Temperature-responsive self-assembled monolayers of oligo(ethylene glycol): control of biomolecular recognition.

Self-assembled monolayers (SAMs) of oligo(ethylene glycol) (OEG)-tethered molecules on gold are important for various biorelevant applications ranging from biomaterials to bioanalytical devices, where surface resistance to nonspecific protein adsorption is needed. Incorporation of a stimuli-responsive character to the OEG SAMs enables the creation of nonfouling surfaces with switchable functionality. Here we present an OEG-derived structure that is highly responsive to temperature changes in the vicinity of the physiological temperature, 37 degrees C. The temperature-responsive solution behavior of this new compound was demonstrated by UV-vis and nuclear magnetic resonance spectroscopy. Its chemisorption onto gold(111), and the retention of responsive behavior after chemisorption have been demonstrated by surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and atomic force and scanning tunneling microscopy. The OEG-derived SAMs have been shown to reversibly switch the wettability of the surface, as determined by contact angle measurements. More importantly, SPR and AFM studies showed that the OEG SAMs can be utilized to control the affinity binding of streptavidin to the biotin-tethered surface in a temperature-dependent manner while still offering the nonspecific protein-resistance to the surface.

[1]  M. Textor,et al.  Biotin-Derivatized Poly(L-lysine)-g-poly(ethylene glycol): A Novel Polymeric Interface for Bioaffinity Sensing , 2002 .

[2]  Marcus Textor,et al.  A Novel Approach to Produce Protein Nanopatterns by Combining Nanoimprint Lithography and Molecular Self-Assembly , 2004 .

[3]  D. Castner,et al.  Temperature dependent activity and structure of adsorbed proteins on plasma polymerized N-isopropyl acrylamide , 2006, Biointerphases.

[4]  D. Castner,et al.  A streptavidin linker layer that functions after drying. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[5]  T. Chinowsky,et al.  Quantitative interpretation of the response of surface plasmon resonance sensors to adsorbed films , 1998 .

[6]  G. Whitesides,et al.  Soft lithography in biology and biochemistry. , 2001, Annual review of biomedical engineering.

[7]  Marcus Textor,et al.  A Combined Photolithographic and Molecular‐Assembly Approach to Produce Functional Micropatterns for Applications in the Biosciences , 2004 .

[8]  Alexander D. Q. Li,et al.  Thermosensitive gold nanoparticles. , 2004, Journal of the American Chemical Society.

[9]  P. Ascenzi,et al.  Poly[(N-isopropylacrylamide-co-acrylamide-co-(hydroxyethylmethacrylate))] thermoresponsive microspheres: An accurate method based on solute exclusion technique to determine the volume phase transition temperature , 2007 .

[10]  D. Briggs,et al.  High resolution XPS of organic polymers , 1992 .

[11]  N. Flynn,et al.  Thermoresponsive behavior of poly(n-isopropylacrylamide) hydrogels containing gold nanostructures. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[12]  Marcus Textor,et al.  Poly(l-lysine)-g-poly(ethylene glycol) Layers on Metal Oxide Surfaces: Surface-Analytical Characterization and Resistance to Serum and Fibrinogen Adsorption , 2001 .

[13]  R. Francis,et al.  Synthesis of poly (N -isopropylacrylamide) copolymer containing anhydride and imide comonomers : A theoretical study on reversal of LCST , 2007 .

[14]  M. Grunze,et al.  Reversible protein adsorption and bioadhesion on monolayers terminated with mixtures of oligo(ethylene glycol) and methyl groups. , 2005, Journal of the American Chemical Society.

[15]  A. Ulman,et al.  Formation and Structure of Self-Assembled Monolayers. , 1996, Chemical reviews.

[16]  J. Hubbell,et al.  Chemisorbed poly(propylene sulphide)-based copolymers resist biomolecular interactions , 2003, Nature materials.

[17]  Ralph G Nuzzo,et al.  Stable antifouling surfaces , 2003, Nature materials.

[18]  Marcus Textor,et al.  Poly(l-lysine)-graft-poly(ethylene glycol) Assembled Monolayers on Niobium Oxide Surfaces: A Quantitative Study of the Influence of Polymer Interfacial Architecture on Resistance to Protein Adsorption by ToF-SIMS and in Situ OWLS , 2003 .

[19]  M. Grunze,et al.  Temperature Dependence of the Protein Resistance of Poly- and Oligo(ethylene glycol)-Terminated Alkanethiolate Monolayers , 2001 .

[20]  Darren M. Jones,et al.  Variable Adhesion of Micropatterned Thermoresponsive Polymer Brushes: AFM Investigations of Poly(N‐isopropylacrylamide) Brushes Prepared by Surface‐Initiated Polymerizations , 2002 .

[21]  C. Alexander,et al.  Thermoresponsive Surface-Grafted Poly(N−isopropylacrylamide) Copolymers: Effect of Phase Transitions on Protein and Bacterial Attachment , 2003 .

[22]  M. Grunze,et al.  Factors that determine the protein resistance of oligoether self-assembled monolayers --internal hydrophilicity, terminal hydrophilicity, and lateral packing density. , 2003, Journal of the American Chemical Society.

[23]  Axel H. E. Müller,et al.  Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities , 2007 .

[24]  C. Barner‐Kowollik,et al.  Well-defined protein-polymer conjugates via in situ RAFT polymerization. , 2007, Journal of the American Chemical Society.

[25]  Michael J. O'Brien,et al.  Molecular Recognition between Genetically Engineered Streptavidin and Surface-Bound Biotin , 1999 .

[26]  R. Glockshuber,et al.  Immobilization of the enzyme beta-lactamase on biotin-derivatized poly(L-lysine)-g-poly(ethylene glycol)-coated sensor chips: a study on oriented attachment and surface activity by enzyme kinetics and in situ optical sensing. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[27]  Robert Langer,et al.  Long-Term Stability of Self-Assembled Monolayers in Biological Media , 2003 .

[28]  A. Schwan,et al.  New deuterated oligo(ethylene glycol) building blocks and their use in the preparation of surface active lipids possessing labeled hydrophilic tethers. , 2008, The Journal of organic chemistry.

[29]  Jinho Hyun,et al.  Capture and release of proteins on the nanoscale by stimuli-responsive elastin-like polypeptide "switches". , 2004, Journal of the American Chemical Society.

[30]  Ali Khademhosseini,et al.  Direct Patterning of Protein‐ and Cell‐Resistant Polymeric Monolayers and Microstructures , 2003 .

[31]  Insung S. Choi,et al.  Grafting Nitrilotriacetic Groups onto Carboxylic Acid-Terminated Self-Assembled Monolayers on Gold Surfaces for Immobilization of Histidine-Tagged Proteins , 2004 .

[32]  M. Grunze,et al.  The interaction of oligo(ethylene oxide) with water: a quantum mechanical study , 2000 .

[33]  A. Middelberg,et al.  Reversible active switching of the mechanical properties of a peptide film at a fluid–fluid interface , 2006, Nature materials.

[34]  G. Whitesides,et al.  Adsorption of proteins onto surfaces containing end-attached oligo(ethylene oxide): a model system using self-assembled monolayers , 1993 .

[35]  S. Lata,et al.  Stable and functional immobilization of histidine-tagged proteins via multivalent chelator headgroups on a molecular poly(ethylene glycol) brush. , 2005, Analytical chemistry.

[36]  Elena E. Dormidontova,et al.  Influence of End Groups on Phase Behavior and Properties of PEO in Aqueous Solutions , 2004 .

[37]  M. Engelhard,et al.  XAS and XPS Characterization of Monolayers Derived from a Dithiol and Structurally Related Disulfide-Containing Polyamides , 2002 .

[38]  I. Navrotskaya,et al.  Thermal and sodium dodecylsulfate induced transitions of streptavidin. , 2004, Biophysical journal.

[39]  K. Nelson,et al.  Surface Characterization of Mixed Self-Assembled Monolayers Designed for Streptavidin Immobilization , 2001 .

[40]  G. Karlstroem.  A new model for upper and lower critical solution temperatures in poly(ethylene oxide) solutions , 1985 .

[41]  Sergio Mendez,et al.  Thermal Response of Poly(N-isopropylacrylamide) Brushes Probed by Surface Plasmon Resonance. , 2003, Langmuir : the ACS journal of surfaces and colloids.

[42]  D. Collard,et al.  Controlling Cell Adhesion to Titanium: Functionalization of Poly[oligo(ethylene glycol)methacrylate] Brushes with Cell‐Adhesive Peptides , 2007 .

[43]  G. Fidelio,et al.  Extremely high thermal stability of streptavidin and avidin upon biotin binding. , 1999, Biomolecular engineering.

[44]  M. Grunze,et al.  MOLECULAR CONFORMATION AND SOLVATION OF OLIGO(ETHYLENE GLYCOL)-TERMINATED SELF-ASSEMBLED MONOLAYERS AND THEIR RESISTANCE TO PROTEIN ADSORPTION , 1997 .

[45]  G. Whitesides,et al.  Self-assembled monolayers of thiolates on metals as a form of nanotechnology. , 2005, Chemical reviews.

[46]  P. Mather,et al.  Responsive materials: soft answers for hard problems. , 2007, Nature materials.

[47]  Yongseok Jun,et al.  Immobilization of oriented protein molecules on poly(ethylene glycol)‐coated Si(111) , 2004, Proteomics.

[48]  D. Bedrov,et al.  Roles of enthalpy, entropy, and hydrogen bonding in the lower critical solution temperature behavior of poly(ethylene oxide)/water solutions , 2003 .

[49]  Jan Feijen,et al.  Effect of comonomer hydrophilicity and ionization on the lower critical solution temperature of N-isopropylacrylamide copolymers , 1993 .

[50]  Leonid Ionov,et al.  Size sorting of protein assemblies using polymeric gradient surfaces. , 2005, Nano letters.

[51]  J. Comyn.  High resolution XPS of organic polymers The Scienta ESCA300 Database , 1993 .

[52]  Marcus Textor,et al.  Nitrilotriacetic Acid Functionalized Graft Copolymers: A Polymeric Interface for Selective and Reversible Binding of Histidine‐Tagged Proteins , 2006 .

[53]  Charles T. Campbell,et al.  Binding and Dissociation Kinetics of Wild-Type and Mutant Streptavidins on Mixed Biotin-Containing Alkylthiolate Monolayers , 2000 .

[54]  Jean-François Lutz,et al.  Point by point comparison of two thermosensitive polymers exhibiting a similar LCST: is the age of poly(NIPAM) over? , 2006, Journal of the American Chemical Society.

[55]  G. Whitesides,et al.  Self-assembled organic monolayers: model systems for studying adsorption of proteins at surfaces , 1991, Science.

[56]  M. Wilchek,et al.  Sodium dodecyl sulfate‐polyacrylamide gel electrophoretic method for assessing the quaternary state and comparative thermostability of avidin and streptavidin , 1996, Electrophoresis.

[57]  Pre-Adsorption of Amphiphilic Polymers on Synthetic Surfaces for Biofouling Retardation , 2006 .

[58]  Y. D. Kim,et al.  Thermally responsive poly(N-isopropylacrylamide) monolayer on gold: synthesis, surface characterization, and protein interaction/adsorption studies , 2004 .