Water‐soluble triply‐responsive homopolymers of N,N‐dimethylaminoethyl methacrylate with a terminal azobenzene moiety

Novel water-soluble triply-responsive homopolymers of N,N-dimethylaminoethyl methacrylate (DMAEMA) containing an azobenzene moiety as the terminal group were synthesized by atom transfer radical polymerization (ATRP) technique. The ATRP process of DMAEMA was initiated by an azobenzene derivative substituted with a 2-bromoisobutyryl group (Azo-Br) in the presence of CuCl/Me₆TREN in 1,4-dioxane as a catalyst system. The molecular weights and their polydispersities of the resulting homopolymers (Azo-PDMAEMA) were characterized by gel permeation chromatography (GPC). The homopolymers are soluble in aqueous solution and exhibit a lower critical solution temperature (LCST) that alternated reversibly in response to Ph and photoisomerization of the terminal azobenzene moiety. It was found that the LCST increased as pH decreased in the range of testing. Under UV light irradiation, the trans-to-cis photoisomerization of the azobenzene moiety resulted in a higher LCST, whereas it recovered under visible light irradiation. This kind of polymers should be particularly interesting for a variety of potential applications in some promising areas, such as drug controlled-releasing carriers and intelligent materials because of the multistimuli responsive property.

[1]  M. Ciampolini,et al.  Five-Coordinated High-Spin Complexes of Bivalent Cobalt, Nickel, andCopper with Tris(2-dimethylaminoethyl)amine , 1966 .

[2]  Masahiro Irie,et al.  Photoresponsive polymers. Photocontrol of the phase separation temperature of aqueous solutions of poly-[N-isopropylacrylamide-co-N-(4-phenylazophenyl)acrylamide] , 1988 .

[3]  C. Imrie,et al.  Synthesis and characterization of spin-labelled and spin-probed side-chain liquid crystal polymers , 1996 .

[4]  Jun Gao,et al.  The coil-to-globule transition of Poly(N-isopropylacrylamide) on the surface of a surfactant-free polystyrene nanoparticle , 1997 .

[5]  K. Jankova,et al.  Synthesis of Amphiphilic PS-b-PEG-b-PS by Atom Transfer Radical Polymerization , 1998 .

[6]  Zhang,et al.  Controlled/"Living" Radical Polymerization of 2-(Dimethylamino)ethyl Methacrylate. , 1998, Macromolecules.

[7]  W. Hennink,et al.  Structure-activity relationships of water-soluble cationic methacrylate/methacrylamide polymers for nonviral gene delivery. , 1999, Bioconjugate chemistry.

[8]  T. Okano,et al.  Gene expression control by temperature with thermo-responsive polymeric gene carriers. , 2000, Journal of controlled release : official journal of the Controlled Release Society.

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

[10]  Xihua Lu,et al.  Phase transition behavior of hydroxypropylcellulose under interpolymer complexation with poly(acrylic acid) , 2002 .

[11]  V. Percec,et al.  Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride. , 2002, Journal of the American Chemical Society.

[12]  Ruth Freitag,et al.  Synthesis and Characterization of Photoresponsive N-Isopropylacrylamide Cotelomers , 2003 .

[13]  K. Matyjaszewski,et al.  ATRP synthesis of amphiphilic random, gradient, and block copolymers of 2-(dimethylamino)ethyl methacrylate and n-butyl methacrylate in aqueous media. , 2003, Biomacromolecules.

[14]  P. Degée,et al.  Solvent-free synthesis and purification of poly[2-(dimethylamino)ethyl methacrylate] by atom transfer radical polymerization. , 2003, Chemical communications.

[15]  Nobuyuki Tamaoki,et al.  Polymers derived from N‐isopropylacrylamide and azobenzene‐containing acrylamides: Photoresponsive affinity to water , 2004 .

[16]  T. Shinbo,et al.  Characteristic Phase Transition of Aqueous Solution of Poly(N-isopropylacrylamide) Functionalized with Spirobenzopyran , 2004 .

[17]  S. Armes,et al.  Synthesis of sterically stabilized polystyrene latex particles using cationic block copolymers and macromonomers and their application as stimulus-responsive particulate emulsifiers for oil-in-water emulsions. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[18]  Yue Zhao,et al.  Preparation of Azobenzene-Containing Amphiphilic Diblock Copolymers for Light-Responsive Micellar Aggregates , 2004 .

[19]  E. Gil,et al.  Stimuli-reponsive polymers and their bioconjugates , 2004 .

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

[21]  A. Dobrynin,et al.  Theory of polyelectrolytes in solutions and at surfaces , 2005 .

[22]  P. Topham,et al.  Controlled growth of poly(2-(diethylamino)ethyl methacrylate) brushes via atom transfer radical polymerisation on planar silicon surfaces , 2006 .

[23]  Krzysztof Matyjaszewski,et al.  Phototunable Temperature-Responsive Molecular Brushes Prepared by ATRP , 2006 .

[24]  V. Percec,et al.  Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 degrees C. , 2006, Journal of the American Chemical Society.

[25]  Nobuyuki Tamaoki,et al.  Synthesis and Photoinduced Phase Transitions of Poly(N-isopropylacrylamide) Derivative Functionalized with Terminal Azobenzene Units , 2007 .

[26]  Krzysztof Matyjaszewski,et al.  Light-induced reversible formation of polymeric micelles. , 2007, Angewandte Chemie.

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

[28]  R. Koepsel,et al.  Antibacterial polypropylene via surface-initiated atom transfer radical polymerization. , 2007, Biomacromolecules.

[29]  V. Percec,et al.  Implications of monomer and initiator structure on the dissociative electron-transfer step of SET-LRP , 2008 .

[30]  Yen Wei,et al.  Synthesis of cellulose-graft-poly(N,N-dimethylamino-2-ethyl methacrylate) copolymers via homogeneous ATRP and their aggregates in aqueous media. , 2008, Biomacromolecules.

[31]  K. Matyjaszewski,et al.  Temperature- and pH-Responsive Dense Copolymer Brushes Prepared by ATRP , 2008 .

[32]  T. Okano,et al.  Preparation of thermoresponsive cationic copolymer brush surfaces and application of the surface to separation of biomolecules. , 2008, Biomacromolecules.

[33]  S. Ganta,et al.  A review of stimuli-responsive nanocarriers for drug and gene delivery. , 2008, Journal of controlled release : official journal of the Controlled Release Society.

[34]  V. Percec,et al.  Ultrafast SET-LRP of methyl acrylate at 25 °C in alcohols , 2008 .

[35]  H. Möhwald,et al.  Two-Stage pH Response of Poly(4-vinylpyridine) Grafted Gold Nanoparticles , 2008 .

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

[37]  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.

[38]  Qian Yang,et al.  AB2-type amphiphilic block copolymers composed of poly(ethylene glycol) and poly(N-isopropylacrylamide) via single-electron transfer living radical polymerization: Synthesis and characterization , 2009 .

[39]  Patrick Theato,et al.  Thermo- and Light-Responsive Polymers Containing Photoswitchable Azobenzene End Groups , 2009 .

[40]  V. Percec,et al.  Surface-Dependent Kinetics of Cu(0)-Wire-Catalyzed Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in DMSO at 25 °C , 2009 .

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

[42]  Yen Wei,et al.  Cellulose-based dual graft molecular brushes as potential drug nanocarriers: stimulus-responsive micelles, self-assembled phase transition behavior, and tunable crystalline morphologies. , 2009, Biomacromolecules.

[43]  Patrick Theato,et al.  Temperature- and Light-Responsive Polyacrylamides Prepared by a Double Polymer Analogous Reaction of Activated Ester Polymers , 2009 .

[44]  Feng Tian,et al.  Facile synthesis of triple‐stimuli (photo/pH/thermo) responsive copolymers of 2‐diazo‐1,2‐naphthoquinone‐mediated poly(N‐isopropylacrylamide‐co‐N‐hydroxymethylacrylamide) , 2009 .

[45]  Yongjun Li,et al.  PNIPAM‐b‐(PEA‐g‐PDMAEA) double‐hydrophilic graft copolymer: Synthesis and its application for preparation of gold nanoparticles in aqueous media , 2009 .

[46]  Yoshinobu Nakamura,et al.  Synthesis of stimuli‐responsive macroazoinitiators and their use as an inistab toward hairy polymer latex particles , 2009 .