In this paper, we describe the successful construction, characteristics and interaction with proteins of stimuli-responsive thin nanostructured films prepared by layer-by-layer (LbL) sequential assembly of PNIPAM-containing polyelectrolytes and PAH. PAA-b-PNIPAM block copolymers were synthesized in order to benefit from (i) the ionizable properties of PAA, to be involved in the LbL assembly, and (ii) the sensitivity of PNIPAM to temperature stimulus. The impact of parameters related to the structure and size of the macromolecules (their molecular weight and the relative degree of polymerization of PAA and PNIPAM), and the interaction with proteins under physico-chemical stimuli, such as pH and temperature, are carefully investigated. The incorporation of PAA-b-PNIPAM into multilayered films is shown to be successful whatever the block copolymer used, resulting in slightly thicker films than the corresponding (PAA/PAH)n film. Importantly, the protein adsorption studies demonstrate that it is possible to alter the adsorption behavior of proteins on (PAA-b-PNIPAM/PAH)n surfaces by varying the temperature and/or the pH of the medium, which seems to be intimately related to two key factors: (i) the ability of PNIPAM units to undergo conformational changes and (ii) the structural changes of the film made of weak polyelectrolytes. The simplicity of construction of these PNIPAM block copolymer-based LbL coatings on a large range of substrates, combined with their highly tunable features, make them ideal candidates to be employed for various biomedical applications requiring the control of protein adsorption
Lavalle Philippe, Voegel Jean-Claude, Vautier Dominique, Senger Bernard, Schaaf Pierre, Ball Vincent, Dynamic Aspects of Films Prepared by a Sequential Deposition of Species: Perspectives for Smart and Responsive Materials, 10.1002/adma.201003309
Boudou Thomas, Crouzier Thomas, Ren Kefeng, Blin Guillaume, Picart Catherine, Multiple Functionalities of Polyelectrolyte Multilayer Films: New Biomedical Applications, 10.1002/adma.200901327
Heuberger R., Sukhorukov G., Vörös J., Textor M., Möhwald H., Biofunctional Polyelectrolyte Multilayers and Microcapsules: Control of Non-Specific and Bio-Specific Protein Adsorption, 10.1002/adfm.200400063
Choi Jeeyoung, Rubner Michael F., Influence of the Degree of Ionization on Weak Polyelectrolyte Multilayer Assembly, 10.1021/ma048596o
Shiratori S. S., Rubner M. F., pH-Dependent Thickness Behavior of Sequentially Adsorbed Layers of Weak Polyelectrolytes, 10.1021/ma991645q
Itano Koji, Choi Jeeyoung, Rubner Michael F., Mechanism of the pH-Induced Discontinuous Swelling/Deswelling Transitions of Poly(allylamine hydrochloride)-Containing Polyelectrolyte Multilayer Films, 10.1021/ma047667g
Burke Susan E., Barrett Christopher J., pH-Dependent Loading and Release Behavior of Small Hydrophilic Molecules in Weak Polyelectrolyte Multilayer Films, 10.1021/ma049445o
Heskins M., Guillet J. E., Solution Properties of Poly(N-isopropylacrylamide), 10.1080/10601326808051910
Jochum Florian D., Theato Patrick, Temperature- and light-responsive smart polymer materials, 10.1039/c2cs35191a
Cooperstein Marta A., Canavan Heather E., Biological Cell Detachment from Poly(N-isopropyl acrylamide) and Its Applications, 10.1021/la902587p
Burkert Sina, Bittrich Eva, Kuntzsch Marco, Müller Martin, Eichhorn Klaus-Jochen, Bellmann Cornelia, Uhlmann Petra, Stamm Manfred, Protein Resistance of PNIPAAm Brushes: Application to Switchable Protein Adsorption, 10.1021/la902505q
Cole Martin A., Jasieniak Marek, Thissen Helmut, Voelcker Nicolas H., Griesser Hans J., Time-of-Flight-Secondary Ion Mass Spectrometry Study of the Temperature Dependence of Protein Adsorption onto Poly(N-isopropylacrylamide) Graft Coatings, 10.1021/ac9009337
Pavlukhina Svetlana, Sukhishvili Svetlana, Polymer assemblies for controlled delivery of bioactive molecules from surfaces, 10.1016/j.addr.2011.03.017
Matyjaszewski Krzysztof, Xia Jianhui, Atom Transfer Radical Polymerization, 10.1021/cr940534g
Webber G. B., Wanless E. J., Armes S. P., Tang Y., Li Y., Biggs S., Nano-Anemones: Stimulus-Responsive Copolymer-Micelle Surfaces, 10.1002/adma.200400086
Tang Tian, Castelletto Valeria, Parras Petros, Hamley Ian W., King Stephen M., Roy Debashish, Perrier Sebastien, Hoogenboom Richard, Schubert Ulrich S., Thermo-responsive Poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) Block Copolymers Synthesized by RAFT Polymerization: Micellization and Gelation, 10.1002/macp.200600309
Cammas S, Suzuki K, Sone C, Sakurai Y, Kataoka K, Okano T, Thermo-responsive polymer nanoparticles with a core-shell micelle structure as site-specific drug carriers, 10.1016/s0168-3659(97)00040-0
Erel Irem, Zhu Zhichen, Sukhishvili Svetlana, Patyukova Elena, Potemkin Igor, Kramarenko Elena, Two Types of Block Copolymer Micelles with Ion-Containing Cores, 10.1002/marc.200900659
Zhu Zhichen, Sukhishvili Svetlana A., Temperature-Induced Swelling and Small Molecule Release with Hydrogen-Bonded Multilayers of Block Copolymer Micelles, 10.1021/nn900655z
Xu Li, Zhu Zhichen, Sukhishvili Svetlana A., Polyelectrolyte Multilayers of Diblock Copolymer Micelles with Temperature-Responsive Cores, 10.1021/la1038014
Erel Irem, Zhu Zhichen, Zhuk Aliaksandr, Sukhishvili Svetlana A., Hydrogen-bonded layer-by-layer films of block copolymer micelles with pH-responsive cores, 10.1016/j.jcis.2010.11.083
Schilli Christine M., Zhang Mingfu, Rizzardo Ezio, Thang San H., Chong ) Y. K., Edwards Katarina, Karlsson Göran, Müller Axel H. E., A New Double-Responsive Block Copolymer Synthesized via RAFT Polymerization: Poly(N-isopropylacrylamide)-block-poly(acrylic acid), 10.1021/ma035838w
Aqil A., Vasseur S., Duguet E., Passirani C., Benoît J. P., Jérôme R., Jérôme C., Magnetic nanoparticles coated by temperature responsive copolymers for hyperthermia, 10.1039/b804003f
Bieker Peter, Schönhoff Monika, Linear and Exponential Growth Regimes of Multilayers of Weak Polyelectrolytes in Dependence on pH, 10.1021/ma1007489
Bromberg Lev, Properties of Aqueous Solutions and Gels of Poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-g-poly(acrylic acid), 10.1021/jp983162e
Philippova Olga E., Hourdet Dominique, Audebert Roland, Khokhlov Alexei R., pH-Responsive Gels of Hydrophobically Modified Poly(acrylic acid), 10.1021/ma970957v
Bieker Peter, Schönhoff Monika, Linear and Exponential Growth Regimes of Multilayers of Weak Polyelectrolytes in Dependence on pH, 10.1021/ma1007489
Burke Susan E., Barrett Christopher J., Acid−Base Equilibria of Weak Polyelectrolytes in Multilayer Thin Films, 10.1021/la026500i
Weijers Mireille, Barneveld Peter A., Cohen Stuart Martien A., Visschers Ronald W., Heat-induced denaturation and aggregation of ovalbumin at neutral pH described by irreversible first-order kinetics, 10.1110/ps.03242803
Müller M., Kessler B., Houbenov N., Bohatá K., Pientka Z., Brynda E., pH Dependence and Protein Selectivity of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers Studied by in Situ ATR-FTIR Spectroscopy, 10.1021/bm050631r
Schwinté P., Ball V., Szalontai B., Haikel Y., Voegel J.-C., Schaaf P., Secondary Structure of Proteins Adsorbed onto or Embedded in Polyelectrolyte Multilayers, 10.1021/bm025547f
Ladam Guy, Gergely Csilla, Senger Bernard, Decher Gero, Voegel Jean-Claude, Schaaf Pierre, Cuisinier Frédéric J. G., Protein Interactions with Polyelectrolyte Multilayers: Interactions between Human Serum Albumin and Polystyrene Sulfonate/Polyallylamine Multilayers, 10.1021/bm005572q
Salloum David S., Schlenoff Joseph B., Protein Adsorption Modalities on Polyelectrolyte Multilayers, 10.1021/bm034522t
Balamurugan S., Mendez Sergio, Balamurugan Sreelatha S., O'Brien Michael J., López Gabriel P., Thermal Response of Poly(N-isopropylacrylamide) Brushes Probed by Surface Plasmon Resonance, 10.1021/la026787j
Ladam Guy, Schaaf Pierre, Cuisinier Frédéric J. G., Decher Gero, Voegel Jean-Claude, Protein Adsorption onto Auto-Assembled Polyelectrolyte Films, 10.1021/la0013087
Rabe Michael, Verdes Dorinel, Seeger Stefan, Understanding protein adsorption phenomena at solid surfaces, 10.1016/j.cis.2010.12.007
Souza Clitor J.F., Garcia-Rojas Edwin E., Effects of salt and protein concentrations on the association and dissociation of ovalbumin-pectin complexes, 10.1016/j.foodhyd.2015.01.010
Quinn Anthony, Tjipto Elvira, Yu Aimin, Gengenbach Thomas R., Caruso Frank, Polyelectrolyte Blend Multilayer Films: Surface Morphology, Wettability, and Protein Adsorption Characteristics, 10.1021/la0634746
Mendelsohn Jonas D., Yang Sung Yun, Hiller Jeri'Ann, Hochbaum Allon I., Rubner Michael F., Rational Design of Cytophilic and Cytophobic Polyelectrolyte Multilayer Thin Films, 10.1021/bm0256101
Dubas Stephan T., Schlenoff Joseph B., Polyelectrolyte Multilayers Containing a Weak Polyacid: Construction and Deconstruction, 10.1021/ma001720t
Harris Jeremy J., Bruening Merlin L., Electrochemical and in Situ Ellipsometric Investigation of the Permeability and Stability of Layered Polyelectrolyte Films, 10.1021/la990620h
Schlenoff Joseph B., Zwitteration: Coating Surfaces with Zwitterionic Functionality to Reduce Nonspecific Adsorption, 10.1021/la500057j
Bibliographic reference
Osypova, Alina ; Magnin, Delphine ; Sibret, P. ; Aqil, A. ; Jerôme, Christine ; et. al. Dual stimuli-responsive coating designed through layer-by-layer assembly of PAA-b-PNIPAM block copolymers for the control of protein adsorption. In: Soft Matter, Vol. 11, no.41, p. 8154-8164 (2015)