制备了两种糖基引发剂(AcCDBr和AcG-lABr),以CuBr/三-(N,N-二甲基氨基乙基)胺(Me6TREN)为催化体系,应用原子转移自由基聚合方法,在60℃下引发N-异丙基丙烯酰胺聚合,脱去乙酰基保护后得到末端分别带有β-环糊精和2-氨基葡萄糖基团的线形聚(N-异丙基丙烯酰胺)(CD-PAM和GlA-PAM)。对产物的结构进行了表征,凝胶渗透色谱(GPC)测得聚合物分子量分布较窄(PDI=1.12~1.20)。采用紫外-可见吸收光谱仪(UV-Vis)和示差扫描量热仪(DSC)对聚合物水溶液的相转变行为进行了测试,结果表明末端引入糖类结构使得PNIPAM的最低临界溶解温度(LCST)升高,并随着分子量的增大而降低,而且相同聚合度的GlA-PAM的LCST比CD-PAM的高3.7℃左右。
Two kinds of derived carbohydrates(AcCDBr and AcGlABr) were synthesized as the initiators for atom transfer radical polymerization(ATRP) of N-isopropylacrylamide.The polymerizations of end-functionalized poly(N-isopropylacrylamide) with different saccharide groups(CD-PAM and GlA-PAM for short) were carried out using CuBr/tris(2-dimethylaminoethyl)amine(Me6TREN) as the catalyst system with the feed ratio of n[monomer]0∶n[initiator]0∶n0∶n[Me6TREN]0 = 50∶1∶1∶1 in DMF/water at 60℃.The structures of the initiators and the polymers were characterized by means of FT-IR and NMR.Low polydispersity indices(PDI = 1.12-1.20) were obtained by gel permeation chromatography(GPC).Ultraviolet-visible spectroscopy(UV-vis) and differential scanning calorimetry(DSC) were employed to measure the lower critical solution temperature(LCST) of the end-functionalized PNIPAMs.The results showed the LCSTs of end-functionalized PNIPAM were increased due to the hydrophilicity of the saccharide groups,and the LCST of GlA-PAM was about 3.7℃ higher than that of CD-PAM.Furthermore,the end-functionalized PNIPAM showed an inverse molecular weight dependence of their cloud points.
参考文献
[1] | Zhang XZ;Zhuo RX;Cui JZ;Zhang JT .A novel thermo-responsive drug delivery system with positive controlled release.[J].International Journal of Pharmaceutics,2002(1/2):43-50. |
[2] | Sivanand S.Pennadam;Chrishtina F.Dutta;Darren Mernagh;Matthieu D.Lavigne .Control of A Multisubunit DNA Motor by a Thermoresponsive Polymer Switch[J].Journal of the American Chemical Society,2004(41):13208-13209. |
[3] | Barker IC.;Cowie JMG.;Huckerby TN.;Shaw DA.;Soutar I.;Swanson L. .Studies of the "smart" thermoresponsive behavior of copolymers of N-isopropylacrylamide and N,N-dimethylacrylamide in dilute aqueous solution[J].Macromolecules,2003(20):7765-7770. |
[4] | Maria Loreta Patrizi;Giovanna Piantanida;Carlo Coluzza;Giancarlo Masci .ATRP synthesis and association properties of temperature responsivedextran copolymers grafted with poly(N-isopropylacrylamide)[J].European Polymer Journal,2009(10):2779-2787. |
[5] | Schilli CM;Zhang MF;Rizzardo E;Thang SH;Chong YK;Edwards K;Karlsson G;Muller AHE .A new double-responsive block copolymer synthesized via RAFT polymerization: Poly(N-isopropylacrylamide)-block-poly(acrylic acid)[J].Macromolecules,2004(21):7861-7866. |
[6] | Kim DJ.;Heo JY.;Kim KS.;Choi IS. .Formation of thermoresponsive poly(nisopropylacrylamide)/dextran particles by atom transfer radical polymerization[J].Macromolecular rapid communications: Publishing the newsletters of the European Polymer Federation,2003(8):517-521. |
[7] | Jin-Shan Wang;Krzysztof Matyjaszewski .Controlled/'Living' Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes[J].Journal of the American Chemical Society,1995(20):5614-5615. |
[8] | Krzysztof Matyjaszewski;Jianhui Xia .Atom Transfer Radical Polymerization[J].Chemical Reviews,2001(9):2921-2990. |
[9] | Masci G;Giacomelli L;Crescenzi V .Atom transfer radical polymerization of N-isopropylacrylamide[J].Macromolecular rapid communications: Publishing the newsletters of the European Polymer Federation,2004(4):559-564. |
[10] | Duan Q;Miura Y;Narumi A;Shen X;Sato S;Satoh T;Kakuchi T .Synthesis and thermoresponsive property of end-functionalized poly(N-isopropylacrylamide) with pyrenyl group[J].Journal of Polymer Science, Part A. Polymer Chemistry,2006(3):1117-1124. |
[11] | Henke C;Steinem C;Janshoff A;Steffan G;Luftmann H;Sieber M .SELF-ASSEMBLED MONOLAYERS OF MONOFUNCTIONALIZED CYCLODEXTRINS ONTO GOLD - A MASS SPECTROMETRIC CHARACTERIZATION AND IMPEDANCE ANALYSIS OF HOST-GUEST INTERACTION[J].Analytical chemistry,1996(18):3158-3165. |
[12] | Jun Shan;Jie Chen;Markus Nuopponen;Heikki Tenhu .Two Phase Transitions of Poly(N-isopropylacrylamide) Brushes Bound to Gold Nanoparticles[J].Langmuir: The ACS Journal of Surfaces and Colloids,2004(11):4671-4676. |
- 下载量()
- 访问量()
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%