Citation: Xiao-jing Dong, Hong-yan Cao, Xu-bao Jiang, Xiang-zheng Kong, Shu-sheng Li. Phase Transition and Fluorescence Emission Characteristics ofMulti-responsive Copolymer of Oligo(ethylene glycol)Methyl Ether Acrylate and Methylacrylic Acid[J]. Acta Polymerica Sinica, ;2019, 50(12): 1314-1321. doi: 10.11777/j.issn1000-3304.2019.19106 shu

Phase Transition and Fluorescence Emission Characteristics ofMulti-responsive Copolymer of Oligo(ethylene glycol)Methyl Ether Acrylate and Methylacrylic Acid

1.
College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022
2.
College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023

Corresponding author: Shu-sheng Li, chm_liss@ujn.edu.cn
Received Date: 12 July 2019
Revised Date: 22 August 2019

Multi-responsive polymers, with cluster-induced luminescence (CIE) featured by non-conjugated chromophores, have attracted great attention in recent years, and the relevant studies have been focused mainly on the polymers with aliphatic amines and carbonyl groups. Although the CIE behaviors of ethylene glycol-based polymers have been previously reported, studies that correlate their luminescent properties with their stimuli-responsiveness are rarely available. In this paper, P(OEGA-MAA), a copolymer responsive to temperature, pH and salt, was prepared by free radical copolymerization of oligo(ethylene glycol) methyl ether acrylate (OEGA) with methylacrylic acid (MAA) in ethanol. The structure of P(OEGA-MAA) was characterized by ¹H-NMR and its molecular weight was determined by GPC. The evolution of light transmittance of the water solution of P(OEGA-MAA) with temperature was measured under different conditions and its fluorescence performance was characterized. The results show that P(OEGA-MAA) not only has responsive to temperature, pH and salt, but also emits visible blue fluorescence under UV. Effects of the polymer composition, pH and salt concentration on the lower critical solution temperature (LCST) and fluorescence properties are studied. And the relationship between fluorescence properties and phase transition process is also describled. As OEGA content decreased in the polymer, the LCST in its aqueous solution (2.0 mg/mL, pH=1) decreased, and the corresponding fluorescence intensity increased first with OEGA content up to 33 mol% (OEGA/MAA = 3.3/6.7, sample P7 ), where it reached a maximum, followed by a decrease with further decrease in OEGA. Effects of pH and NaCl concentration were also studied with P7 as an example. With increased pH in the aqueous solution (2.0 mg/mL) of P7 , the LCST increased and the fluorescence intensity decreased; With the increase in NaCl concentration, the LCST decreased, while no obverious change was detected for the fluorescence intensity. Furthermore, when the polymer concentration was increased, the LCST decreased, and the fluorescence intensity increased obviously. All the results indicate that the fluorescence emission was caused by aggregation of oxygen atoms in polymer segments. This study provides therefore a novel type of materials for potential applications in biomedical fields, and it is also of great significance for understanding the luminescence mechanism of PEG-based stimuli-responsive polymers.
1. [1]
  Yamada A, Hiruta Y, Wang J, Ayano E, Kanazawa H. Biomacromolecules, 2015, 16: 2356 − 2362 doi: 10.1021/acs.biomac.5b00591
2. [2]
  Wang H, Ke F, Mararenko A, Wei Z, Banerjee P, Zhou S. Nanoscale, 2014, 6: 7443 − 7452 doi: 10.1039/C4NR01030B
3. [3]
  Park C H, Lee S, Pornnoppadol G, Nam Y S, Kim S H, Kim B J. ACS Appl Mater Interfaces, 2018, 10: 9023 − 9031 doi: 10.1021/acsami.7b19468
4. [4]
  Kim T H, Swager T M. Angew Chem Int Ed, 2003, 42: 4803 − 4806 doi: 10.1002/anie.200352075
5. [5]
  Wu W, Huang F, Pan S, Mu W, Meng X, Yang H, Xu Z, Ragauskas A J, Deng Y. J Mater Chem A, 2015, 3: 1995 − 2005 doi: 10.1039/C4TA04761C
6. [6]
  Shang C, Wei N, Zhuo H, Shao Y, Zhang Q, Zhang Z, Wang H. J Mater Chem C, 2017, 5: 8082 − 8090 doi: 10.1039/C7TC02381B
7. [7]
  Taniguchi R, Yamada T, Sada K, Kokado K. Macromolecules, 2014, 47: 6382 − 6388 doi: 10.1021/ma501198d
8. [8]
  Lin J, Zeng X, Xiao Y, Tang L, Nong J, Liu Y, Zhou H, Ding B, Xu F, Tong H, Deng Z, Hong X. Chem Sci, 2019, 10: 1219 − 1226 doi: 10.1039/C8SC04363A
9. [9]
  Chen M, Li L, Wu H, Pan L, Li S, He B, Zhang H, Sun J Z, Qin A, Tang B Z. ACS Appl Mater Interfaces, 2018, 10: 12181 − 12188 doi: 10.1021/acsami.8b03178
10. [10]
  Chai J, Wu Y, Yang B, Liu B. J Mater Chem C, 2018, 6: 4057 − 4064 doi: 10.1039/C8TC00509E
11. [11]
  Wang X, Li J, Yan Q, Chen Y, Fan A, Wang Z, Zhao Y. Macromol Biosci, 2018, 18: 1700339 doi: 10.1002/mabi.201700339
12. [12]
  Ekbote A, Han S H, Jadhav T, Mobin S M, Lee J Y, Misra R. J Mater Chem C, 2018, 6: 2077 − 2087 doi: 10.1039/C7TC05450E
13. [13]
  Zeng G, Liu M, Jiang R, Huang Q, Huang L, Wan Q, Dai Y, Wen Y, Zhang X, Wei Y. Polym Chem, 2017, 8: 4746 − 4751 doi: 10.1039/C7PY00884H
14. [14]
  Lin Y K, Fang J Y, Wang S W, Lee R S. React Funct Polym, 2018, 130: 29 − 42 doi: 10.1016/j.reactfunctpolym.2018.05.008
15. [15]
  Saghebasl S, Davaran S, Rahbarghazi R, Montaseri A, Salehi R, Ramazani A. J Biomat Sci-Polym Ed, 2018, 29: 1185 − 1206 doi: 10.1080/09205063.2018.1447627
16. [16]
  Saeki S, Kuwahara N, Nakata M, Kaneko M. Polymer, 1976, 17: 685 − 689 doi: 10.1016/0032-3861(76)90208-1
17. [17]
  Cao H, Wang Q, Li M, Chen Z. Colloid Polym Sci, 2015, 293: 441 − 451 doi: 10.1007/s00396-014-3422-6
18. [18]
  Sun X, Zebibula A, Dong X, Zhang G, Zhang D, Qian J, He S. ACS Appl Mater Interfaces, 2018, 10: 25037 − 25046 doi: 10.1021/acsami.8b05546
19. [19]
  Liu Y, Mao L, Liu X, Liu M, Xu D, Jiang R, Deng F, Li Y, Zhang X, Wei Y. Mater Sci Eng C, 2017, 79: 590 − 595 doi: 10.1016/j.msec.2017.05.108
20. [20]
  Long Z, Liu M, Jiang R, Wan Q, Mao L, Wan Y, Deng F, Zhang X, Wei Y. Chem Eng J, 2017, 308: 527 − 534 doi: 10.1016/j.cej.2016.09.053
21. [21]
  Kafer F, Liu F, Stahlschmidt U, Jérôme V, Freitag R, Karg M, Agarwa S. Langmuir, 2015, 31: 8940 − 8946 doi: 10.1021/acs.langmuir.5b02006
22. [22]
  Wang Y, Bin X, Chen X, Zheng S, Zhang Y, Yuan W Z. Macromol Rapid Commun, 2018, 39: 1800528 doi: 10.1002/marc.201800528
23. [23]
  Miao X, Liu T, Zhang C, Geng X, Meng Y, Li X. Phys Chem Chem Phys, 2016, 18: 4295 − 4299 doi: 10.1039/C5CP07134H
24. [24]
  Pucci A, Rausa R, Ciardelli F. Macromol Chem Phys, 2008, 209: 900 − 906 doi: 10.1002/macp.200700581
25. [25]
  Lutz J F, Weichenhan K, Akdemirö, Hoth A. Macromolecules, 2007, 40: 2503 − 2508 doi: 10.1021/ma062925q
26. [26]
  Can A, Zhang Q, Rudolph T, Schacher F, Gohy J F, Schubert U, Richard H. Eur Polym J, 2015, 69: 460 − 471 doi: 10.1016/j.eurpolymj.2015.04.008
27. [27]
  Luzon M, Boyer C, Peinado C, Corrales T, Whittaker M, Tao L, Davis T P. J Polym Sci, Part A: Polym Chem, 2010, 48: 2783 − 2792 doi: 10.1002/pola.24027
28. [28]
  Lu H, Feng L, Li S, Zhang J, Lu H, Feng S. Macromolecules, 2015, 48: 476 − 482 doi: 10.1021/ma502352x
29. [29]
  Guan X, Meng L, Jin Q, Lu B, Chen Y, Li Z, Wang L, Lai S, Lei Z. Macromol Mater Eng, 2018, 303: 1700553 doi: 10.1002/mame.201700553
30. [30]
  Huang H, Hou L, Zhu F, Li J, Xu M. RSC Adv, 2018, 8: 9334 − 9343 doi: 10.1039/C8RA01018H
31. [31]
  Cao H, Guo F, Chen Z, Kong X Z. Nanoscale Res Lett, 2018, 13: 209 − 218 doi: 10.1186/s11671-018-2610-6
32. [32]
  Park T G, Hoffman A. Macromolecules, 1993, 26: 5045 − 5048 doi: 10.1021/ma00071a010
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Phase Transition and Fluorescence Emission Characteristics ofMulti-responsive Copolymer of Oligo(ethylene glycol)Methyl Ether Acrylate and Methylacrylic Acid

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com