同步质子转移驱动的吡啶基双噻唑胺桥联杯[4]吡咯对磷酸二氢根的选择性识别

doi:10.6023/cjoc202510016

有机化学 ›› 2026, Vol. 46 ›› Issue (6): 2442-2449.DOI: 10.6023/cjoc202510016 上一篇下一篇

研究论文

同步质子转移驱动的吡啶基双噻唑胺桥联杯[4]吡咯对磷酸二氢根的选择性识别

闫艳梅^a, 霍瑞萍^a^,^*(), 何迎春^b^,^*()

^a 太原师范学院化学与材料学院山西晋中 030619
^b 山西大学应用化学研究所山西太原 030006

收稿日期:2026-01-21 修回日期:2026-03-03 发布日期:2026-03-27
通讯作者: 霍瑞萍, 何迎春
基金资助:
山西省高等学校科技创新计划(2021L446); 山西省基础研究计划(202203021221038); 山西省基础研究计划(202403021221183); 山西省基础研究计划联合基金(202503011241002)

Pyridinebisthiazolamine-Strapped Calix[4]pyrrole: An Anion Receptor Selectively Binding Dihydrogenphosphate via Simultaneous Proton Transfer Events

Yanmei Yan^a, Ruiping Huo^a^,^*(), Yingchun He^b^,^*()

^a College of Chemistry and Materials, Taiyuan Normal University, Jinzhong, Shanxi 030619
^b Institute of Applied Chemistry, Shanxi University, Taiyuan, Shanxi 030006

Received:2026-01-21 Revised:2026-03-03 Published:2026-03-27
Contact: Ruiping Huo, Yingchun He
Supported by:
Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L446); Fundamental Research Program of Shanxi Province(202203021221038); Fundamental Research Program of Shanxi Province(202403021221183); Joint Fund Fundamental Research Program of Shanxi Province(202503011241002)

文章分享

1. 262442S.pdf(2291KB)

摘要/Abstract

通过¹H NMR和UV-Vis光谱分析, 系统探究了溶液体系中多种阴离子与吡啶基双噻唑胺桥联杯[4]吡咯(2)的相互作用. 结果表明, 在乙腈介质中, 受体2对磷酸二氢根离子展现出高度的选择性和强结合能力. 结合¹H NMR光谱分析及密度泛函理论(DFT)计算证实, 在受体2对磷酸二氢根离子的识别过程中, 同步发生了质子转移行为: 即一个噻唑氮原子质子化形成氢键供体, 而噻唑连接的NH去质子化形成氢键受体. 此外, 受体2可作为阴离子识别的pH调控分子开关: 中性条件下选择性结合 ${{\text{H}}_{2}}\text{PO}_{4}^{}$, 酸性条件下则切换为结合硫酸氢根( $\text{HSO}_{4}^{}$), 这一特性由桥联结构中噻唑基团的pH响应型质子化/去质子化过程调控实现.

关键词: 杯[4]吡咯, 阴离子识别, 磷酸二氢根, 质子转移

The binding interactions between various test anions and the pyridinebisthiazolamine-strapped calix[4]pyrrole (2) were investigated in CH₃CN solution via ¹H NMR and UV-vis spectroscopic analyses. The results demonstrated that receptor 2 exhibits high affinity and selectivity toward dihydrogenphosphate ( ${{\text{H}}_{2}}\text{PO}_{4}^{}$). On the basis of ¹H NMR spectroscopic analyses and density functional theory (DFT) calculations, it was concluded that simultaneous proton transfer events occur between receptor 2 and ${{\text{H}}_{2}}\text{PO}_{4}^{}$ during the recognition process, where one thiazole nitrogen is protonated to form a hydrogen bond donor and the thiazole-linked NH is deprotonated to generate a hydrogen bond acceptor. Furthermore, receptor 2 acts as a pH-controlled molecular switch for anion recognition: it binds ${{\text{H}}_{2}}\text{PO}_{4}^{}$ preferentially under neutral conditions and switches to $\text{HSO}_{4}^{}$ binding under acidic conditions, which is enabled by the pH-responsive protonation/deprotonation of the thiazole moieties in the strap.

Key words: calix[4]pyrrole, anion recognition, dihydrogenphosphate, proton transfer

引用此文

闫艳梅, 霍瑞萍, 何迎春. 同步质子转移驱动的吡啶基双噻唑胺桥联杯[4]吡咯对磷酸二氢根的选择性识别[J]. 有机化学, 2026, 46(6): 2442-2449.

Yanmei Yan, Ruiping Huo, Yingchun He. Pyridinebisthiazolamine-Strapped Calix[4]pyrrole: An Anion Receptor Selectively Binding Dihydrogenphosphate via Simultaneous Proton Transfer Events[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2442-2449.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 6

Figure 1. (a) Chemical structures of receptors 1 and 2; (b) Hydrogen phosphate binding mode in the pyridinebisthiazolamine- strapped calix[4]pyrrole 2 in its protonated form discovered previously by our group[16]; (c) Dihydrogenphosphate binding mode in the pyridinebisthiazolamine-strapped calix[4]pyrrole 2

Scheme 1. Preparation of pyridinebisthiazolamine-strapped calix[4]pyrrole 2

Figure 2. 1H NMR (600 MHz) spectra of 2 (2.0 mmol/L) upon the addition of TBAH2PO4 in CD3CN (receptor: a~f, ${{\text{H}}_{2}}\text{PO}_{4}^{}$ complex: a'~f') 1H NMR δ

Figure 3. (Left) Computed simultaneous proton transfer transition states TS1 with M062X density functional (def2tzvp level) (The relative electronic energy barriers (ΔE) in acetonitrile solvent are given in kJ/mol); (Right) The optimized molecular structure of receptor 2 with dihydrogenphosphate as calculated in CH3CN

Figure 4. 1H NMR (CD3CN, 600 MHz) spectra of 2 in the presence of 1 equiv. of various anions 1H NMR δ

Figure 5. Partial 1H NMR spectra of receptor 2 (2.0 mmol/L in CD3CN) ¹H NMR δ (a) Free receptor; (b) in the presence of 1.0 equiv. TBAH2PO4; (c) after adding 1.0 equiv. TBAHSO4 to (b); (d) after adding 1.5 equiv. HNO3 to (c); (e) after further adding 1.5 equiv. TBAOH to (d); (f) after further adding 1.5 equiv. HNO3 to (e); (g) in the presence of 1.0 equiv. TBAHSO4 and 1.5 equiv. HNO3; (h) in the presence of 1.0 equiv. TBAHSO4.

参考文献 23

[1]	Saenger, V. W. Principles of Nucleic Acid Sructure, Springer-Verlag, Berlin, 1984, p. 762.
[2]	Lee, G. J.; Marks, J. Pediatr. Nephrol. 2015, 30, 363.
[3]	Hansen, N. M.; Felix, R.; Bisaz, S.; Fleisch, H. Biochim. Biophys. Acta 1976, 451, 549.
[4]	Crook, M.; Swaminathan, R. Ann. Clin. Biochem. 1996, 33, 376.
[5]	Ryther, J. H.; Dunstan, W. M. Science 1971, 171, 1008.
[6]	(a) Ebbesen, P. J. Immunol. 1972, 109, 1296.
	(b) Jalava, P. I.; Salonen, R. O.; Pennanen, A. S.; Happo, M. S.; Penttinen, P.; Halinen, A. I.; Sillanpaa, M.; Hillamo, R.; Hirvonen, M. R. Toxicol. Appl. Pharmacol. 2008, 229, 146.
	(c) Grahame, T. J.; Schlesinger, R. B. Inhalation Toxicol. 2005, 17, 15.
[7]	Bhattacharyya, A. Synlett 2012, 23, 2142.
[8]	Pal, S.; Ghosh, T. K.; Ghosh, R.; Mondal, S; Ghosh, P. Coord. Chem. Rev. 2020, 405, 213128.
[9]	(a) Sessler, J. L.; Katayev, E.; Pantos, G. D.; Ustynyuk, Y. A. Chem. Commun. 2004, 1276.
	(b) Katayev, E. A.; Boev, N. V.; Khrustalev, V. N.; Ustynyuk, Y. A.; Tananaev, I. G.; Sessler, J. L. J. Org. Chem. 2007, 72, 2886.
	(c) Katayev, E. A.; Pantos, M. D. Reshetova, V. N. Khrustalev, V. M. Lynch, Y. A. Ustynyuk, C. D.; Sessler, J. L. Angew. Chem., Int. Ed. 2005, 44, 7386.
	(d) Sessler, J. L.; Katayev, E.; Pantos, G. D.; Scherbakov, P.; Reshetova, M. D.; Khrustalev, V. N.; Lynch, V. M.; Ustynyuk, Y. A. J. Am. Chem. Soc. 2005, 127, 11442.
	(e) Katayev, E. A.; Sessler, J. L.; Khrustalev, V. N.; Ustynyuk, Y. A. J. Org. Chem. 2007, 72, 7244.
	(f) Saha, S.; Akhuli, B.; Chakraborty, S.; Ghosh, P. J. Org. Chem. 2013, 78, 8759.
	(g) Song, N. R.; Moon, J. H.; Choi, J.; Jun, E. J.; Kim, Y.; Kim, S.-J.; Lee, J. Y.; Yoon, J. Chem. Sci. 2013, 4, 1765.
	(h) Deng, C. L.; Bard, J. P.; Lohrman, J. A.; Barker, J. E.; Zakharon, L. N.; Johnson, D. W.; Haley, M. M. Angew. Chem., Int. Ed. 2019, 58, 3934.
[10]	Chang, Y. X.; Qin, H. J.; Wang, X.; Li, X. P.; Li, M. M.; Yang, H.; Xu, K. X.; Qing, G. Y. ACS Sens. 2020, 5, 2438.
[11]	(a) Gale, P. A.; Anzenbacher Jr., P.; Sessler, J. L. Coord. Chem. Rev. 2001, 222, 57.
	(b) Anzenbacher Jr, P.; Nishiyabu, R.; Palacios, M. A. Coord. Chem. Rev. 2006, 250, 2929.
	(c) Saha, I.; Lee, J. T.; Lee, C.-H. Eur. J. Org. Chem. 2015, 18, 3859.
[12]	Gale, P. A.; Sessler, J. L.; Král, V.; Lynch, V. J. Am. Chem. Soc. 1996, 118, 5140.
[13]	(a) Kim, S. K.; Gross, D. E.; Cho, D.-G.; Lynch, V. M.; Sessler, J. L. J. Org. Chem. 2011, 76, 1005.
	(b) Park, J. S.; Karnas, E.; Ohkubo, K.; Chen, P.; Kadish, K. M.; Fukuzumi, S.; Blelawski, C. W.; Hudnall, T. W.; Lynch, V. M.; Sessler, J. L. Science 2010, 329, 1324.
	(c) Liu, Y. L.; Minami, T.; Nishiya-bu, R.; Wang, Z.; Anzenbacher Jr, P. J. Am. Chem. Soc. 2013, 135, 7705.
	(d) Nishiyabu, R.; Palacios, M. A.; Dehaen, W.; Anzenbacher, P. J. Am. Chem. Soc. 2006, 128, 11496.
	(e) Palacios, M. A.; Nishiyabu, R.; Marquez, M.; Anzenbacher, P. J. Am. Chem. Soc. 2007, 129, 7538.
	(f) Pushina, M.; Koutnik, P.; Nishiyabu, R.; Minami, T.; Savechenkov, P.; Anzenbacher Jr, P. Chem.-Eur. J. 2018, 24, 4879.
[14]	(a) He, Y. C.; Yan, Y. M.; Tong, H. B.; Ren Z, X.; Wang, J. H.; Zhang, Y. B.; Chao, J. B.; Wang, M. L. Chem. Commun. 2020, 56, 9364.
	(b) Lee, C. H.; Miyaji, H.; Yoon, D. W. Chem. Commun. 2008, 24.
	(c) Ko, S. K.; Kim, S. K.; Share, A.; Lynch, V. M.; Park, J. H.; Namkung, W.; Rossom, W. V.; Busschaert, N.; Gale, P. A.; Sessler, J. L.; Shin, I. Nat. Chem. 2014, 6, 885.
	(d) Peng, S. S.; He, Q.; Vargas-Zúñiga, G. I.; Qin, L.; Hwang, I. H.; Kim, S. K.; Heo, N. J.; Lee, C. H.; Dutta, R. J.; Sessler, J. L. Chem. Soc. Rev. 2020, 49, 865.
	(e) He, Y. C.; Ren, Z. X.; Zhao, X. F.; Zhang, Y. B.; Wang, J. H.; Chao, J. B.; Wang, M. L. Tetrahedron 2019, 75, 130491.
	(f) Chang, K.-C.; Minami, T.; Koutnik, P.; Savechenkov, P. Y.; Liu, Y. L.; Anzenbacher Jr, P. J. Am. Chem. Soc. 2014, 136, 1520.
[15]	Heo, N. J.; Yang, J. H.; Lynch, V. M.; Ko, B. J.; Sessler, J. L.; Kim, S. K. Chem. Sci. 2020, 11, 8288.
[16]	He, Y. C.; Tong, H. B.; Xu, C. G.; Ren, Z. X.; Wang, Y. Z.; Yan, Y. M.; Wang, M. L. Org. Lett. 2023, 25, 1737.
[17]	Oh, J. H.; Kim, J. H.; Kim, D. S.; Han, H. J.; Lynch, V. M.; Sessler, J. L.; Kim, S. K. Org. Lett. 2019, 21, 4336.
[18]	Bourson, J.; Pouget, J.; Valeur, B. J. Phys. Chem. 1993, 97, 4552.
[19]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B. Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford, CT, 2013.
[20]	Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215.
[21]	Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2005, 7, 3297.
[22]	Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378.
[23]	Eichkorn, K.; Weigend, F.; Treutler, O.; Ahlrichs, R. Theor. Chem. Acc. 1997, 97, 119.

同步质子转移驱动的吡啶基双噻唑胺桥联杯[4]吡咯对磷酸二氢根的选择性识别

Pyridinebisthiazolamine-Strapped Calix[4]pyrrole: An Anion Receptor Selectively Binding Dihydrogenphosphate via Simultaneous Proton Transfer Events

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 6

参考文献 23

相关文章 15

编辑推荐

相关统计

本文评价

[1]	刘依雨, 胡喻栋, 张清伟. 金属催化的非活化炔烃氢膦酰化反应的机理研究进展[J]. 有机化学, 2024, 44(12): 3678-3685.
[2]	刘梦, 黄延茹, 孙小飞, 汤立军. 一种基于“聚集诱导发光+激发态分子内质子转移”机制的苯并噻唑衍生物荧光探针及其对次氯酸根的识别[J]. 有机化学, 2023, 43(1): 345-351.
[3]	郭钺甜, 潘永鑫, 汤立军. 聚集诱导发光(AIE)和激发态分子内质子转移(ESIPT)结构融合的反应型荧光探针的研究进展[J]. 有机化学, 2022, 42(6): 1640-1650.
[4]	王瑞祥, 赖晓静, 邱观音生, 刘晋彪. 基于激发态分子内质子转移(ESIPT)原理的反应型荧光探针研究进展[J]. 有机化学, 2019, 39(4): 952-960.
[5]	刘钰, 汤永星, 罗月阳, 朱叶婷, 杨进, 魏欣雨, 刘雄, 赵云辉. 含巴比妥结构荧光探针的合成及其应用研究[J]. 有机化学, 2019, 39(10): 2980-2984.
[6]	李翔, 林奇, 曲文娟, 李乔, 程晓斌, 李文婷, 张有明, 姚虹, 魏太保. 一种咪唑并吩嗪内酰胺反应型识别氰离子的荧光探针[J]. 有机化学, 2017, 37(4): 889-895.
[7]	谭赞, 杜欢, 吕新阳, 鲍小平. 含氨基蒽醌信号单元的咔唑磺胺类阴离子受体的合成及识别性能研究[J]. 有机化学, 2016, 36(6): 1389-1394.
[8]	赵飞飞, 伍宏伟, 刘传祥, 毛海舫. 基于芳基炔醛共轭延伸的1,8-萘酰亚胺的高选择性比色和荧光氰离子探针[J]. 有机化学, 2016, 36(11): 2689-2694.
[9]	蹇军友, 闫柏任, 潘顶伍, 谭赞, 吕新阳, 杜欢, 鲍小平. 含苯胺基硫脲单元的咔唑衍生物的合成及其对阴离子的识别传感研究[J]. 有机化学, 2015, 35(5): 1069-1074.
[10]	卓继斌, 晏希泉, 王小雪, 谢莉莉, 袁耀锋. 双核开链茂铁咪唑受体的合成与阴离子识别研究[J]. 有机化学, 2015, 35(5): 1090-1096.
[11]	晏希泉, 卓继斌, 王吉成, 谢莉莉, 袁耀锋. 苯并香豆素硫脲类受体分子的设计、合成与阴离子识别研究[J]. 有机化学, 2015, 35(10): 2184-2190.
[12]	马拓, 张瑾, 刘龙珠, 贺云, 张尊听. Al³⁺可视化水溶性分子荧光探针的合成及其作用研究[J]. 有机化学, 2014, 34(9): 1780-1785.
[13]	张鹏, 张有明, 林奇, 姚虹, 魏太保. 金属离子响应型荧光传感分子的设计原理及研究进展[J]. 有机化学, 2014, 34(7): 1300-1321.
[14]	刘瑞源, 勇雪, 杨小东, 严轶琛, 路新卫, 瞿金清. 基于2-硫代海因的氟离子探针[J]. 有机化学, 2014, 34(3): 561-565.
[15]	黄志斌, 刘学成, 胡明华, 林伟, 史达清. 吡啶并[2,3-d]嘧啶衍生物受体的合成及对阴离子识别研究[J]. 有机化学, 2014, 34(2): 382-386.