AIE荧光聚合物RAFT可控合成与表征及光物理性质研究

doi:10.3866/PKU.DXHX201912030

University Chemistry ›› 2020, Vol. 35 ›› Issue (4): 81-89.doi: 10.3866/PKU.DXHX201912030

Special Issue: 全国大学生化学实验创新设计竞赛

Previous Articles Next Articles

RAFT Controlled Synthesis, Characterization and Photophysical Properties of the Prepared AIE Fluorescent Polymers

Tianrui Liu¹, Weiguang Zhao², Yanxin Zhang¹, Kaixuan Feng¹, Tianchi Xu², Wenwei Zhang¹^,*(), Dongzhong Chen¹^,²^,*()

¹ National Demonstration Center for Experimental Chemistry Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China
² Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China

Received:2019-12-06 Accepted:2019-12-29 Published:2020-02-17
Contact: Wenwei Zhang,Dongzhong Chen E-mail:wwzhang@nju.edu.cn;cdz@nju.edu.cn

Abstract

Abstract:

The aggregation-induced emission (AIE) molecules are novel organic fluorescent materials that present distinct photophysical properties in contrast to conventional aggregation-caused quenching fluorescent dyes. In virtue of their unique properties, they can be widely used in many fields such as chemical/biological sensing, biological probing and imaging, diagnosis and treatment integration and optoelectronic devices. In this paper, based on innovative experimental competition, tetraphenylethylene (TPE) side-chain polyacrylate AIE polymers have been synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization. With the optimization and exploration of the experimental conditions, the initiator of 2, 2'-azobis-2, 4-dimethylvaleronitrile (ABVN) with shorter half-life and higher activity was adopted to replace the conventional azobisisobutyronitrile (AIBN). As a result, the frontier scientific research experiment, which would have required more than 12 hours reaction, was adapted into a shorter polymerization time of 3-5 hours with moderate yields and good polymer product quality. Thus, the research experiment was remoulded as an experiment suitable for undergraduate laboratory teaching. A range of modern laboratory techniques, such as the anhydrous oxygen-free operation, the column chromatography separation and purification operation, the RAFT controlled polymerization, the gel-permeation chromatography molecular characterization, FTIR, NMR, UV-Vis, and fluorescence emission spectroscopy, have been involved and practised. The photophysical properties of the synthesized TPE side-chain AIE polymers were investigated, with the relative fluorescence quantum yield in the THF/water mixture solution of high water fraction reached a high value of 17%.

Key words: Tetraphenylethylene (TPE), AIE polymer, RAFT controlled polymerization, Photophysical properties, Innovation experiment

MSC2000:

Tianrui Liu, Weiguang Zhao, Yanxin Zhang, Kaixuan Feng, Tianchi Xu, Wenwei Zhang, Dongzhong Chen. RAFT Controlled Synthesis, Characterization and Photophysical Properties of the Prepared AIE Fluorescent Polymers[J].University Chemistry, 2020, 35(4): 81-89.

Figures/Tables 12

References 15

1	Lakowicz, J. Principles of Fluorescence Spectroscopy; Springer: New York, NY, USA, 2006.
2	Tang L. ; Jin J. K. ; Qin A. ; Yuan W. Z. ; Mao Y. ; Mei J. ; Sun J. Z. ; Tang B. Z. Chem. Commun. 2009, 4974.
3	Luo J. ; Xie Z. ; Lam J. W. Y. ; Cheng L. ; Tang B. Z. ; Chen H. ; Qiu C. ; Kwok H. S. ; Zhan X. ; Liu Y. ; et al Chem. Commun. 2001, 1740.
4	Tang B. Z. ; Zhan X. ; Yu G. ; Lee P. P. S. ; Liu Y. ; Zhu D. J. Mater. Chem. 2001, 11, 2974. doi: 10.1039/b102221k
5	Hu R. ; Leung N. L. ; Tang B. Z. Chem. Soc. Rev. 2014, 13, 4494.
6	Mei J. ; Leung N. L. C. ; Kwok R. T. K. ; Lam J. W. Y. ; Tang B. Z. Chem. Rev. 2015, 115, 11718. doi: 10.1021/acs.chemrev.5b00263
7	Ma C. ; Ling Q. ; Xu S. ; Zhu H. ; Zhang G. ; Zhou X. ; Chi Z. ; Liu S. ; Zhang Y. ; Xu J. Macromol. Biosci. 2014, 2, 235.
8	Ishiwari F. ; Hasebe H. ; Matsumura S. ; Hajjaj F. ; Horii-Hayashi N. ; Nishi M. ; Someya T. ; Fukushima T. Sci. Rep. 2016, 24275.
9	Zhan R. ; Pan Y. ; Manghnani P. N. ; Liu B. Macromol. Biosci. 2017, 17, 1600433.
10	Zhang X. ; Wang K. ; Liu M. ; Zhang X. ; Tao L. ; Chen Y. ; Wei Y. Nanoscale 2015, 7, 11486. doi: 10.1039/C5NR01444A
11	Li Q. ; Li X. ; Wu Z. Y. ; Sun Y. H. ; Fang J. L. ; Chen D. Z. Polym. Chem. 2018, 9, 4150. doi: 10.1039/C8PY00710A
12	Li X. ; Sun Y. H. ; Chen J. ; Wu Z. Y. ; Cheng P. ; Li Q. ; Fang J. L. ; Chen D. Z. Polym. Chem. 2019, 13, 1575.
13	Chiefari J. ; Chong Y. K. ; Ercole F. ; Krstina J. ; Jeffery J. ; Le T. P. T. ; Mayadunne R. T. A. ; Meijs G. F. ; Moad C. L. ; Moad G. ; et al Macromolecules 1998, 31, 5559. doi: 10.1021/ma9804951
14	Moad G. ; Rizzardo E. ; Thang S. H. Aust. J. Chem. 2012, 65, 985. doi: 10.1071/CH12295
15	Zhou H. ; Li J. ; Chua M. H. ; Yan H. ; Tang B. Z. ; Xu J. Polym. Chem. 2014, 5, 5628. doi: 10.1039/C4PY00518J

引发剂	链转移剂	优化批次号^*	单体用量/g	聚合物产量/mg	聚合物产率/%
AIBN	CTA1	/	0.30	21.8	7.3
AIBN	CPDB	/	0.30	32.7	10.9
ABVN	CPDB	/	0.30	7.7	2.6
ABVN	CTA1	1	0.30	144.2	48.1
		2	0.30	123.6	41.2
		3	0.30	161.4	53.8
		4	0.30	122.6	40.9

参数	批次1	批次2	批次3	批次4
Peak RV	17.05	17.17	17.37	17.50
Mn	2880	2810	2420	2110
Mw	3580	3220	2800	2530
Mz	4320	3670	3200	2960
Mp	3280	3010	2620	2390
Mw/Mn	1.24	1.14	1.16	1.20

样品	最大吸收波长/nm	最大吸光度	激发波长/nm	最大发射波长/nm	积分荧光强度	荧光量子产率Φ_F
硫酸奎宁	346.0	0.045	346.0	447.0	20300	0.54
AIE聚合物	322.0	0.044	322.0	470.0	6350	0.17

[1]	Niu Xiaoyu, Li Zhibin, Wang Kai, Fang Yaling, Chen Jing, Zhu Yujun. Preparation, Characterization and Catalytic Transesterification Performance of KF/La₂O₂CO₃ as Solid Base Catalyst: A Comprehensive Innovation Experiment [J]. University Chemistry, 2020, 35(4): 37-42.
[2]	Hua-Nai LIU,Xiao-Yan LUO,Yong YE. A Comprehensive Innovation Experiment of Pharmaceutical Engineering on Extraction and Identification of Rutin, Preparation of Different Dosage Forms and Correlation with in Vivo Release [J]. University Chemistry, 2017, 32(10): 39-46.
[3]	Wen Lili, Hu Zongqiu, Wan Jian. Exploration on Innovation Experiments for Tuition-free Normal College Students Majored in Chemistry [J]. University Chemistry, 2015, 30(4): 26-29.

RAFT Controlled Synthesis, Characterization and Photophysical Properties of the Prepared AIE Fluorescent Polymers

RichHTML

PDF (PC)

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 15

Related Articles 3

Metrics

Recommended 0