Thickness Dependence of Bovine Serum Albumin Adsorption on Thin Thermoresponsive Poly(diethylene glycol) Methyl Ether Methacrylate Brushes by Surface Plasmon Resonance Measurements.

This study reports on the dependence of the temperature-induced changes in the properties of thin thermoresponsive poly(diethylene glycol) methyl ether methacrylate (PDEGMA) layers of end-tethered chains on polymer thickness and grafting density. PDEGMA layers with a dry ellipsometric thickness of 5-40 nm were synthesized by surface-initiated atom transfer radical polymerization on gold. To assess the temperature-induced changes, the adsorption of bovine serum albumin (BSA) was investigated systematically as a function of film thickness, temperature, and grafting density by surface plasmon resonance (SPR), complemented by wettability and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. BSA adsorption on PDEGMA brushes is shown to differ significantly above and below an apparent transition temperature. This surface transition temperature was found to depend linearly on the PDEGMA thickness and changed from 35 °C at 5 nm thickness to 48 °C at 23 nm. Similarly, a change of the grafting density enables the adjustment of this transition temperature presumably via a transition from the mushroom to the brush regime. Finally, BSA that adsorbed irreversibly on polymer brushes at temperatures above the transition temperature can be desorbed by reducing the temperature to 25 °C, underlining the reversibly switchable properties of PDEGMA brushes in response to temperature changes.

[1]  J. Genzer,et al.  Salt‐Induced Depression of Lower Critical Solution Temperature in a Surface‐Grafted Neutral Thermoresponsive Polymer , 2006 .

[2]  J. Lutz,et al.  Polymerization of oligo(ethylene glycol) (meth)acrylates: Toward new generations of smart biocompatible materials , 2008 .

[3]  H. Tenhu,et al.  Cytotoxicity of thermosensitive polymers poly(N-isopropylacrylamide), poly(N-vinylcaprolactam) and amphiphilically modified poly(N-vinylcaprolactam). , 2005, Biomaterials.

[4]  M. Jonsson,et al.  Understanding Copper-Based Atom-Transfer Radical Polymerization in Aqueous Media , 2004 .

[5]  T. Ederth,et al.  Chemistry-specific surface adsorption of the barnacle settlement-inducing protein complex , 2015, Interface Focus.

[6]  K. Yamamoto,et al.  Conformational change of bovine serum albumin by heat treatment , 1989, Journal of protein chemistry.

[7]  A. Sieron,et al.  Poly[tri(ethylene glycol) ethyl ether methacrylate]-coated surfaces for controlled fibroblasts culturing. , 2013, ACS applied materials & interfaces.

[8]  H. Byrne,et al.  Intracellular localisation, geno- and cytotoxic response of polyN-isopropylacrylamide (PNIPAM) nanoparticles to human keratinocyte (HaCaT) and colon cells (SW 480). , 2010, Toxicology letters.

[9]  H. Schönherr,et al.  Tailored (Bio)Interfaces via Surface Initiated Polymerization: Control of Grafting Density and New Responsive Diblock Copolymer Brushes , 2013 .

[10]  K. Matyjaszewski,et al.  ATRP Synthesis of Thermally Responsive Molecular Brushes from Oligo(ethylene oxide) Methacrylates , 2007 .

[11]  G. Baker,et al.  Surface-initiated atom transfer radical polymerization on gold at ambient temperature , 2000 .

[12]  M. Rahimi,et al.  Cytotoxic evaluation of N-isopropylacrylamide monomers and temperature-sensitive poly(N-isopropylacrylamide) nanoparticles , 2009 .

[13]  M. Houška,et al.  Complete identification of proteins responsible for human blood plasma fouling on poly(ethylene glycol)-based surfaces. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[14]  R. Tilton,et al.  Coverage-Dependent Orientation of Lysozyme Adsorbed on Silica , 2003 .

[15]  B. Nysten,et al.  Surface and bulk collapse transitions of thermoresponsive polymer brushes. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[16]  Jinho Hyun,et al.  “Non‐Fouling” Oligo(ethylene glycol)‐ Functionalized Polymer Brushes Synthesized by Surface‐Initiated Atom Transfer Radical Polymerization , 2004 .

[17]  Emi Watanabe,et al.  Secondary structural change of bovine serum albumin in thermal denaturation up to 130 degrees C and protective effect of sodium dodecyl sulfate on the change. , 2008, The journal of physical chemistry. B.

[18]  Teruo Okano,et al.  Temperature-Responsive Polymer Modified Surface for Cell Sheet Engineering , 2012 .

[19]  Cornelia G Palivan,et al.  Stimuli-Responsive Polymers and Their Applications in Nanomedicine , 2012, Biointerphases.

[20]  T. Ishizone,et al.  Synthesis of Thermally Sensitive Water-Soluble Polymethacrylates by Living Anionic Polymerizations of Oligo(ethylene glycol) Methyl Ether Methacrylates , 2003 .

[21]  D. Leckband,et al.  Protein adsorption mechanisms determine the efficiency of thermally controlled cell adhesion on poly(N-isopropyl acrylamide) brushes. , 2013, Biomacromolecules.

[22]  Masayuki Yamato,et al.  Micropatterned thermoresponsive polymer brush surfaces for fabricating cell sheets with well-controlled orientational structures. , 2011, Biomacromolecules.

[23]  M. Alini,et al.  Tailoring thermoreversible hyaluronan hydrogels by "click" chemistry and RAFT polymerization for cell and drug therapy. , 2010, Biomacromolecules.

[24]  Hongwei Ma,et al.  Surface engineering strategies for control of protein and cell interactions , 2004 .

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

[26]  H. Schönherr,et al.  Nanomechanical Properties of Oligo(ethylene glycol methacrylate) Polymer Brush‐Based Biointerfaces , 2011 .

[27]  M. Cooperstein,et al.  Assessment of cytotoxicity of (N-isopropyl acrylamide) and Poly(N-isopropyl acrylamide)-coated surfaces , 2013, Biointerphases.

[28]  B. Mattiasson,et al.  Smart polymers: Physical forms and bioengineering applications , 2007 .

[29]  Y. Zhu,et al.  Comb-shaped conjugates comprising hydroxypropyl cellulose backbones and low-molecular-weight poly(N-isopropylacryamide) side chains for smart hydrogels: synthesis, characterization, and biomedical applications. , 2010, Bioconjugate chemistry.

[30]  V. Šubr,et al.  Polymer brushes showing non-fouling in blood plasma challenge the currently accepted design of protein resistant surfaces. , 2011, Macromolecular rapid communications.

[31]  Erik Wischerhoff,et al.  Controlled cell adhesion on PEG-based switchable surfaces. , 2008, Angewandte Chemie.

[32]  Teruo Okano,et al.  Temperature-responsive intelligent interfaces for biomolecular separation and cell sheet engineering , 2009, Journal of The Royal Society Interface.

[33]  Q. Su,et al.  Multi-Ligand-Binding Flavoprotein Dodecin as a Key Element for Reversible Surface Modification in Nano-biotechnology. , 2015, ACS nano.

[34]  K. Matyjaszewski,et al.  Densely-Grafted and Double-Grafted PEO Brushes via ATRP. A Route to Soft Elastomers , 2003 .

[35]  K. Kono,et al.  Temperature‐sensitive hyperbranched poly(glycidol)s with oligo(ethylene glycol) monoethers , 2010 .

[36]  D. Leckband,et al.  Protein adsorption on poly(N-isopropylacrylamide) brushes: dependence on grafting density and chain collapse. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[37]  R. Schasfoort,et al.  Angle-scanning SPR imaging for detection of biomolecular interactions on microarrays. , 2008, Biosensors & bioelectronics.

[38]  S. Bartelt-Hunt,et al.  Investigation of Bovine Serum Albumin (BSA) Attachment onto Self-Assembled Monolayers (SAMs) Using Combinatorial Quartz Crystal Microbalance with Dissipation (QCM-D) and Spectroscopic Ellipsometry (SE) , 2015, PloS one.

[39]  T. Okano,et al.  High stability of thermoresponsive polymer-brush-grafted silica beads as chromatography matrices. , 2012, ACS applied materials & interfaces.

[40]  Y. Maeda.  IR Spectroscopic Study on the Hydration and the Phase Transition of Poly(vinyl methyl ether) in Water , 2001 .

[41]  M. Kröger,et al.  Theoretical considerations on mechanisms of harvesting cells cultured on thermoresponsive polymer brushes. , 2012, Biomaterials.

[42]  H. Abruña,et al.  Preventing nonspecific adsorption on polymer brush covered gold electrodes using a modified ATRP initiator. , 2009, Biomacromolecules.

[43]  J. Lutz,et al.  About the Phase Transitions in Aqueous Solutions of Thermoresponsive Copolymers and Hydrogels Based on 2-(2-methoxyethoxy)ethyl Methacrylate and Oligo(ethylene glycol) Methacrylate , 2007 .

[44]  R. Schasfoort,et al.  Handbook of surface plasmon resonance , 2008 .

[45]  Alain M. Jonas,et al.  Thermo-responsive polymer brushes with tunable collapse temperatures in the physiological range , 2007 .

[46]  Ruth Freitag,et al.  Influence of the synthesis conditions and ionic additives on the swelling behaviour of thermo-responsive polyalkylacrylamide hydrogels , 2005 .

[47]  Matthew D. Miller,et al.  Kinetics of surface-initiated atom transfer radical polymerization , 2003 .

[48]  Ronald P. Manginell,et al.  Programmed Adsorption and Release of Proteins in a Microfluidic Device , 2003, Science.

[49]  M. Santore,et al.  Adsorption and reorientation kinetics of lysozyme on hydrophobic surfaces , 2002 .

[50]  Shiping Zhu,et al.  Chain conformation of a new class of PEG-based thermoresponsive polymer brushes grafted on silicon as determined by neutron reflectometry. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[51]  Roderick Y. H. Lim,et al.  Non-interacting molecules as innate structural probes in surface plasmon resonance. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[52]  Kurt Binder,et al.  Polymer brushes on flat and curved surfaces: How computer simulations can help to test theories and to interpret experiments , 2012 .

[53]  N. Ayres.  Polymer brushes: Applications in biomaterials and nanotechnology , 2010 .

[54]  A. Dirani,et al.  Temperature Dependence of the Surface and Volume Hydrophilicity of Hydrophilic Polymer Brushes. , 2016, Langmuir : the ACS journal of surfaces and colloids.

[55]  D. Débarre,et al.  The Conformation of Thermoresponsive Polymer Brushes Probed by Optical Reflectivity. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[56]  Manihar A. Singh,et al.  The Studies of Density, Apparent Molar Volume, and Viscosity of Bovine Serum Albumin, Egg Albumin, and Lysozyme in Aqueous and RbI, CsI, and DTAB Aqueous Solutions at 303.15 K , 2005, Chemistry & biodiversity.

[57]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[58]  G. Olofsson.  Microtitration calorimetric study of the micellization of three poly(oxyethylene)glycol dodecyl ethers , 1985 .

[59]  W. Brittain,et al.  A structural definition of polymer brushes , 2007 .

[60]  M. Urban,et al.  Recent advances and challenges in designing stimuli-responsive polymers , 2010 .

[61]  Tong Cai,et al.  Thermoresponsive oligo(ethylene glycol)-methacrylate- based polymers and microgels , 2010 .

[62]  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.

[63]  Bharat Bhushan,et al.  Smart polymer brushes and their emerging applications , 2012 .

[64]  R. Zhuo,et al.  Fluorescent, thermo-responsive biotin-P(NIPAAm-co-NDAPM)- b-PCL micelles for cell-tracking and drug delivery , 2007 .

[65]  Masayuki Yamato,et al.  Controlled chain length and graft density of thermoresponsive polymer brushes for optimizing cell sheet harvest. , 2010, Biomacromolecules.

[66]  Jean-François Lutz,et al.  Preparation of Ideal PEG Analogues with a Tunable Thermosensitivity by Controlled Radical Copolymerization of 2-(2-Methoxyethoxy)ethyl Methacrylate and Oligo(ethylene glycol) Methacrylate , 2006 .

[67]  Scott T. Milner,et al.  Theory of the grafted polymer brush , 1988 .

[68]  D. Leckband,et al.  Protein Adsorption Modes Determine Reversible Cell Attachment on Poly(N‐isopropyl acrylamide) Brushes , 2012 .

[69]  A. Jonas,et al.  Temperature‐Responsive Polymer Brushes Switching from Bactericidal to Cell‐Repellent , 2010, Advanced materials.

[70]  M. Ward,et al.  Thermoresponsive Polymers for Biomedical Applications , 2011 .

[71]  A. Jonas.  Physicochemical properties of bovine serum high density lipoprotein. , 1972, The Journal of biological chemistry.

[72]  Ashutosh Chilkoti,et al.  In Pursuit of Zero: Polymer Brushes that Resist the Adsorption of Proteins , 2009 .

[73]  H. Klok,et al.  Temperature-controlled masking/unmasking of cell-adhesive cues with poly(ethylene glycol) methacrylate based brushes. , 2014, Biomacromolecules.

[74]  Bridgette M Budhlall,et al.  Temperature dependence of serum protein adsorption in PEGylated PNIPAm microgels. , 2013, Colloids and surfaces. B, Biointerfaces.

[75]  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.