激光调控自缩合表面引发原子转移自由基聚合制备超支化聚乙二醇刷

马康; 马玉录; 赵海利; 刘嵩; 谢林生; 沙金

doi:10.11777/j.issn1000-3304.2017.17178

您当前的位置：

首页 >

文章列表页 >

激光调控自缩合表面引发原子转移自由基聚合制备超支化聚乙二醇刷

研究论文 | 更新时间：2021-01-26

- 激光调控自缩合表面引发原子转移自由基聚合制备超支化聚乙二醇刷
- Fabrication of Hyperbranched PEG Brushes viaLaser-mediated Self-condensing Surface-initiated Atom Transfer Radical Polymerization
- 高分子学报 2018年0卷第5期页码：571-580
- 作者机构：
  
  绿色高效过程装备与节能教育部工程研究中心华东理工大学机械与动力工程学院　上海 200237
- 作者简介：
  
  E-mail: sjin@ecust.edu.cn Jin Sha, sjin@ecust.edu.cn
- 基金信息：
  
  国家自然科学青年基金(基金号 51503065)资助项目()
- DOI：10.11777/j.issn1000-3304.2017.17178
  中图分类号：
- 纸质出版日期：2018-5，
  
  收稿日期：2017-7-7，
  
  修回日期：2017-7-30，
扫描看全文
马康, 马玉录, 赵海利, 刘嵩, 谢林生, 沙金. 激光调控自缩合表面引发原子转移自由基聚合制备超支化聚乙二醇刷[J]. 高分子学报, 2018,0(5):571-580.

Kang Ma, Yu-lu Ma, Hai-li Zhao, Song Liu, Lin-sheng Xie, Jin Sha. Fabrication of Hyperbranched PEG Brushes viaLaser-mediated Self-condensing Surface-initiated Atom Transfer Radical Polymerization[J]. Acta Polymerica Sinica, 2018,0(5):571-580.
马康, 马玉录, 赵海利, 刘嵩, 谢林生, 沙金. 激光调控自缩合表面引发原子转移自由基聚合制备超支化聚乙二醇刷[J]. 高分子学报, 2018,0(5):571-580. DOI： 10.11777/j.issn1000-3304.2017.17178.

Kang Ma, Yu-lu Ma, Hai-li Zhao, Song Liu, Lin-sheng Xie, Jin Sha. Fabrication of Hyperbranched PEG Brushes viaLaser-mediated Self-condensing Surface-initiated Atom Transfer Radical Polymerization[J]. Acta Polymerica Sinica, 2018,0(5):571-580. DOI： 10.11777/j.issn1000-3304.2017.17178.

摘要

采用二溴异丁基酯化低聚乙二醇甲基丙烯酸酯(OEGMA-Br)为自引发性单体，以三(2-苯基吡啶)合铱为光氧化还原催化剂，通过激光调控自缩合表面引发原子转移自由基聚合(SI-ATRP)，在硅片表面制备超支化聚乙二醇(PEG)聚合物刷. 在对硅片-溶液界面与硅片表面溶液中自引发性单体OEGMA-Br自缩合ATRP反应机理推导的基础上，硅片表面反应溶液的核磁共振(

H-NMR)表征及聚合物刷表面活性末端官能团的光电子能谱(XPS)表征证实了所得表面PEG聚合物刷的超支化结构；椭圆偏光仪对不同反应条件下聚合物刷厚度的表征表明过高或过低的自引发性单体浓度均不利于超支化PEG聚合物刷的生长，同时其生长过程受到聚合时间和光辐照强度的影响；采用异硫氰酸荧光素(FITC)标记牛血清蛋白表面吸附实验证明PEG聚合物刷微图案的非特异性抗蛋白吸附性能.

Abstract

Surface polymer brushes have been extensively studied to modify the surface properties of substrates and to implement multifunctionality. Compared to comb type brushes

hyperbranched-structure polymer brushes show significant advantages in thermal stability

compatibility and functionalization potential. The preparation study of surface hyperbranched polymer brushes is fundamental to explode polymer brushes applications. Here

laser-mediated surface-initiated atom transfer radical polymerization (SI-ATRP) is firstly introduced to conduct self-condensing polymerization

with 2-bromoisobutyrate ester of oligo (ethylene glycol) methacrylate (OEGMA-Br) as AB

-type inimer and Ir(ppy)

as the photo-redox catalyst

to prepare hyperbranched poly(ethylene glycol)(PEG) brushes on a silicon substrate. Based on the discussion on the mechanism of OEGMA-Br inimer self-condensing polymerization on solid-liquid interface and at surface solution on silicon surface

five microstructures are proposed for the constitution of the hyperbranched PEG brushes and the corresponding signals are further confirmed by

H-NMR spectra analysis. X-ray photoelectron spectroscopy (XPS) characterization is conducted to investigate the chemical composition of hyperbranched PEG brushes. The high resolution C1s and Br3d spectra indicate the preservation of surface bromine density on hyperbranched PEG brushes in comparison to initiator surface on silicon substrate

implying the hyperbranched microstructure and high active site densities. Then

the thickness of hyperbranched PEG brushes corresponding to different inimer concentrations is investigated by ellipsometry

which indicates an increase first in the thickness and a subsequant decrease trend as the inimer concentration increased. A competitive mechanism for the surface polymerization is proposed to depict the growth of the hyperbranched PEG brushes on a silicon substrate

which refers to a competition between the solid-liquid interface polymerization and the surface solution polymerization. An increase of inimer concentration would promote the self-condensing polymerization of the inimer in solution

which consequently inhibits the solid-liquid interface polymerization and is unfavorable to the hyperbranched PEG brushes growth. Furthermore

laser confocal microscopy observation of the absorption of 5-isothiocyanatofluorescein (FITC) labeled bovine serum albumin (BSA) on hyperbranched PEG brushes micropatterns proves the significant anti-fouling property. The research extends the application of photo-catalyzed SI-ATRP in the preparation of surface hyperbranched-structure polymer brushes

and provides fundamental technical support to expand the applications of the hyperbranched PEG brushes in drug transport

biosensing and high-throughput cell screening.

关键词

表面引发原子转移自由基聚合超支化结构聚乙二醇刷微图案

Keywords

Surface-initiated atom transfer radical polymerizationHyperbranched structurePoly(ethylene glycol) brushMicropattern

references

Nie Z, Kumacheva E . Nat Mater , 2008 . 7 277 - 290 . DOI:10.1038/nmat2109http://doi.org/10.1038/nmat2109 .

Olivier A, Meyer F, Raquez J M, Damman P, Dubois P . Prog Polym Sci , 2012 . 37 157 - 181 . DOI:10.1016/j.progpolymsci.2011.06.002http://doi.org/10.1016/j.progpolymsci.2011.06.002 .

Ishihara K, Kitagawa T, Inoue Y . ACS Biomater Sci Eng , 2015 . 1 103 - 109 . DOI:10.1021/ab500048whttp://doi.org/10.1021/ab500048w .

Ramakrishna S N, Cirelli M, Divandari M, Benetti E M . Langmuir , 2017 . 33 4164 - 4171 . DOI:10.1021/acs.langmuir.7b00217http://doi.org/10.1021/acs.langmuir.7b00217 .

Farrukh A, Ashraf F, Kaltbeitzel A, Ling X, Wagner M, Duran H, Ghaffar A, ur Rehman H, Parekh S H, Domke K F . Polym Chem , 2015 . 6 5782 - 5789 . DOI:10.1039/C5PY00514Khttp://doi.org/10.1039/C5PY00514K .

Zhou G Y, Lee A W, Chang J Y, Huang C H, Chen J K . J Mater Chem C , 2014 . 2 8226 - 8234 . DOI:10.1039/C4TC01380Hhttp://doi.org/10.1039/C4TC01380H .

Wei Qiangbing(魏强兵), Cai Meili(蔡美荣), Zhou Feng(周峰). Acta Polymerica Sinica(高分子学报), 2012, (10): 1102 − 1107

Shen Y, Qi L, Wei X, Zhang R, Mao L . Polymer , 2011 . 52 3725 - 3731 . DOI:10.1016/j.polymer.2011.06.041http://doi.org/10.1016/j.polymer.2011.06.041 .

Li Z, Wei J, Shan F, Yang J, Wang X . J Polym Sci, Part B: Polym Phys , 2008 . 46 751 - 758 . DOI:10.1002/(ISSN)1099-0488http://doi.org/10.1002/(ISSN)1099-0488 .

Ma H, Hyun J, Stiller P, Chilkoti A . Adv Mater , 2004 . 16 338 - 341 . DOI:10.1002/(ISSN)1521-4095http://doi.org/10.1002/(ISSN)1521-4095 .

Kieviet B D, Schön P M, Vancso G J . Lab Chip , 2014 . 14 4159 - 4170 . DOI:10.1039/C4LC00784Khttp://doi.org/10.1039/C4LC00784K .

Hui C M, Pietrasik J, Schmitt M, Mahoney C, Choi J, Bockstaller M R, Matyjaszewski K . Chem Mater , 2013 . 26 745 - 762.

Li Bin(李斌), Yu Bo(于波), Zhou Feng(周峰). Acta Polymerica Sinica(高分子学报), 2016, (10): 1312 − 1329

Patil R R, Turgman Cohen S, Šrogl J í, Kiserow D, Genzer J . Langmuir , 2015 . 31 2372 - 2381 . DOI:10.1021/la5044766http://doi.org/10.1021/la5044766 .

Lilge I, Schönherr H . Angew Chem , 2016 . 128 13308 - 13311 . DOI:10.1002/ange.201607078http://doi.org/10.1002/ange.201607078 .

Wang X, Chen X, Xing L, Mao C, Yu H, Shen J . J Mater Chem B , 2013 . 1 5036 - 5044 . DOI:10.1039/c3tb20855ahttp://doi.org/10.1039/c3tb20855a .

Han S W, Lee S, Hong J, Jang E, Lee T, Koh W G . Biosens Bioelectron , 2013 . 45 129 - 135 . DOI:10.1016/j.bios.2013.01.062http://doi.org/10.1016/j.bios.2013.01.062 .

Wang D, Jin Y, Zhu X, Yan D . Prog Polym Sci , 2017 . 64 114 - 153 . DOI:10.1016/j.progpolymsci.2016.09.005http://doi.org/10.1016/j.progpolymsci.2016.09.005 .

Lebedeva I O, Zhulina E B, Leermakers F A, Borisov O V . Langmuir , 2017 . 33 1315 - 1325 . DOI:10.1021/acs.langmuir.6b04285http://doi.org/10.1021/acs.langmuir.6b04285 .

Haag R, Stumbé J F, Sunder A, Frey H, Hebel A . Macromolecules , 2000 . 33 8158 - 8166 . DOI:10.1021/ma000831phttp://doi.org/10.1021/ma000831p .

Siegers C, Biesalski M, Haag R . Chem Eur J , 2004 . 10 2831 - 2838 . DOI:10.1002/(ISSN)1521-3765http://doi.org/10.1002/(ISSN)1521-3765 .

Totani M, Ando T, Terada K, Terashima T, Kim I Y, Ohtsuki C, Xi C, Kuroda K, Tanihara M . Biomater Sci , 2014 . 2 1172 - 1185 . DOI:10.1039/C4BM00034Jhttp://doi.org/10.1039/C4BM00034J .

Wang Z L, Xu J T, Du B Y, Fan Z Q . J Colloid Interface Sci , 2012 . 384 29 - 37 . DOI:10.1016/j.jcis.2012.06.067http://doi.org/10.1016/j.jcis.2012.06.067 .

Pu Ming(浦鸣), Ji Jian(计剑), Li Xiaolin(李晓林), Shen Jiacong(沈家骢). Acta Polymerica Sinica(高分子学报), 2006, (5): 703-706

Ignatova M, Voccia S, Gabriel S, Gilbert B, Cossement D, Jérôme R, Jérôme C . Langmuir , 2008 . 25 891 - 902.

Zheng Y, Li S, Weng Z, Gao C . Chem Soc Rev , 2015 . 44 4091 - 4130 . DOI:10.1039/C4CS00528Ghttp://doi.org/10.1039/C4CS00528G .

Pranantyo D, Xu L Q, Neoh K G, Kang E T, Teo S L M . Ind Eng Chem Res , 2016 . 55 1890 - 1901 . DOI:10.1021/acs.iecr.5b03735http://doi.org/10.1021/acs.iecr.5b03735 .

Khan M, Huck W T . Macromolecules , 2003 . 36 5088 - 5093 . DOI:10.1021/ma0340762http://doi.org/10.1021/ma0340762 .

Murota M, Sato S, Tsubokawa N . Polym Adv Technol , 2002 . 13 144 - 150 . DOI:10.1002/(ISSN)1099-1581http://doi.org/10.1002/(ISSN)1099-1581 .

Moore E, Delalat B, Vasani R, McPhee G, Thissen H, Voelcker N H . ACS Appl Mater Interfaces , 2014 . 6 15243 - 15252 . DOI:10.1021/am503570vhttp://doi.org/10.1021/am503570v .

Muthukrishnan S, Erhard D P, Mori H, Müller A H . Macromolecules , 2006 . 39 2743 - 2750 . DOI:10.1021/ma052575shttp://doi.org/10.1021/ma052575s .

Schüll C, Frey H . Polymer , 2013 . 54 5443 - 5455 . DOI:10.1016/j.polymer.2013.07.065http://doi.org/10.1016/j.polymer.2013.07.065 .

Rodda A E, Ercole F, Nisbet D R, Forsythe J S, Meagher L . Macromol Biosci , 2015 . 15 799 - 811 . DOI:10.1002/mabi.v15.6http://doi.org/10.1002/mabi.v15.6 .

Ouchi M, Terashima T, Sawamoto M . Chem Rev , 2009 . 109 4963 - 5050 . DOI:10.1021/cr900234bhttp://doi.org/10.1021/cr900234b .

Feng Q, Tang D, Lv H, Zhang W, Li W . RSC Adv , 2015 . 5 62024 - 62032 . DOI:10.1039/C5RA07301Dhttp://doi.org/10.1039/C5RA07301D .

Lee B S, Kim J Y, Park J H, Cho W K, Choi I S . J Nanosci Nanotechnol , 2016 . 16 3106 - 3109 . DOI:10.1166/jnn.2016.11098http://doi.org/10.1166/jnn.2016.11098 .

Mori H, Böker A, Krausch G, Müller A H . Macromolecules , 2001 . 34 6871 - 6882 . DOI:10.1021/ma0019048http://doi.org/10.1021/ma0019048 .

Treat N J, Fors B P, Kramer J W, Christianson M, Chiu C Y, Read de Alaniz J, Hawker C J . ACS Macro Lett , 2014 . 3 580 - 584 . DOI:10.1021/mz500242ahttp://doi.org/10.1021/mz500242a .

Dadashi Silab S, Atilla Tasdelen M, Yagci Y . J Polym Sci, Part A: Polym Chem , 2014 . 52 2878 - 2888 . DOI:10.1002/pola.27327http://doi.org/10.1002/pola.27327 .

Yang Q, Lalevée J, Poly J . Macromolecules , 2016 . 49 7653 - 7666 . DOI:10.1021/acs.macromol.6b01808http://doi.org/10.1021/acs.macromol.6b01808 .

Fors B P, Hawker C J . Angew Chem Int Ed , 2012 . 51 8850 - 8853 . DOI:10.1002/anie.v51.35http://doi.org/10.1002/anie.v51.35 .

Wischerhoff E, Uhlig K, Lankenau A, Börner H G, Laschewsky A, Duschl C, Lutz J F . Angew Chem Int Ed , 2008 . 47 5666 - 5668 . DOI:10.1002/anie.v47:30http://doi.org/10.1002/anie.v47:30 .

Liu S, Weaver J V, Save M, Armes S P . Langmuir , 2002 . 18 8350 - 8357 . DOI:10.1021/la020496thttp://doi.org/10.1021/la020496t .

Matyjaszewski K, Miller P J, Shukla N, Immaraporn B, Gelman A, Luokala B B, Siclovan T M, Kickelbick G, Vallant T, Hoffmann H . Macromolecules , 1999 . 32 8716 - 8724 . DOI:10.1021/ma991146phttp://doi.org/10.1021/ma991146p .

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

空心纳米网络结构聚苯乙烯及其炭材料的制备与结构调控