A Chiral Polymer of Intrinsic Microporosity for Fluorescent Recognition

doi:10.6023/A24060191

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (8): 914-918.DOI: 10.6023/A24060191 Previous Articles

Article

一种手性自具微孔聚合物的合成及手性荧光识别

王玉^a, 于聪^a, 夏艳芳^b, 林蓝^c^,^*(), 陈强^d, 王新波^a^,^*()

a 山东大学环境科学与工程学院山东环境过程与健康重点实验室青岛 266237
b 山东长泽新材料科技有限公司枣庄 277212
c 滨州魏桥国科高等技术研究院滨州 256606
d 南京工业大学苏州未来膜技术创新中心苏州 215519

投稿日期:2024-06-11 发布日期:2024-07-18
基金资助:
国家自然科学基金(22078174); 教育部产学合作协同育人项目(231106429150016); 江苏省创新能力建设计划——江苏省技术创新中心课题(KF2024004)

A Chiral Polymer of Intrinsic Microporosity for Fluorescent Recognition

Yu Wang^a, Cong Yu^a, Yanfang Xia^b, Lan Lin^c^,^*(), Qiang Chen^d, Xinbo Wang^a^,^*()

a School of Environmental Science and Engineering, Shandong Key Laboratory of Environmental Processes and Health, Shandong University, Qingdao 266237, China
b Shandong Changze New Material Technology Co., Ltd, Zaozhuang 277212, China
c Binzhou Institute of Technology, Weiqiao-UCAS Science and Technology Park, Binzhou 256606, China
d NJTECH University Suzhou Future Membrane Technology Innovation Center, Suzhou 215519, China

Received:2024-06-11 Published:2024-07-18
Contact: * E-mail: linlan@wqucas.com; wangxb@sdu.edu.cn
Supported by:
National Natural Science Foundation of China(22078174); University-Industry Collaborative Education Program(231106429150016); Jiangsu Future Membrane Technology Innovation Center(KF2024004)

1. .pdf(919KB)

Abstract

Chirality, a ubiquitous phenomenon in nature, profoundly influences material properties. The precise synthesis of chiral compounds and enantiomer recognition techniques hold promise as pivotal advancements in the realms of medicine, informatics, and materials science, yet remain a formidable challenge. In this paper, we prepared a monochiral self-forming microporous polymers ((R)-HSBI-Is) through direct-synthesis method, and applied it for chiral recognition of phenylalanine. First, commencing with bisphenol A, racematic 3,3,3',3'-tetramethyl-1,1'-spirodine-7,7'-diol (6,6'-TMSOL) was synthesized, and form transitional complex derivates through adding chiral reagents (L-menthyl chloroformate). After three times recrystallization under －18 ℃, the diastereoisomers of the complex derivates were successfully separated due to their different solubility. After hydrolysis reaction, the auxiliary groups were removed and chiral monomer was synthesized. This study achieved the artful synthesis of pure (R)-3,3,3',3'-tetramethyl-1,1'-spirodine-7,7'-diol ((R)-6,6'-TMSOL). Subsequently, chiral polymer of intrinsic microporosity ((R)-HSBI-Is) were crafted through Friedel-Crafts reaction with isatin molecules. And we delved the mechanism of synthesizing chiral polymers. These polymers were comprehensively evaluated using techniques such as nuclear magnetic resonance, infrared spectroscopy, UV spectroscopy, specific surface area and pore size analysis, and thermogravimetric analysis. Our findings reveal that the polymer boasts a high specific surface area and robust fluorescence. It also shows a great performance in thermal stability. The fluorescence experiments on chiral molecules (phenylalanine, tryptophan, 1,1'-binaphthyl-2,2'-diol (BINOL), 1,1'-spirobiindane (SPINOL) and 1-phenylethanol) were carried out to testify the recognition performance of chiral polymer. The results proved that the polymer exhibits a remarkable selective fluorescence enhancement towards L-phenylalanine. Specifically, the L- and D-configuration selectivity achieved is 34.9, positioning it as an exceptional chiral recognition agent for L-phenylalanine.

Key words: chirality, polymers of intrinsic microporosity, chiral recognition, fluorescence recognition, phenylalanine

Cite this article

Yu Wang, Cong Yu, Yanfang Xia, Lan Lin, Qiang Chen, Xinbo Wang. A Chiral Polymer of Intrinsic Microporosity for Fluorescent Recognition[J]. Acta Chimica Sinica, 2024, 82(8): 914-918.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 5

Scheme 1. Synthesis of chiral monomer

Figure 1. (a) HPLC spectra of complex derivative 2 before and after recrystallization; (b) 1H NMR spectra of (R)-1 and (R)-HSBI-Is; (c) FT-IR spectra of 6,6'-TMSOL, HSBI-Is and (R)-HSBI-Is; (d) adsorption isothermal curves of (R)-HSBI-Is, insert the pore size distribution of (R)-HSBI-Is; (e) TGA spectra of (R)-HSBI-Is; (f) UV-Vis and FL curves of (R)-HSBI-Is in methanol

Scheme 2. Synthesis of chiral polymer (R)-HSBI-Is

Figure 2. Fluorescence spectra of (R)-HBSI-Is with or without D-phenylalanine/L-phenylalanine

Figure 3. Fluorescence intensity change with small molecule additives. The stars represent the chiral selectivity S

References 23

[1]	Youatt, J. B.; Brown, R. D. Science 1981, 212, 1145. pmid: 17815225
[2]	Maier, N. M.; Franco, P.; Lindner, W. J. Chromatogr. A 2001, 906, 3. pmid: 11215893
[3]	Amako, Y.; Woo, C. M. Nat. Chem. 2019, 11, 1080. doi: 10.1038/s41557-019-0380-0 pmid: 31758156
[4]	Teng, Y.; Gu, C.-L.; Chen, Z.-H.; Jiang, H.; Xiong, Y.; Liu, D.; Xiao, D. Chirality 2022, 34, 1094. doi: 10.1002/chir.23453 pmid: 35676772
[5]	D'orazio, G.; Fanali, C.; Asensio-Ramos, M.; Fanali, S. TrAC, Trends Anal. Chem. 2017, 96, 151.
[6]	Abad-Gil, L.; Marina, M. L. J. Chromatogr. Open 2023, 4, 100099.
[7]	Scriba, G. K. E. J. Chromatogr. A 2016, 1467, 56.
[8]	(a) Zou, J.; Zhao, G.-Q.; Zhao, G.-L.; Yu, J.-G. Coord. Chem. Rev. 2022, 471, 214732.
	(b) Niu, X.-H.; Yang, X.; Li, H.-X.; Liu, J.; Liu, Z.-Y.; Wang, K.-J. Microchim. Acta 2020, 187, 676.
[9]	(a) Lu, S.-Y.; Liang, Y.; Wang, L.-M.; Huang, S.; Xiao, Q. Spectrosc. Spectr. Anal. 2016, 36(S1), 10 (in Chinese).
	(卢双燕, 梁瑜, 王鲁敏, 黄珊, 肖琦, 光谱学与光谱分析, 2016, 36(S1), 10.)
	(b) Tian, X.-M.; Lin, Y.-Q.; Zhu, H.; Huang, C.; Zhu, B.-X. Acta Chim. Sinica 2023, 81, 20 (in Chinese).
	(田小茂, 林悦群, 朱菡, 黄超, 朱必学, 化学学报, 2023, 81, 20.) doi: 10.6023/A22090400
[10]	(a) Zhao, Y.; Liu, H.-L.; Sun, B.-G. Sens. Actuators, B 2022, 354, 131253.
	(b) Chen, J.; Wang, Y.-T.; Yu, Y.-L.; Wang, J.-H.; Liu, J.-W.; Ihara, H.; Qiu, H.-D. Exploration 2023, 3, 20220144.
[11]	Chen, A.-L.; Zhong, Y.-J.; Yin, X.-H.; Li, R.-J.; Deng, Q.-F.; Yang, R. Sens. Actuators, B 2023, 393, 134262.
[12]	Anum, D.; Bwambok, D. K. J. Mol. Liq. 2023, 390, 123141.
[13]	Zhao, Y.-W.; Guo, L.-E.; Zhang, F.-Q.; Yao, J.; Zhang, X.-M. ACS Appl. Mater. Interfaces 2021, 13, 20821.
[14]	(a) Lu, Z.-Y.; Lu, X.-T.; Zhong, Y.-H.; Hu, Y.-F.; Li, G.-K.; Zhang, R.-K. Anal. Chim. Acta 2019, 1050, 146.
	(b) Chen, L.-Y.; Tan, M.-X.; Jin, J.-N.; Zhang, Z.-B.; Huang, F.-H.; Li, S.-J.; Li, Y.-X. Chinese J. Org. Chem. 2024, 44, DOI: 10.6023/cjoc202401011 (in Chinese).
	(陈璐怡, 谭梦霞, 金迦南, 张子彬, 黄飞鹤, 李世军, 李云霞, 有机化学, 2024, 44, DOI: 10.6023/cjoc202401011.)
[15]	Jafari, M.; Tashkhourian, J.; Absalan, G. Spectrochim. Acta, Part A 2017, 185, 77.
[16]	Wang, X.-B.; Guo, H.; Yu, C.; Jing, Y.-J.; Han, Z.-B.; Ma, X.-H.; Yang, C.-C.; Liu, M.-H.; Zhai, D.; Zheng, D.-Y.; Pan, Y.-P.; Li, X.-X.; Ding, K.-L. Macromolecules 2021, 54, 11180.
[17]	Weng, X.-L.; Baez, J. E.; Khiterer, M.; Hoe, M. Y.; Bao, Z.-B.; Shea, K. J. Angew. Chem. Int. Ed. 2015, 54, 11214.
[18]	Zhang, Q.-P.; Wang, Z.; Zhang, Z.-W.; Zhai, T.-L.; Chen, J.-J.; Ma, H.; Tan, B.-E.; Zhang, C. Angew. Chem. Int. Ed. 2021, 60, 12781.
[19]	Feizi, F.; Shamsipur, M.; Gholivand, M. B.; Taherpour, A.; Barati, A.; Shamsipur, H.; Mohajerani, E.; Budd, P. J. Mater. Chem. C 2020, 8, 13827.
[20]	Chen, W.-F.; Lin, H.-Y.; Dai, S.-A. Org. Lett. 2004, 6, 2341.
[21]	Zhu, Z.-Y.; Dong, H.; Li, K.-H.; Li, Q.-X.; Li, J.-X.; Ma, X.-H. Sep. Purif. Technol. 2021, 262, 118313.
[22]	Luo, H.-H.; Yang, F.; Li, C.; Zhong, Y.-F.; Cheng, C.; Wang, S.-L.; Jin, S.-B. Chem. Eng. J. 2023, 476, 146611.
[23]	(a) Xu, C.-M.; Qi, Y.-S.; Yang, X.-S.; Li, X.-F.; Li, Z.-P.; Bai, L. Org. Lett. 2021, 23, 2890.
	(b) Lin, X.-F.; Yao, L.-X.; Chang, S.-R.; Wang, L. CN108659041A, 2017 [Chem. Abstr. 2017, 169, 526105] (in Chinese).
	(林旭锋, 姚林曦, 常时瑞, 王雷, CN108659041A, 2017, [Chem. Abstr. 2017, 169, 526105].)

一种手性自具微孔聚合物的合成及手性荧光识别

A Chiral Polymer of Intrinsic Microporosity for Fluorescent Recognition

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 23

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Xiaozhen Li, Qingfu Sun. Research Progress of Rare Earth-Based Circularly Polarized Luminescent Materials [J]. Acta Chimica Sinica, 2024, 82(6): 707-730.
[2]	Haoning Zheng, Jinyu Liu. Research Progress on Organocatalytic Functionalization of Indole in the Carbocyclic Ring [J]. Acta Chimica Sinica, 2024, 82(6): 641-657.
[3]	Jinyue Ma, Lufei Huang, Baowen Zhou, Lin Yao. Construction and Catalysis Advances of Inorganic Chiral Nanostructures [J]. Acta Chimica Sinica, 2022, 80(11): 1507-1523.
[4]	Qing-Ru Zhao, Ru Jiang, Shu-Li You. Ir-catalyzed Sequential Asymmetric Allylic Substitution/Olefin Isomerization for the Synthesis of Axially Chiral Compounds [J]. Acta Chimica Sinica, 2021, 79(9): 1107-1112.
[5]	Chen Zhonghang, Han Zongsu, Shi Wei, Cheng Peng. Design, Synthesis and Applications of Chiral Metal-Organic Frameworks [J]. Acta Chimica Sinica, 2020, 78(12): 1336-1348.
[6]	Wang Qiang, Gu Qing, You Shu-Li. Recent Progress on Transition-Metal-Catalyzed Asymmetric C-H Bond Functionalization for the Synthesis of Biaryl Atropisomers [J]. Acta Chim. Sinica, 2019, 77(8): 690-704.
[7]	Cai Qian, Ma Haowen. Recent Advances of Chiral Hypervalent Iodine Reagents [J]. Acta Chim. Sinica, 2019, 77(3): 213-230.
[8]	Li Qi, Jia Yi, Li Junbai. Controlled Assembly of Chiral Structure of Diphenylalanine Peptide [J]. Acta Chimica Sinica, 2019, 77(11): 1173-1176.
[9]	Li Meng, Lin Wei-Bin, Fang Lei, Chen Chuan-Feng. Recent Progress on Circularly Polarized Luminescence of Chiral Organic Small Molecules [J]. Acta Chim. Sinica, 2017, 75(12): 1150-1163.
[10]	Gao Guanbin, Gong Dejun, Zhang Mingxi, Sun Taolei. Chiral Gold Nanoclusters: A New Near-Infrared Fluorescent Probe [J]. Acta Chim. Sinica, 2016, 74(4): 363-368.
[11]	Gao Yuxi, Hu Jun, Ju Yong. Supramolecular Self-Assembly Based on Natural Small Molecules [J]. Acta Chim. Sinica, 2016, 74(4): 312-329.
[12]	Hong Chuanmin, Wang Haishui. Effect of D-Cysteine Self-assembled Monolayers on the Crystallization and Growth of D- or L-Aspartic Acid [J]. Acta Chimica Sinica, 2014, 72(6): 739-742.
[13]	PU Xue-Wei, LI Lian-Zhi, DONG Jian-Fang, HUANG Lei, BIAN Lin. Synthesis, Crystal Structure and DNA Interaction of a Copper(II) Complex with Ligands of L-Phenylalanine Schiff Base and 1,10-Phenanthroline [J]. Acta Chimica Sinica, 2011, 69(06): 647-652.
[14]	ZHANG Qing-You, LONG Hai-Lin, ZHOU Yan-Mei, HAO Jun-Feng, XU Lu, LENG Ji-Yan. Studies on Quantitative 2D Chirality Degrees of Benzenoids [J]. Acta Chimica Sinica, 2011, 69(03): 311-315.
[15]	JIANG Shan-Shan, LIU Zhong-Fang, HU Xiao-Li, LIU Shao-Pu, XU Qian-Ying, TIAN Lun-Fu. Fluorescence Quenching Method for the Determination of Colchicine with Some Aromatic Amino Acids as Probes [J]. Acta Chimica Sinica, 2010, 68(22): 2325-2330.