Random Copolymer Films with Molecular‐Scale Compositional Heterogeneities that Interfere with Protein Adsorption

Smooth surfaces with compositional heterogeneities at a molecular-length scale are presented with the goal of disrupting surface-protein interactions. These surfaces are synthesized by utilizing photoinitiated chemical vapor deposition (piCVD) to deposit thin films of random copolymers consisting of highly hydrophilic and highly hydrophobic comonomers. Swellability, wettability, and surface roughness could be systematically controlled by tuning the copolymer composition. The surface composition was dynamic, and the surface reconstructed based on the hydration state of the film. Proteins adsorbed to the copolymer films less readily than to either of the respective homopolymers, indicating a synergistic effect resulting from the random copolymer presenting molecular-scale compositional heterogeneity. These results provide direct evidence that protein adsorption can be disrupted by such surfaces and a simple analytical model suggests that the heterogeneities occur over areas encompassing 4-5 repeat units of the polymer. The synthetic method used to create these films can be used to coat arbitrary geometries, enabling practical utility in a number of applications.

[1]  S. Baxamusa,et al.  Thin Hydrogel Films With Nanoconfined Surface Reactivity by Photoinitiated Chemical Vapor Deposition , 2009 .

[2]  C. Jérôme,et al.  Controlled synthesis of carboxylic acid end‐capped poly(heptadecafluorodecyl acrylate) and copolymers with 2‐hydroxyethyl acrylate , 2007 .

[3]  J. Andrade.  Surface and Interfacial Aspects of Biomedical Polymers , 1985 .

[4]  B. Liedberg,et al.  Photografted poly(ethylene glycol) matrix for affinity interaction studies. , 2007, Biomacromolecules.

[5]  Karen L. Wooley,et al.  Amphiphilic and hydrophobic surface patterns generated from hyperbranched fluoropolymer/linear polymer networks: Minimally adhesive coatings via the crosslinking of hyperbranched fluoropolymers , 2003 .

[6]  Fredrik Höök,et al.  Quartz crystal microbalance setup for frequency and Q‐factor measurements in gaseous and liquid environments , 1995 .

[7]  Zhongyi Zhang,et al.  Synthesis and characterization of low surface energy fluoropolymers as potential barrier coatings in oral care. , 2008, Journal of biomedical materials research. Part A.

[8]  D. Hobara,et al.  Preferential Adsorption of Horse Heart Cytochrome c on Nanometer-Scale Domains of a Phase-Separated Binary Self-Assembled Monolayer of 3-Mercaptopropionic Acid and 1-Hexadecanethiol on Au(111) , 2002 .

[9]  H. Brown,et al.  Self‐Initiated Photopolymerization and Photografting of Acrylic Monomers , 2004 .

[10]  B. Tighe,et al.  Synthetic hydrogels. VI. Hydrogel composites as wound dressings and implant materials. , 1989, Biomaterials.

[11]  S. Sablani,et al.  Fouling of Reverse Osmosis and Ultrafiltration Membranes: A Critical Review , 2005 .

[12]  K. Gleason,et al.  All-dry synthesis and coating of methacrylic acid copolymers for controlled release. , 2007, Macromolecular bioscience.

[13]  Marcus Textor,et al.  A comparative study of protein adsorption on titanium oxide surfaces using in situ ellipsometry, optical waveguide lightmode spectroscopy, and quartz crystal microbalance/dissipation , 2002 .

[14]  A. Jackson,et al.  The role of nanostructure in the wetting behavior of mixed-monolayer-protected metal nanoparticles , 2008, Proceedings of the National Academy of Sciences.

[15]  O. Wichterle,et al.  Hydrophilic Gels for Biological Use , 1960, Nature.

[16]  Anne Simmons,et al.  The effect of charged groups on protein interactions with poly(HEMA) hydrogels. , 2006, Biomaterials.

[17]  I J Constable,et al.  Poly(2-hydroxyethyl methacrylate) sponges as implant materials: in vivo and in vitro evaluation of cellular invasion. , 1993, Biomaterials.

[18]  S. Baxamusa,et al.  Protection of sensors for biological applications by photoinitiated chemical vapor deposition of hydrogel thin films. , 2008, Biomacromolecules.

[19]  J. Kressler,et al.  Synthesis and characterization of random copolymers of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate and 2,3-dihydroxypropyl methacrylate , 2007 .

[20]  K. Eichhorn,et al.  Insights on structural variations of protein adsorption layers on hydrophobic fluorohydrocarbon polymers gained by spectroscopic ellipsometry (part I) , 1999 .

[21]  S. Baxamusa,et al.  Initiated and oxidative chemical vapor deposition: a scalable method for conformal and functional polymer films on real substrates. , 2009, Physical chemistry chemical physics : PCCP.

[22]  Karen L Wooley,et al.  The antifouling and fouling-release performance of hyperbranched fluoropolymer (HBFP)-poly(ethylene glycol) (PEG) composite coatings evaluated by adsorption of biomacromolecules and the green fouling alga Ulva. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[23]  B. Liedberg,et al.  Synthesis and self-assembly of galactose-terminated alkanethiols and their ability to resist proteins. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[24]  M. Anthamatten,et al.  Multicomponent vapor deposition polymerization of poly(methyl methacrylate) in an axisymmetric vacuum reactor , 2008 .

[25]  F. Macritchie.  Proteins at interfaces. , 1978, Advances in protein chemistry.

[26]  S. Baxamusa,et al.  Thin Polymer Films with High Step Coverage in Microtrenches by Initiated CVD , 2008 .

[27]  S. Sugihara,et al.  Thermosensitive Random Copolymers of Hydrophilic and Hydrophobic Monomers Obtained by Living Cationic Copolymerization1 , 2004 .

[28]  E. Kramer,et al.  Settlement of Ulva zoospores on patterned fluorinated and PEGylated monolayer surfaces. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[29]  Sheelagh L. Conlan,et al.  Poly(ethylene glycol)-containing hydrogel surfaces for antifouling applications in marine and freshwater environments. , 2008, Biomacromolecules.

[30]  K. L. Tan,et al.  Surface functionalization of low density polyethylene films with grafted poly(ethylene glycol) derivatives , 2001 .

[31]  J. C. Yarbrough,et al.  Contact Angle Analysis, Surface Dynamics, and Biofouling Characteristics of Cross-Linkable, Random Perfluoropolyether-Based Graft Terpolymers , 2006 .

[32]  K. Gleason,et al.  Initiated chemical vapor deposition of linear and cross-linked poly(2-hydroxyethyl methacrylate) for use as thin-film hydrogels. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[33]  H. Dahms,et al.  Inhibition of biofouling by marine microorganisms and their metabolites , 2006, Biofouling.

[34]  C. Tanford,et al.  The hydrophobic effect and the organization of living matter. , 1978, Science.

[35]  K. Gleason,et al.  Initiated Chemical Vapor Deposition (iCVD) of Poly(alkyl acrylates): A Kinetic Model , 2006 .

[36]  A. Thünemann,et al.  Low surface energy coatings from waterborne nano-dispersions of polymer complexes. , 1999 .

[37]  Francesco Stellacci,et al.  Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayer-protected nanoparticles , 2004, Nature materials.

[38]  T. Desai,et al.  Controlling Nonspecific Protein Interactions in Silicon Biomicrosystems with Nanostructured Poly(ethylene glycol) Films , 2002 .

[39]  A. Hexemer,et al.  Anti-biofouling properties of comblike block copolymers with amphiphilic side chains. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[40]  K. Gleason,et al.  Vapor-Deposited Fluorinated Glycidyl Copolymer Thin Films with Low Surface Energy and Improved Mechanical Properties , 2006 .

[41]  K. Gleason,et al.  Initiated chemical vapor deposition of poly(1H,1H,2H,2H-perfluorodecyl acrylate) thin films. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[42]  E. Chiellini,et al.  Nanostructured films of amphiphilic fluorinated block copolymers for fouling release application. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[43]  Bengt Herbert Kasemo,et al.  A simple setup to simultaneously measure the resonant frequency and the absolute dissipation factor of a quartz crystal microbalance , 1996 .

[44]  Michael V Sefton,et al.  Biomaterial-associated thrombosis: roles of coagulation factors, complement, platelets and leukocytes. , 2004, Biomaterials.