Multiresponsive polymers: nano-sized assemblies, stimuli-sensitive gels and smart surfaces

The complex function of living systems is dictated by their inherent cooperative response to multiple external stimuli which induce dynamic changes in their physicochemical properties. Advances in the areas of nano- and bio-technology demand for the development of “smart” synthetic materials that would resemble the living systems in their complex behaviour as a response to applied stimuli. This reversible response directs the formation of hierarchical self-assemblies or stimulates changes in the volume, the shape or the surface characteristics of the system. Progress in this rapidly expanding area can lead to the development of dynamically multiresponsive constructs in the form of polymers, particles, gels or surfaces, for potential use in a wide range of applications such as drug delivery, tissue engineering, self-healing materials, bioseparations, sensors and actuators. This review highlights the recent advances in polymer chemistry to design multiresponsive polymeric materials that recognize independently or synergistically more than one stimulus exhibiting collective responses. Emerging developments, challenges and future trends in this exciting field are also discussed.

[1]  C. R. Becer,et al.  Metal‐free synthesis of responsive polymers: Cloud point tuning by controlled “click” reaction , 2010 .

[2]  M. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001 .

[3]  Jie Yin,et al.  Poly(ether tert‐amine): A novel family of multiresponsive polymer , 2009 .

[4]  S. Armes,et al.  Effect of Partial Quaternization on the Aqueous Solution Properties of Tertiary Amine-Based Polymeric Surfactants: Unexpected Separation of Surface Activity and Cloud Point Behavior , 2001 .

[5]  Kinam Park,et al.  Environment-sensitive hydrogels for drug delivery , 2001 .

[6]  C. R. Becer,et al.  Lower Critical Solution Temperature Behavior of Comb and Graft Shaped Poly(oligo(2-ethyl-2-oxazoline)methacrylate)s , 2009 .

[7]  Andrew A. Burns,et al.  Fluorescent core-shell silica nanoparticles: towards "Lab on a Particle" architectures for nanobiotechnology. , 2006, Chemical Society reviews.

[8]  Erhan Pişkin,et al.  Functional copolymers of N-isopropylacrylamide for bioengineering applications , 2007 .

[9]  Sergiy Minko,et al.  Stimuli-responsive nanoparticles, nanogels and capsules for integrated multifunctional intelligent systems , 2010 .

[10]  Shin-ichi Nakao,et al.  Development of a Fast Response Molecular Recognition Ion Gating Membrane , 1999 .

[11]  A. Metters,et al.  Swelling Behavior of Multiresponsive Poly(methacrylic acid)‐block‐‐poly(N‐isopropylacrylamide) Brushes Synthesized Using Surface‐Initiated Photoiniferter‐Mediated Photopolymerization , 2008 .

[12]  M. Prato,et al.  Synthesis of multifunctional composite microgels via in situ Ni growth on pNIPAM-coated Au nanoparticles. , 2009, ACS nano.

[13]  C. Fotakis,et al.  From superhydrophobicity and water repellency to superhydrophilicity: smart polymer-functionalized surfaces. , 2010, Chemical communications.

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

[15]  Cameron Alexander,et al.  Ion-sensitive "isothermal" responsive polymers prepared in water. , 2008, Journal of the American Chemical Society.

[16]  Jinming Hu,et al.  Responsive Polymers for Detection and Sensing Applications: Current Status and Future Developments , 2010 .

[17]  A. Scherz,et al.  Stimuli responsive materials: new avenues toward smart organic devices , 2005 .

[18]  Jia Guo,et al.  Preparation and characterization of multiresponsive polymer composite microspheres with core–shell structure , 2007 .

[19]  S. Armes,et al.  Responsive core-shell latex particles as colloidosome microcapsule membranes. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[20]  Lei Jiang,et al.  Switchable wettability on cooperative dual-responsive poly-L-lysine surface. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[21]  J. Mano Stimuli‐Responsive Polymeric Systems for Biomedical Applications , 2008 .

[22]  Shoji Kimura,et al.  Development of a molecular recognition ion gating membrane and estimation of its pore size control. , 2002, Journal of the American Chemical Society.

[23]  Masayoshi Watanabe,et al.  A thermally adjustable multicolor photochromic hydrogel. , 2007, Angewandte Chemie.

[24]  H. Adler,et al.  Temperature and pH dependent solubility of novel poly(N‐isopropylacrylamide)‐copolymers , 2000 .

[25]  J. Youngblood,et al.  Self‐Cleaning and Anti‐Fog Surfaces via Stimuli‐Responsive Polymer Brushes , 2007 .

[26]  Dong Wang,et al.  Click Chemistry, A Powerful Tool for Pharmaceutical Sciences , 2008, Pharmaceutical Research.

[27]  Lei Jiang,et al.  Temperature/light dual-responsive surface with tunable wettability created by modification with an azobenzene-containing copolymer , 2006 .

[28]  Paul V Braun,et al.  Glucose-sensitive inverse opal hydrogels: analysis of optical diffraction response. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[29]  Xiaohong Wang,et al.  Reversibly Switchable Double-Responsive Block Copolymer Brushes , 2007 .

[30]  Xi Zhang,et al.  Tuning the Amphiphilicity of Building Blocks: Controlled Self‐Assembly and Disassembly for Functional Supramolecular Materials , 2009 .

[31]  Richard A. Evans,et al.  Photo-responsive systems and biomaterials: photochromic polymers, light-triggered self-assembly, surface modification, fluorescence modulation and beyond , 2010 .

[32]  Jie Yin,et al.  Multistimuli Responsive Amphiphilic Graft Poly(ether amine): Synthesis, Characterization, and Self-Assembly in Aqueous Solution , 2010 .

[33]  C. Detrembleur,et al.  In-situ nitroxide-mediated radical polymerization (NMP) processes: their understanding and optimization. , 2008, Chemical reviews.

[34]  C. R. Becer,et al.  Libraries of Statistical Hydroxypropyl Acrylate Containing Copolymers with LCST Properties Prepared by NMP , 2008 .

[35]  Jin Xie,et al.  Nanoparticle-based theranostic agents. , 2010, Advanced drug delivery reviews.

[36]  Leroy Cronin,et al.  Controlled polymer synthesis--from biomimicry towards synthetic biology. , 2010, Chemical Society reviews.

[37]  Shiyong Liu,et al.  FRET-derived ratiometric fluorescent K+ sensors fabricated from thermoresponsive poly(N-isopropylacrylamide) microgels labeled with crown ether moieties. , 2010, The journal of physical chemistry. B.

[38]  Keisuke Suzuki,et al.  Oligomeric catechins: an enabling synthetic strategy by orthogonal activation and C(8) protection. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[39]  J. Lyskawa,et al.  Tetrathiafulvalene end-functionalized poly(N-isopropylacrylamide): a new class of amphiphilic polymer for the creation of multistimuli responsive micelles. , 2010, Journal of the American Chemical Society.

[40]  S. Rowan,et al.  Multistimuli, multiresponsive metallo-supramolecular polymers. , 2003, Journal of the American Chemical Society.

[41]  B. Olsen,et al.  Self-assembly of rod–coil block copolymers , 2008 .

[42]  Craig J Hawker,et al.  Precise synthesis of molecularly defined oligomers and polymers by orthogonal iterative divergent/convergent approaches. , 2011, Macromolecular rapid communications.

[43]  C. Bowman,et al.  Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis. , 2010, Chemical Society reviews.

[44]  Anna Gutowska,et al.  Lessons from nature: stimuli-responsive polymers and their biomedical applications. , 2002, Trends in biotechnology.

[45]  Shi-zhong Luo,et al.  Two-stage collapse of unimolecular micelles with double thermoresponsive coronas. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[46]  Carmen Alvarez-Lorenzo,et al.  Temperature- and light-responsive blends of pluronic F127 and poly(N,N-dimethylacrylamide-co-methacryloyloxyazobenzene). , 2007, Langmuir : the ACS journal of surfaces and colloids.

[47]  H. Kolb,et al.  The growing impact of click chemistry on drug discovery. , 2003, Drug discovery today.

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

[49]  Maria Vamvakaki,et al.  Multiresponsive Spiropyran-Based Copolymers Synthesized by Atom Transfer Radical Polymerization , 2010 .

[50]  S. Minko,et al.  Multiresponsive Biopolyelectrolyte Membrane , 2008 .

[51]  Anders Hult,et al.  Intelligent dual-responsive cellulose surfaces via surface-initiated ATRP. , 2008, Biomacromolecules.

[52]  Ying Li,et al.  Dual redox responsive assemblies formed from diselenide block copolymers. , 2010, Journal of the American Chemical Society.

[53]  Daniel J. Burke,et al.  Applications of orthogonal "click" chemistries in the synthesis of functional soft materials. , 2009, Chemical reviews.

[54]  Yong Huang,et al.  Self-assembly and dual-stimuli sensitivities of hydroxypropylcellulose-graft-poly(N,N-dimethyl aminoethyl methacrylate) copolymers in aqueous solution. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[55]  S. Armes,et al.  Characterisation of the dispersion stability of a stimulus responsive core-shell colloidal latex , 2010 .

[56]  Mark W Rutland,et al.  Tunable nanolubrication between dual-responsive polyionic grafts. , 2009, Nano letters.

[57]  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.

[58]  B. Sumerlin,et al.  Triply-responsive boronic acid block copolymers: solution self-assembly induced by changes in temperature, pH, or sugar concentration. , 2009, Chemical communications.

[59]  S. Armes,et al.  Stimuli-Responsive Polymer Ultrathin Films with a Binary Architecture: Combined Layer-by-Layer Polyelectrolyte and Surface-Initiated Polymerization Approach , 2008 .

[60]  Zhishen Ge,et al.  Synthesis and Self-Assembly of Coil−Rod Double Hydrophilic Diblock Copolymer with Dually Responsive Asymmetric Centipede-Shaped Polymer Brush as the Rod Segment , 2009 .

[61]  J. Iturri,et al.  Multiresponsive PEDOT–Ionic Liquid Materials for the Design of Surfaces with Switchable Wettability , 2009 .

[62]  Jianping Gao,et al.  Multiresponsive Inverse‐Opal Hydrogels , 2007 .

[63]  Yi Chen,et al.  Dual Stimuli‐Responsive Supramolecular Polypeptide‐Based Hydrogel and Reverse Micellar Hydrogel Mediated by Host–Guest Chemistry , 2010 .

[64]  Stephen Mann,et al.  Life as a nanoscale phenomenon. , 2008, Angewandte Chemie.

[65]  Lei Jiang,et al.  Dual‐Responsive Surfaces That Switch between Superhydrophilicity and Superhydrophobicity , 2006 .

[66]  Luc Tremblay,et al.  Doubly photoresponsive and water‐soluble block copolymers: Synthesis and thermosensitivity , 2010 .

[67]  Weitai Wu,et al.  Multifunctional hybrid nanogel for integration of optical glucose sensing and self-regulated insulin release at physiological pH. , 2010, ACS nano.

[68]  A. P. Silva,et al.  A supramolecular chemistry basis for molecular logic and computation , 2007 .

[69]  R. Ulijn,et al.  Phosphatase/temperature responsive poly(2-isopropyl-2-oxazoline) , 2011 .

[70]  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.

[71]  Jie Yin,et al.  Multistimuli Responsive Organosilica Hybrid Nanoparticles Based on Poly(ether amine) , 2010 .

[72]  Probal Banerjee,et al.  Smart Core—Shell Hybrid Nanogels with Ag Nanoparticle Core for Cancer Cell Imaging and Gel Shell for pH-Regulated Drug Delivery , 2010 .

[73]  Natalio Krasnogor,et al.  Diol–boronic acid complexes integrated by responsive polymers—a route to chemical sensing and logic operations , 2009 .

[74]  Günter Mayer,et al.  Biologically active molecules with a "light switch". , 2006, Angewandte Chemie.

[75]  Mei-Jia Yang,et al.  Preparation and characterization of novel cationic pH-responsive poly(N,N'-dimethylamino ethyl methacrylate) microgels. , 2007, Journal of colloid and interface science.

[76]  Y. Harada,et al.  Hydrophilic fluorescent nanogel thermometer for intracellular thermometry. , 2009, Journal of the American Chemical Society.

[77]  S. Armes,et al.  Synthesis of Controlled Structure Water-Soluble Diblock Copolymers via Oxyanionic Polymerization , 1999 .

[78]  S. Perrier,et al.  Bioapplications of RAFT polymerization. , 2009, Chemical reviews.

[79]  T. Aoyagi,et al.  Stimuli-responsive properties of N-isopropylacrylamide-based ultrathin hydrogel films prepared by photo-cross-linking. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[80]  S. Minko Responsive Polymer Brushes , 2006 .

[81]  Mingyu Guo,et al.  Dual Stimuli-Responsive Supramolecular Hydrogel Based on Hybrid Inclusion Complex (HIC) , 2010, Macromolecules.

[82]  C. Alexander,et al.  Control of bacterial aggregation by thermoresponsive glycopolymers. , 2007, Journal of the American Chemical Society.

[83]  Ulrich S. Schubert,et al.  Libraries of methacrylic acid and oligo(ethylene glycol) methacrylate copolymers with LCST behavior , 2008 .

[84]  Lei Jiang,et al.  Integrating Ionic Gate and Rectifier Within One Solid‐State Nanopore via Modification with Dual‐Responsive Copolymer Brushes , 2010 .

[85]  Bin Zhao,et al.  Thermosensitive aqueous gels with tunable sol-gel transition temperatures from thermo- and pH-responsive hydrophilic ABA triblock copolymer. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[86]  Sergiy Minko,et al.  Stimuli‐Responsive Porous Hydrogels at Interfaces for Molecular Filtration, Separation, Controlled Release, and Gating in Capsules and Membranes , 2010, Advanced materials.

[87]  Lei Jiang,et al.  Chemical Dual-Responsive Wettability of Superhydrophobic PANI-PAN Coaxial Nanofibers , 2007 .

[88]  Wim Bras,et al.  Reciprocating power generation in a chemically driven synthetic muscle. , 2006, Nano letters.

[89]  S Thayumanavan,et al.  Multi-stimuli sensitive amphiphilic block copolymer assemblies. , 2009, Journal of the American Chemical Society.

[90]  T. Peng,et al.  PNIPAAm and PMAA co-grafted porous PE membranes: living radical co-grafting mechanism and multi-stimuli responsive permeability , 2001 .

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

[92]  G. Gerlach,et al.  Chemical sensors based on multiresponsive block copolymer hydrogels , 2007 .

[93]  K. Matyjaszewski,et al.  The effect of structure on the thermoresponsive nature of well‐defined poly(oligo(ethylene oxide) methacrylates) synthesized by ATRP , 2008 .

[94]  C. Alexander,et al.  Stimuli responsive polymers for biomedical applications. , 2005, Chemical Society reviews.

[95]  Roeland J. M. Nolte,et al.  A Polymersome Nanoreactor with Controllable Permeability Induced by Stimuli‐Responsive Block Copolymers , 2009 .

[96]  K. Leong,et al.  Dual‐Sensitive Micellar Nanoparticles Regulate DNA Unpacking and Enhance Gene‐Delivery Efficiency , 2010, Advanced materials.

[97]  Lei Tao,et al.  Synthesis of azide/alkyne-terminal polymers and application for surface functionalisation through a [2 + 3] Huisgen cycloaddition process, "click chemistry". , 2007, Soft matter.

[98]  C. R. Becer,et al.  Dual Responsive Methacrylic Acid and Oligo(2-ethyl-2-oxazoline) Containing Graft Copolymers , 2010 .

[99]  Yong Huang,et al.  Dual-stimuli sensitive nanogels fabricated by self-association of thiolated hydroxypropyl cellulose , 2011 .

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

[101]  Yukishige Ito,et al.  Orthogonal Glycosylation Strategy in Oligosaccharide Synthesis , 1994 .

[102]  Toshiyuki Kanamori,et al.  Photoresponsive properties of poly(N-isopropylacrylamide) hydrogel partly modified with spirobenzopyran. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[103]  L. Jiang,et al.  Multiresponsive Surfaces Change Between Superhydrophilicity and Superhydrophobicity , 2007 .

[104]  S. Minko,et al.  Multiresponsive, Hierarchically Structured Membranes: New, Challenging, Biomimetic Materials for Biosensors, Controlled Release, Biochemical Gates, and Nanoreactors , 2009 .

[105]  Haifeng Yu,et al.  Multiresponsive reversible gels based on a carboxylic azo polymer , 2010 .

[106]  Vladimir I Minkin,et al.  Photo-, thermo-, solvato-, and electrochromic spiroheterocyclic compounds. , 2004, Chemical reviews.

[107]  J. Rodríguez-Hernández,et al.  Structured multistimuli‐responsive functional polymer surfaces obtained by interfacial diffusion of amphiphilic block copolymers , 2010 .

[108]  M. Finn,et al.  Click chemistry: function follows form. , 2010, Chemical Society reviews.

[109]  Shiyong Liu,et al.  Thermo- and light-regulated fluorescence resonance energy transfer processes within dually responsive microgels , 2011 .