通过酶促反应和可逆加成-断裂链转移聚合(RAFT)聚合得到温度敏感性的双糖无规聚合物聚(二聚乙二醇单甲醚甲基丙烯酸酯-6-O-乙烯基己二酸-D-吡喃型葡萄糖/半乳糖酯)[Poly(DEGMA-co-OVNGmix)];利用还原剂将聚合物末端的硫酯键还原,得到末端为—SH的聚合物分子以S—Au键修饰到金纳米星表面。采用傅里叶红外光谱仪、透射电镜和核磁氢谱等手段对聚合物和复合金纳米星的理化性质和光热转化能力进行研究。结果表明:AuNSs@Poly(DEGMA-co-OVNGmix)成功制备,该复合粒子的平均粒径为50～100nm,并且具有良好的稳定性。光热性能测试结果表明,复合粒子的光热转换效率达到50.54%,说明经修饰的金纳米星具有优异的光热转换能力。
The temperature-sensitive random glycopolymer,Poly(DEGMA-co-OVNGmix) was synthesized by enzymatic reaction and fracture chain transfer (RAFT) polymerization.After the thioester bond at the end of the glycopolymer was reduced by reductant,the glycopolymer molecule with the end of the S—H bond was obtained and modified to the surface of the gold nanostar (AuNS) by the S—Au bond.The structure and photothermal properties of the grafted AuNSs were characterized by Fourier transform infrared spectroscopy (FT-IR),nuclear magnetic resonance (1H-NMR) and transmission electron microscopy (TEM).The results showed that AuNSs@Poly (DEGMA-co-OVNGmix) was successfully prepared and its stability was greatly improved by the modification of glycopolymer.The average sizes of the grafted nanoparticles were 50～100nm.The results of photothermal performance test proved that the photothermal conversion efficiency of these nanostars achieved 50.54%.In addition,the modified gold nanoparticles had excellent photothermal conversion capability.
[1] Liu D,Wang Q,Hu J.Fabrication and characterization of highly ordered Au nanocone array-patterned glass with enhanced SERS and hydrophobicity[J].Applied Surface Science,2015,356:364-369.
[2] Nikoobakht B,El-Sayed M A.Preparation and growth mechanism of gold nanorods (NRs) using seed-mediated growth method[J].Chemstry of Materials,2003,15(10):1957-1962.
[3] 高燕红,张念椿,冯炫,等.晶种法制备单分散的金纳米粒子及光学性能研究[J].贵金属,2010,31(4):15-19.
[4] 杨生春,董守安,唐春.金纳米粒子自球形向棒状的转变和生长的光化学法研究[J].化学学报,2012,63(11):873-879.
[5] Kan C X,Wang C S,Li H C,et al.gold microplates with well-defined shapes[J].Small,2010,6(16):1768-1775.
[6] Liu K,Zheng Y,Lu X,et al.Biocompatible gold nanorods:one-step surface functionalization,highly colloidal stability,and low cytotoxicity[J].Langmuir,2015,31(17):4973-4980.
[7] Saha K,Agasti S S,Kim C,et al.Gold nanoparticles in chemical and biological sensing[J].Chem Rev,2012,112(5):2739-2779.
[8] Kong T,Zeng J,Wang X,et al.Enhancement of radiation cytotoxicity in breast-cancer cells by localized attachment of gold nanoparticles[J].Small,2008,4(9):1537-1543.
[9] D'Souza A A,Devarajan P V.Asialoglycoprotein receptor mediated hepatocyte targeting-strategies and applications[J].Journal of Controlled Release,2015,203:126-139.
[10] Ting S R S,Chen G,Stenzel M H.Synthesis of glycopolymers and their multivalent recognitions with lectins[J].Polymer Chemistry,2010,1(9):1392-1412.
[11] De la Fuente J M,Penades S.Glyconanoparticles:types,synthesis and applications in glycoscience,biomedicine and material science[J].Biochim Biophys Acta,2006,1760(4):636-651.
[12] Munoz-Bonilla A,Heuts J P A,Fernandez-Garcia M.Glycoparticles and bioactive films prepared by emulsion polymerization using a well-defined block glycopolymer stabilizer[J].Soft Matter,2011,7(6):2493-2499.
[13] Becer C R.The glycopolymer code:synthesis of glycopolymers and multivalent carbohydrate-lectin interactions[J].Macromolecular Rapid Communications,2012,33(9):742-752.
[14] Gerke C,Ebbesen M F,Jansen D,et al.Sequence-controlled glycopolymers via step-growth polymerization of precision glycomacromolecules for lectin receptor clustering[J].Biomacromolecules,2017,18(3):787-796.
[15] Xu M R,Shi M,Bremner D H,et al.Facile fabrication of P(OVNG-co-NVCL) thermoresponsive double-hydrophilic glycopolymer nanofibers for sustained drug release[J].Colloids and Surfaces B:Biointerfaces,2015,135:209-216.
[16] Quan J,Shen F W,Cai H,et al.Galactose-functionalized double-hydrophilic block glycopolymers and their thermoresponsive self-assembly dynamics[J].Langmuir,2018,34:10721-10731.
[17] Shao D,Wu H,Shen F,et al.Carbon dioxide-modified polyethylenimine as a novel gene delivery vector and its in vitro validation[J].Journal of Biomaterials Applications,2017,31:1257-1266.
[18] Sun K,Xu M,Zhou K,et al.Thermoresponsive diblock glycopolymer by RAFT polymerization for lectin recognition[J].Materials Science & Engineering C Materials Biological Applications,2016,68:172-176.
[19] Yuan H,Khoury C G,Hwang H,et al.Gold nanostars:surfactant-free synthesis,3D modelling,and two-photon photoluminescence imaging[J].Nanotechnology,2012,23(7):075102-075112.
[20] 吴頔,樊淼,张露云,等.金纳米星/双锥的可控制备、光热转换及体外光热治疗[J].发光学报,2018,39(3):280-286.
[21] Roper D K,Ahn W,Hoepfner M.Microscale heat transfer transduced by surface plasmon resonant gold nanoparticles[J].J Phys Chem C,2007,111:3636-3641.
基金资助
国家自然科学基金(21303014);聚合物分子工程国家重点实验室(复旦大学)开放课题(K2017-18)
PDF
(2915KB)
