具有聚集诱导发光效应的水溶性糖基荧光聚合物的制备及性能

doi:10.7503/cjcu20170747

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (6): 1319.doi: 10.7503/cjcu20170747

具有聚集诱导发光效应的水溶性糖基荧光聚合物的制备及性能

凌瑶¹, 刘雪静¹, 郝海景¹, 郝晓辉²(), 白利斌¹(), 武永刚¹

1. 河北大学化学与环境科学学院
2. 物理科学与技术学院, 保定 071002

收稿日期:2017-11-17 出版日期:2018-06-10 发布日期:2018-04-09
基金资助:
国家自然科学基金(批准号: 51703048, 21706049)和河北省自然科学基金(批准号: B2018201281)资助.

Synthesis and Properties of Water-soluble Glycosyl Fluorescent Polymer with Aggregation-induced Emission Effect^†

LING Yao¹, LIU Xuejing¹, HAO Haijing¹, HAO Xiaohui^2,^*(), BAI Libin^1,^*(), WU Yonggang¹

1. College of Chemistry and Environmental Science
2. College of Physics Science & Technology, Hebei University, Baoding 071002, China

Received:2017-11-17 Online:2018-06-10 Published:2018-04-09
Contact: HAO Xiaohui,BAI Libin E-mail:haoxiaohui@hbu.edu.cn;zhonggou556@hbu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51703048, 21706049) and the Natural Science Foundation of Hebei Province, China(No.B2018201281).

摘要/Abstract

摘要：

首先以吡喃型D-甘露糖为原料, 合成糖单体2-(2,3,4,6-四-O-乙酰-α-D-吡喃甘露糖)甲基丙烯酸乙酯, 并通过可逆加成断裂链转移(RAFT)聚合法制备了含双硫酯片段的聚2-(2,3,4,6-四-O-乙酰-α-D-吡喃甘露糖)甲基丙烯酸乙酯(PAcManEMA); 再以PAcManEMA和1,2-二苯基-1,2-二[4'-(2″,3″-环氧丙氧基)苯基]乙烯(TPE-2DGE)为原料, 通过“一锅法”得到结构规整的A-B-A型聚糖(PAcManEMA-TPE); 最后脱去乙酰化保护得到水溶性荧光聚糖(PManEMA-TPE), 产率为90%. 通过核磁共振谱、傅里叶红外光谱、凝胶渗透色谱、荧光光谱以及细胞毒性实验等表征手段对所制备的聚合物进行结构、性能以及生物毒性研究. 实验结果表明, 目标荧光聚糖PAcManEMA-TPE和PManEMA-TPE均表现出明显的聚集诱导发光效应, 且PManEMA-TPE表现出较低毒性或者无毒性, 具有作为生物医学探针的潜能.

关键词: 四苯乙烯, 水溶性荧光聚糖, 聚集诱导发光效应, 可逆加成断裂链转移

Abstract:

A glycopolymer{poly[2-(2,3,4,6-four-O-acetyl-α-D-mannopyranose) ethyl methacrylate]-tetraphenylethene}(PAcManEMA-TPE) with defined structure was synthesized by one-pot method, which the reduction of dithioester and Click reaction between thiol and epoxy group were conducted simultaneously. The water-soluble glycopolymer(poly[2-(2,3,4,6-four-O-acetyl-α-D-mannopyranose) ethyl methacrylate]-tetraphenylethene)(PManEMA-TPE) was obtained in a high yield(90%) after the deprotection reaction of PAcManEMA-TPE was carried out. The structure and aggregation-induced emission(AIE) of PManEMA-TPE were characterized by Fourier transform infrared spectrometer, nuclear magnetic resonance spectrometer, gel permeation chromatograph, UV-Vis spectroscopy and photoluminescence. Moreover, the cell toxicity of PManEMA-TPE was assayed by MTT, proving its non-toxicity and showing its potential application as a biomedical probe.

Key words: Tetrapheny ethylene, Water-soluble fluorescent polysaccharide, Aggregation-induced emission effect, Reversible addition-fragmentation chain transfer polymerization

中图分类号:

O636

TrendMD:

凌瑶, 刘雪静, 郝海景, 郝晓辉, 白利斌, 武永刚. 具有聚集诱导发光效应的水溶性糖基荧光聚合物的制备及性能. 高等学校化学学报, 2018, 39(6): 1319.

LING Yao, LIU Xuejing, HAO Haijing, HAO Xiaohui, BAI Libin, WU Yonggang. Synthesis and Properties of Water-soluble Glycosyl Fluorescent Polymer with Aggregation-induced Emission Effect^†. Chem. J. Chinese Universities, 2018, 39(6): 1319.

图/表 7

Scheme 1 Mechanism of the “one pot” reaction for the preparation of PManEMA-TPE

Fig.1 1H NMR spectra of PAcManEMA(a) and PAcManEMA-TPE(b) polymer(A) and PManEMA-TPE polymer(B)

Fig.2 FTIR spctra of TPE-2DGE(a), PAcManEMA(b), PAcManEMA-TPE(c) and PManEMA-TPE(d)

Fig.3 GPC chromatograms for PAcManEMA(a) and PAcManEMA-TPE(b)(A) and PManEMA(a), PManEMA-TPE(b) and standard(c)(B)

Fig.4 UV-Vis absorbance spectra of TPE-2DGE(a), PAcManEMA-TPE in H2O/DMSO(99/1)(b) and PManEMA-TPE in H2O/DMSO(1/99)(c)

Fig.5 PL spectra of PAcManEMA-TPE(10 μmol/L) at different volume fractions of water(fw)(A) and different volume fractions of DMSO(fD)(B)Inset in (A): plot of relative PL intensity(F/F0). F is PL intensity at any fw at 460 nm, and F0 is the PL intensity measured at fw=90% at 460 nm. λex=320 nm, slits 5, 5 nm; inset in (B): plot of relative PL intensity(F/F0). F is PL intensity at any fD at 476 nm, and F0 is the PL intensity measured at fD=100% at 476 nm. λex=320 nm, slits 5, 5 nm.

Fig.6 Cell viability of PManEMA-TPE at different concentrationsConcentration/(mg·mL-1): a. 0.005; b. 0.001; c. 0.005; d. 0.10; e. 0.50; f. 1.00.

参考文献 27

[1]	Kren V., Martínková L., Current Medicinal Chemistry, 2001, 8(11), 1303—1328
[2]	Nothaft H., Szymanski C.M., Nature Reviews Microbiology, 2010, 8(8), 765—778
[3]	Tharakaraman K., Jayaraman A., Raman R., Cell, 2013, 153(7), 1486—1493
[4]	Li L., Gao F., Ye J., Chen Z., Li Q., Gao W., Analytical Chemistry, 2003, 85(20), 9721—9727
[5]	Cao S., Pei Z., Xu Y., Pei Y., Chemistry of Materials, 2016, 28(12), 4501—4506
[6]	An B. K., Kwon S. K., Jung S. D., Journal of the American Chemical Society, 2002, 124(48), 14410—14415
[7]	Kim S., Zheng Q., He G., Advanced Functional Materials, 2006, 16(18), 2317—2323
[8]	Liu Y., Xu T., Wang F.Z., Journal of Physical Chemistry C, 2007, 111(17), 6544—6549
[9]	Ding D., Li K., Liu B., Tang B.Z., Accounts of Chemical Research, 2013, 46(11), 2441—2453
[10]	Hong Y., Lam Jacky W. Y., Tang B. Z., Chemical Communications, 2009, (29), 4332—4353
[11]	Matyjaszewski K., American Chemical Society, 2000, 768(12), 4167—4171
[12]	Perrier S., Takolpuckdee P., James W.A., Macromolecules, 2004, 37(8), 23—36
[13]	Barner L., Barnerkowollik C., Davis T.P., Australian Journal of Chemistry, 2004, 57(1), 19—24
[14]	Convertine A. J., Lokitz B. S., Vasileva Y., Macromolecules, 2006, 39(5), 1724—1730
[15]	Gramlich P. M. E., Wirges C. T., Gierlich J., Carell T., Organic Letters, 2008, 10(2), 249—251
[16]	Huang J., Habraken G., Audouin F., Heise A., Macromolecules, 2010, 43(14), 6050—6057
[17]	Tsarevsky N. V., Bencherif S. A., Matyjaszewski K., Macromolecules, 2007, 40(13), 4439—4445
[18]	Watt J. A., Williams S. J., Organic & Biomolecular Chemistry, 2005, 3(10), 1982—1992
[19]	Obata M., Shimizu M., Ohta T., Polymer Chemistry, 2011, 2(3), 651—658
[20]	Harvison M. A., Davis T. P., Lowe A. B., Polymer Chemistry, 2011, 2(6), 1347—1354
[21]	Obata M., Kobori T., Hirohara S., Tanihara M., Polymer Chemistry, 2015, 6(10), 1793—1804
[22]	Yu C., Wu Y., Zeng F., Li X., Shi J., Wu S., Biomacromolecules, 2013, 14(12), 4507—4514
[23]	Ryu B. Y., Emrick T., Macromolecules, 2011, 44(14), 5693—5700
[24]	Zhao H. C., Ma S. X., Wang Y. H., Li J. T., Chen S. H., Wang M. M., China Synthetic Resin and Plastics, 2013, 30, 38—42
	(赵洪池, 马双霞, 王耀辉, 李江涛, 陈世辉, 王苗苗. 合成树脂及塑料, 2013, 30, 38—42)
[25]	Tong H., Dong Y., Lam Jacky W.Y., Chemical Communications, 2006, (10), 1133—1135
[26]	Dong Y., Lam Jacky W. Y., Qin A., Sun J., Liu J., Li Z., Chemical Communications, 2007, (31), 3255—3257
[27]	Qin A., Lam Jacky W. Y., Mahtab F., Jim Cathy K. W., Tang L., Sun J., Applied Physics Letters, 2009, 94(25), 253—308

具有聚集诱导发光效应的水溶性糖基荧光聚合物的制备及性能

Synthesis and Properties of Water-soluble Glycosyl Fluorescent Polymer with Aggregation-induced Emission Effect^†

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具有聚集诱导发光效应的水溶性糖基荧光聚合物的制备及性能

Synthesis and Properties of Water-soluble Glycosyl Fluorescent Polymer with Aggregation-induced Emission Effect†

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Synthesis and Properties of Water-soluble Glycosyl Fluorescent Polymer with Aggregation-induced Emission Effect^†