NMR Study on Multiple Environmental Response Behaviors of Poly[2-(diethylamino)ethylmethacry-late](PDMAEMA)

Abstract

Abstract:

Poly[2-(diethylamino)ethylmethacry-late](PDMAEMA) with narrow molecular-weight distribution was synthesized by the atom transfer radical polymerization (ATRP) method. The thermo-sensitive, pH-sensitive and ionic sensitive behaviors of PDMAEMA chains in D₂O solution were investigated by measuring ¹H NMR spectra and relaxation times. It was found that the mobility, temperature-induced lower critical solution temperature (LCST) transition and ionic-strength-induced phase separation of PDMAEMA chains depend on pH of the solution. The mobility of PDMAEMA chains decreased with increasing pH value at room temperature. Ionic-strength-induced phase separation was observed at lower pH values, but not LCST transition. On the contrary, the LCST transition occurred at higher pH values, but not the ionic-strength-induced phase separation.

Key words: thermo-sensitive, ionic sensitive, NMR, PDMAEMA, pH sensitive

CLC Number:

O482.53

XU Yang-Lin, LUO Jing-Ming, RU Ge-Ying, FENG Ji-Wen. NMR Study on Multiple Environmental Response Behaviors of Poly[2-(diethylamino)ethylmethacry-late](PDMAEMA)[J]. Chinese Journal of Magnetic Resonance, 2012, 29(2): 278-287.

References

[1] Rosler A, Vandermeulen G W M, Klok H A. Advanced drug delivery devices via self-assembly of amphiphilic block copolymers[J]. Adv Drug Delivery Rev, 2001, 53(1): 95-108.

[2] Chang Y, Powell E S, Allcock H. R. Environmentally responsive micelles from polystyrene-poly[bis(potassium carboxylatophenoxy)phosphazene\] block copolymers[J]. J Polym Sci Part A: Polym Chem, 2005, 43(13): 2 912-2 920. 

[3] Huang C J, Chang F C. Polypeptide diblock copolymers: syntheses and properties of poly(N-isopropylacrylamide)-b-polylysine[J]. Macromolecules, 2008, 41(19): 7 041-7 052.

[4] Wang D, Wu T, Wan X, et al. Purely salt-responsive micelle formation and inversion based on a novel schizophrenic sulfobetaine block copolymer: structure and kinetics of micellization[J]. Langmuir, 2007, 23(23): 11 866-11 874.

[5] Liu S Y, Armes S P. The facile one-pot synthesis of shell cross-linked micelles in aqueous solution at high solids[J]. J Am Chem Soc, 2001, 123(40): 9 910-9 911.

[6] Liu S Y, Weaver J V M, Tang Y Q, et al. Synthesis of shell cross-linked micelles with pH-responsive cores using ABC triblock copolymers[J]. Macromolecules, 2002, 35(16): 6 121-6 131.

[7] Plamper F A, Ruppel M, Schmalz A, et al. Tuning the thermoresponsive properties of weak polyelectrolytes: Aqueous solutions of starshaped and linear Poly(N,N-dimethylaminoethyl Methacrylate) [J]. Macromolecules, 2007, 40(23): 8 361-8 366.

[8] Plamper F A, Schmalz A, Müller A H E, et al. Tuning the thermoresponsiveness of weak polyelectrolytes by pH and light: lower and upper criticalsolution temperature of Poly(N,N-dimethylaminoethyl methacrylate) [J]. J Am Chem Soc, 2007, 129(47): 14 538-14 539.

[9] Plamper F A, McKee J R, Laukkanen A, et al. Miktoarm stars of poly(ethylene oxide) and poly(dimethylaminoethyl methacrylate): manipulation of micellization by temperature and light[J]. Soft Matter, 2009, 5(9): 1 812-1 821.

[10] Schacher F, Ulbricht M, Müller A H E. Self-supporting, double stimuli- responsive porous membranes from polystyrene-block-poly (N, N-dimethylaminoethyl methacrylate) diblock copolymers[J]. Adv Funct Mater, 2009, 19(7): 1 040-1 045.

[11] Roy D, Knapp J S, Guthrie J T, et al. Antibacterial Cellulose Fiber via RAFT surface graft polymerization[J]. Biomacromolecules, 2008, 9(1): 91-99.

[12] Zhang N, Liu M, Shen Y, et al. Preparation, properties, and drug release of thermo- and pH- sensitive poly ((2-dimethyl amino) ethyl methacrylate)/poly (N, N-diethylacrylamide) semi-IPN hydrogels[J]. J Mater Sci, 2011, 46(5): 1 523-1 534.

[13] Zeng F, Tong Z, Feng H Q. NMR investigation of phase separation in poly (N-isopropyl acrylamide)/water solutions[J]. Polymer, 1997, 38(22): 5 539- 5 544.

[14] Tokuhiro T, Amiya T, Mamada A, et al. NMR study of poly (N-isopropylacrylamide) gels near phase transition[J]. Macromolecules, 1991, 24(10): 2 936- 2 943.

[15] Wang Nian(王念), Ru Ge-ying(茹阁英), Feng Ji-wen(冯继文), et al. NMR studies on phase separation of linear PNIPAM and gel in binary solvents(PNIPAM线性链与凝胶在二元溶剂中相变的变温NMR研究)[J]. Chinese J Magn Reson(波谱学杂志), 2010, 27(3): 461-469.

[16] Wang Lin-lin(王琳琳), Zhao xin(赵新), Sun Wan-fu(孙万赋). Studies on molecular motion of PVP in mixed solvents H₂O/C₃H₆O(PVP在水/丙酮混合溶剂中分子运动行为的研究)[J]. Chinese J Magn Reson(波谱学杂志), 2010, 27(4): 540-547.

[17] Wetering P, Cherng J Y, Talsma H, et al. 2-(Dimethylamino) ethyl methacrylate based (co) polymers as gene transfer agents[J]. J Control Release, 1998, 53(1-3): 145-153. 

[18] Jiang X L, Lok M C, Hennink W E. Degradable-brushed pHEMA-pDMAEMA synthesized via ATRP and click chemistry for gene delivery[J]. Bioconjugate Chem, 2007, 18(6): 2 077-2 084.

[19] Jiang X L, Horst A, Steenbergen M J. Molar-Mass characterization of cationic polymers for gene delivery by aqueous size-exclusion chromatography [J]. Pharmaceut Res, 2006, 23(3): 595-603.

[20] Qiu Zu-wen(裘祖文) , Pei Feng-kui(裴奉奎). Spectroscopy of Nuclear Magnetic Resonance(核磁共振波谱) [M]. Beijing(北京): Science Press(科学出版社), 1989.