Absorption Properties. , 2015, ACS applied materials & interfaces.

[13]  F. Bates,et al.  SELF-ASSEMBLY AND POLYMERIZATION OF EPOXY RESIN-AMPHIPHILIC BLOCK COPOLYMER NANOCOMPOSITES , 1997 .

[14]  E. Thomas,et al.  Ordered bicontinuous nanoporous and nanorelief ceramic films from self assembling polymer precursors , 1999, Science.

[15]  I. Martin,et al.  Nanostructuration in Thin Epoxy-Amine Films Inducing Controlled Specific Phase Etherification: Effect on the Glass Transition Temperatures , 2011 .

[16]  R. Ho,et al.  Well-ordered nanohybrids and nanoporous materials from gyroid block copolymer templates. , 2015, Chemical Society reviews.

[17]  R. Ho,et al.  Nanoporous Gyroid Nickel from Block Copolymer Templates via Electroless Plating , 2011, Advanced materials.

[18]  T. Pinnavaia,et al.  Reinforcement of a Rubbery Epoxy Polymer by Mesostructured Silica and Organosilica with Wormhole Framework Structures , 2008 .

[19]  M. Boyce,et al.  Enhanced energy dissipation in periodic epoxy nanoframes. , 2010, Nano letters.

[20]  E. D. Jong,et al.  On the specific surface area of nanoporous materials , 2011 .

[21]  R. Ho,et al.  Bicontinuous ceramics with high surface area from block copolymer templates. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[22]  Haoshen Zhou,et al.  Surface Photovoltage NO Gas Sensor with Properties Dependent on the Structure of the Self‐Ordered Mesoporous Silicate Film , 2002 .

[23]  E. Thomas,et al.  Shifting Networks to Achieve Subgroup Symmetry Properties , 2014, Advanced materials.

[24]  G. Fredrickson,et al.  Block copolymer thermodynamics: theory and experiment. , 1990, Annual review of physical chemistry.

[25]  L. Bergström,et al.  Impact of Cross-Linking Density and Glassy Chain Dynamics on Pore Stability in Mesoporous Poly(styrene) , 2009 .

[26]  Yan Jin,et al.  Novel glycidyl methacrylated dextran (Dex-GMA)/gelatin hydrogel scaffolds containing microspheres loaded with bone morphogenetic proteins: formulation and characteristics. , 2007, Journal of controlled release : official journal of the Controlled Release Society.

[27]  Sixun Zheng,et al.  Nanostructured Thermosetting Blends of Epoxy Resin and Amphiphilic Poly(ε-caprolactone)-block-polybutadiene-block-poly(ε-caprolactone) Triblock Copolymer , 2006 .

[28]  Marc A. Hillmyer,et al.  Nanoporous materials from block copolymer precursors , 2005 .

[29]  K. Harata.  X-ray structure of monoclinic turkey egg lysozyme at 1.3 A resolution. , 1993, Acta crystallographica. Section D, Biological crystallography.

[30]  J. Atwood,et al.  Carbon Dioxide Capture in a Self-Assembled Organic Nanochannels , 2007 .

[31]  Christopher Harrison,et al.  Block copolymer lithography: Periodic arrays of ~1011 holes in 1 square centimeter , 1997 .

[32]  Brad H. Jones,et al.  Nanoporous Materials Derived from Polymeric Bicontinuous Microemulsions , 2010 .

[33]  Song Qiu,et al.  Synthesis of nestlike ZnO hierarchically porous structures and analysis of their gas sensing properties. , 2012, ACS applied materials & interfaces.

[34]  Edwin L. Thomas,et al.  The gyroid: A new equilibrium morphology in weakly segregated diblock copolymers , 1994 .

[35]  Schick,et al.  Stable and unstable phases of a diblock copolymer melt. , 1994, Physical review letters.

[36]  Sergey Vyazovkin,et al.  Mechanism and Kinetics of Epoxy-Amine Cure Studied by Differential Scanning Calorimetry , 1996 .

[37]  J. Pascault,et al.  Epoxy polymers : new materials and innovations , 2010 .

[38]  Fei Chen,et al.  Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)-block-poly(dimethylsiloxane) diblock copolymer , 2006 .

[39]  C. Stafford,et al.  Nanoscopic Templates from Oriented Block Copolymer Films , 2000 .

[40]  Marc A. Hillmyer,et al.  Mesoporous Polystyrene Monoliths , 2001 .

[41]  Yan Liu,et al.  Engineering Homochiral Metal‐Organic Frameworks for Heterogeneous Asymmetric Catalysis and Enantioselective Separation , 2010, Advanced materials.

[42]  E. White,et al.  New Porous Biomaterials by Replication of Echinoderm Skeletal Microstructures , 1971, Nature.

[43]  L. Leibler,et al.  ABC Triblock Copolymers/Epoxy−Diamine Blends. 1. Keys To Achieve Nanostructured Thermosets , 2002 .

[44]  W. Tong,et al.  Manganese oxide mesoporous structures: Mixed-valent semiconducting catalysts , 1997 .