Facile surface modification of silicone rubber with zwitterionic polymers for improving blood compatibility.

A facile approach to modify silicone rubber (SR) membrane for improving the blood compatibility was investigated. The hydrophobic SR surface was firstly activated by air plasma, after which an initiator was immobilized on the activated surface for atom transfer radical polymerization (ATRP). Three zwitterionic polymers were then grafted from SR membrane via surface-initiated atom transfer radical polymerization (SI-ATRP). The surface composition, wettability, and morphology of the membranes before and after modification were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (WCA) measurement, and atomic force microscopy (AFM). Results showed that zwitterionic polymers were successfully grafted from SR surfaces, which remarkably improved the wettability of the SR surface. The blood compatibility of the membranes was evaluated by protein adsorption and platelet adhesion tests in vitro. As observed, all the zwitterionic polymer modified surfaces have improved resistance to nonspecific protein adsorption and have excellent resistance to platelet adhesion, showing significantly improved blood compatibility. This work should inspire many creative uses of SR based materials for biomedical applications such as vessel, catheter, and microfluidics.

[1]  Jian Shen,et al.  Surface modification of cellulose membranes with zwitterionic polymers for resistance to protein adsorption and platelet adhesion , 2010 .

[2]  Grant D. Smith,et al.  Crosslinked polydimethylsiloxane exposed to oxygen plasma studied by neutron reflectometry and other surface specific techniques , 2000 .

[3]  Jiang Yuan,et al.  Platelet adhesive resistance of segmented polyurethane film surface-grafted with vinyl benzyl sulfo monomer of ammonium zwitterions. , 2003, Biomaterials.

[4]  Shaoyi Jiang,et al.  A switchable biocompatible polymer surface with self-sterilizing and nonfouling capabilities. , 2008, Angewandte Chemie.

[5]  K. Aratani,et al.  Experimental study of the relation between contact angle and surface roughness , 1972 .

[6]  Kinam Park,et al.  Grafting of PEO to glass, nitinol, and pyrolytic carbon surfaces by γ irradiation , 1997 .

[7]  Jian Shen,et al.  Ozone-induced grafting phosphorylcholine polymer onto silicone film grafting 2-methacryloyloxyethyl phosphorylcholine onto silicone film to improve hemocompatibility , 2003 .

[8]  D. M. Kim,et al.  Platelet adhesion onto segmented polyurethane film surfaces modified by addition and crosslinking of PEO-containing block copolymers. , 2000, Biomaterials.

[9]  Robert N. Wenzel,et al.  Surface Roughness and Contact Angle. , 1949 .

[10]  Joseph D. Andrade,et al.  Blood compatibility of polyethylene oxide surfaces , 1995 .

[11]  Tomasz Ciach,et al.  Determination of urethral catheter surface lubricity , 2008, Journal of materials science. Materials in medicine.

[12]  Jiang Yuan,et al.  Enhanced blood compatibility of polyurethane functionalized with sulfobetaine. , 2008, Colloids and surfaces. B, Biointerfaces.

[13]  Shiping Zhu,et al.  Non-biofouling materials prepared by atom transfer radical polymerization grafting of 2-methacryloloxyethyl phosphorylcholine: separate effects of graft density and chain length on protein repulsion. , 2006, Biomaterials.

[14]  A S Hoffman,et al.  Protein adsorption to poly(ethylene oxide) surfaces. , 1991, Journal of biomedical materials research.

[15]  S. Michel,et al.  Surface functionalization of silicone rubber for permanent adhesion improvement. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[16]  K. Ishihara,et al.  Surface tethering of phosphorylcholine groups onto poly(dimethylsiloxane) through swelling--deswelling methods with phospholipids moiety containing ABA-type block copolymers. , 2008, Biomaterials.

[17]  G. Whitesides,et al.  Correlation Between Surface Free Energy and Surface Constitution , 1992, Science.

[18]  Delara Motlagh,et al.  Hemocompatibility evaluation of poly(glycerol-sebacate) in vitro for vascular tissue engineering. , 2006, Biomaterials.

[19]  J. Marchal,et al.  Caractérisation de réactions primaires de dégradation oxydante au cours de l'autoxydation des poly(oxyéthylène)s à 25°C: Étude en solution aqueuse avec amorçage par radiolyse du solvant, 8. Étude cinétique en fonction du ph compris entre 1 et 13† , 1976 .

[20]  A. Ledwith,et al.  Thermal and photochemical cationic polymerisations induced by AgPF6 in the presence of free radical initiators , 1978, Polymer Bulletin.

[21]  Xizeng Feng,et al.  Biocompatible Hydrophilic Modifications of Poly(dimethylsiloxane) Using Self-Assembled Hydrophobins , 2007 .

[22]  Jiang Yuan,et al.  Platelet adhesion and protein adsorption on silicone rubber surface by ozone-induced grafted polymerization with carboxybetaine monomer. , 2005, Colloids and surfaces. B, Biointerfaces.

[23]  Wantai Yang,et al.  Developments and new applications of UV-induced surface graft polymerizations , 2009 .

[24]  Bin Wang,et al.  Surface characterization using chemical force microscopy and the flow performance of modified polydimethylsiloxane for microfluidic device applications , 2003, Electrophoresis.

[25]  Miss A.O. Penney.  (b) , 1974, The New Yale Book of Quotations.

[26]  Jinyi Wang,et al.  Solution-phase surface modification in intact poly(dimethylsiloxane) microfluidic channels. , 2006, Analytical Chemistry.

[27]  G. Whitesides,et al.  Direct measurement of interfacial interactions between semispherical lenses and flat sheets of poly(dimethylsiloxane) and their chemical derivatives , 1991 .

[28]  T. Horbett,et al.  Proteins at Interfaces II-Fundamentals and Applications- , 1995 .

[29]  Dany J. Munoz-Pinto,et al.  Photo-cross-linked PDMSstar-PEG hydrogels: synthesis, characterization, and potential application for tissue engineering scaffolds. , 2010, Biomacromolecules.

[30]  X. Xia,et al.  Air plasma assisting microcontact deprinting and printing for gold thin film and PDMS patterns. , 2010, ACS applied materials & interfaces.

[31]  Chunfeng Ma,et al.  Preparation of polyurethane with zwitterionic side chains and their protein resistance. , 2011, ACS applied materials & interfaces.

[32]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[33]  J. West-Mays,et al.  EGF-grafted PDMS surfaces in artificial cornea applications. , 2005, Biomaterials.

[34]  Jingjing Xu,et al.  Conformal, Amine-Functionalized Thin Films by Initiated Chemical Vapor Deposition (iCVD) for Hydrolytically Stable Microfluidic Devices , 2010 .

[35]  Ernesto Occhiello,et al.  On the aging of oxygen plasma-treated polydimethylsiloxane surfaces , 1990 .

[36]  Yan Han,et al.  Molecular dynamics simulation study on zwitterionic structure to maintain the normal conformations of Glutathione , 2007 .

[37]  K. Ishihara,et al.  Graft copolymerization of 2‐methacryloyloxyethyl phosphorylcholine to cellulose in homogeneous media using atom transfer radical polymerization for providing new hemocompatible coating materials , 2008 .

[38]  David Farrar,et al.  Interpretation of protein adsorption: surface-induced conformational changes. , 2005, Journal of the American Chemical Society.

[39]  Shu-Kun Lin.  Polymers – A New Open Access Scientific Journal on Polymer Science , 2009 .

[40]  Helmut Thissen,et al.  Effects of cloud-point grafting, chain length, and density of PEG layers on competitive adsorption of ocular proteins. , 2002, Biomaterials.

[41]  Y. Bae,et al.  PDMS-based polyurethanes with MPEG grafts: synthesis, characterization and platelet adhesion study. , 1999, Biomaterials.

[42]  G. Whitesides,et al.  Effect of Surface Wettability on the Adsorption of Proteins and Detergents , 1998 .

[43]  Bingcheng Lin,et al.  Grafting epoxy-modified hydrophilic polymers onto poly(dimethylsiloxane) microfluidic chip to resist nonspecific protein adsorption. , 2006, Lab on a chip.

[44]  G. Whitesides,et al.  A Survey of Structure−Property Relationships of Surfaces that Resist the Adsorption of Protein , 2001 .

[45]  D. Wayner,et al.  A simple approach to micropatterning and surface modification of poly(dimethylsiloxane). , 2004, Langmuir : the ACS journal of surfaces and colloids.

[46]  A. Simmons,et al.  Biostability and biological performance of a PDMS-based polyurethane for controlled drug release. , 2008, Biomaterials.

[47]  Saif A. Khan,et al.  UV-defined flat PDMS stamps suitable for microcontact printing. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[48]  Jing Fan,et al.  Covalent modified hydrophilic polymer brushes onto poly(dimethylsiloxane) microchannel surface for electrophoresis separation of amino acids. , 2008, Journal of chromatography. A.

[49]  J. Brash.  Exploiting the current paradigm of blood–material interactions for the rational design of blood-compatible materials , 2000, Journal of biomaterials science. Polymer edition.

[50]  P. Chu,et al.  The effect of high-dose nitrogen plasma immersion ion implantation on silicone surfaces , 2000 .

[51]  J. Kennedy,et al.  Synthesis, permeability and biocompatibility of tricomponent membranes containing polyethylene glycol, polydimethylsiloxane and polypentamethylcyclopentasiloxane domains. , 2003, Biomaterials.

[52]  George M. Whitesides,et al.  Polymeric Thin Films That Resist the Adsorption of Proteins and the Adhesion of Bacteria , 2001 .

[53]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[54]  Shifang Luan,et al.  Improved biocompatibility and antifouling property of polypropylene non-woven fabric membrane by sur , 2011 .

[55]  J. Genzer,et al.  Formation of silicone elastomer networks films with gradients in modulus , 2010 .

[56]  G. Whitesides,et al.  Rapid Prototyping of Microfluidic Systems in Poly(dimethylsiloxane). , 1998, Analytical chemistry.

[57]  Harm-Anton Klok,et al.  Polymer brushes via surface-initiated controlled radical polymerization: synthesis, characterization, properties, and applications. , 2009, Chemical reviews.

[58]  Shaoyi Jiang,et al.  Zwitterionic polymers exhibiting high resistance to nonspecific protein adsorption from human serum and plasma. , 2008, Biomacromolecules.

[59]  J. Vacanti,et al.  Tissue engineering : Frontiers in biotechnology , 1993 .

[60]  Yung Chang,et al.  Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization. , 2011, ACS applied materials & interfaces.

[61]  M. Refojo,et al.  Biological oxygen apparent transmissibility of hydrogel contact lenses with and without organosilicon moieties. , 2004, Biomaterials.

[62]  M. Brook,et al.  Biocompatible, hyaluronic acid modified silicone elastomers. , 2010, Biomaterials.

[63]  Krzysztof Matyjaszewski,et al.  Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes , 1995 .

[64]  Shaoyi Jiang,et al.  Surface grafted sulfobetaine polymers via atom transfer radical polymerization as superlow fouling coatings. , 2006, The journal of physical chemistry. B.

[65]  D. Edell,et al.  Pulsed-PECVD Films from Hexamethylcyclotrisiloxane for Use as Insulating Biomaterials , 2000 .

[66]  R. Barbucci,et al.  Fibrinogen conformation and platelet reactivity in relation to material-blood interaction: effect of stress hormones. , 2003, Biomacromolecules.

[67]  N Nakabayashi,et al.  Why do phospholipid polymers reduce protein adsorption? , 1998, Journal of biomedical materials research.