测定氨基酸浓度和对映体组成的手性荧光探针

doi:10.6023/cjoc202401022

有机化学

研究论文

测定氨基酸浓度和对映体组成的手性荧光探针

李非凡^a, 余康^a, 倪传志^b, 朱园园^b,*, 曾婕^c,*, 古双喜^a,c,*

^a绿色化工过程教育部重点实验室,新型反应器与绿色化学工艺湖北省重点实验室,化工与制药学院,武汉工程大学,武汉,430205;
^b化学与环境工程学院,武汉工程大学,武汉,430205;
^c药物研究院,武汉工程大学,武汉,430205

收稿日期:2024-01-16 修回日期:2024-05-08
基金资助:
国家自然科学基金(No. 22074114, 22377097, 21877087); 湖北省自然科学基金(No. 2020CFB623, 2021CFB556); 磷资源开发利用教育部工程研究中心开放基金(No. LCX202305); 武汉工程大学研究生教学研究项目(No. 2022JYXM09, 2021JYXM07); 武汉工程大学研究生创新基金(No. CX2022450).

Chiral Fluorescent Probes for Determination of Both Concentration and Enantiomeric Composition of Amino Acids

Fei-Fan Li^a, Kang Yu^a, Chuan-Zhi Ni^b, Yuan-Yuan Zhu^b,*, Jie Zeng^c,*, Shuang-Xi Gu^a,c,*

^aKey Laboratory for Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering & Pharmacy, Pharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205;
^bSchool of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205;
^cPharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205

Received:2024-01-16 Revised:2024-05-08
Contact: * E-mail: yyzhu531@163.com, jiezeng116964@163.com, shuangxigu@163.com
Supported by:
National Natural Science Foundation of China (No. 22074114, 22377097, 21877087); Natural Science Foundation of Hubei Province of China (No. 2020CFB623, 2021CFB556), Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education (No. LCX202305), Wuhan Institute of Technology Graduate Education and Teaching Reform Research Project (No. 2022JYXM09, 2021JYXM07) and Wuhan Institute of Technology Graduate Innovation Fund (No. CX2022450)

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摘要/Abstract

设计并合成了基于BINOL骨架的新型荧光探针(R)-2及其异构体(R)-3。在探针分子的3'位引入的喹啉亚胺基团,通过N原子与Zn(II)的络合作用参与氨基酸的分子识别,协同增强了BINOL手性醛对氨基酸的对映选择性。探针分子对多种氨基酸在438 nm表现出与手性无关的荧光增强,而在513 nm显示出优异的对映选择性荧光响应。研究了以上两个不同发射峰强度分别与精氨酸浓度和对映体过量（ee）的依赖函数关系,并应用拟合的函数方程测定了多个精氨酸样品的浓度和ee值。利用¹H NMR和高分辨质谱研究了在Zn²⁺存在条件下,探针分子与不同手性构型的精氨酸分子之间的作用机理,并采用高斯16计算了D-或L-精氨酸/探针/Zn(II)络合物的热力学稳定性,进一步阐明了探针分子对氨基酸对映选择性的本质原因。本研究实现了单一探针测定7个手性氨基酸（Glu, Arg, Gln, Ser, Thr, Met, Ala）的浓度和对映体组成两个重要参数。

关键词: 荧光探针, 手性识别, 对映选择性, 对映体过量, 氨基酸

A novel BINOL-based fluorescent probe (R)-2 and its isomer (R)-3, featuring quinoline imine groups at 3'-position, were designed and synthesized through simple aldimine condensation reactions. The quinoline imine groups of the probes are involved in the molecular recognition of amino acids through complexation between N atom and Zn(II), which synergically enhances the enantioselectivity of BINOL-aldehyde to amino acids. Excitation at two different wavelengths made (R)-2 or (R)-3 exhibit prominent fluorescent enhancement at two emission peaks, which correspond to 438 nm with no dependence on amino acid chirality, and 513 nm with high enantioselectivity. The fitted equations of I₄₃₈ versus concentration, and I₅₁₃ versus ee values were applied to determine the concentration and enantiomeric excess of arginine with low absolute errors. The interaction mechanism between (R)-2 and D-/L-arginine in the presence of Zn²⁺ was investigated by ¹H NMR and high-resolution mass spectrometry. The thermodynamic stability of the arginine enantiomer/probe/Zn(II) complexes were calculated by Gaussian 16 program to elucidate the origin of the enantioselectivity. This work affords a platform for the determination of the concentration and enantiomeric composition of 7 amino acids (Glu, Arg, Gln, Ser, Thr, Met, Ala) through a single probe.

Key words: Fluorescent probe, Chiral recognition, Enantioselectivity, Enantiomeric excess, Amino acids

引用此文

李非凡, 余康, 倪传志, 朱园园, 曾婕, 古双喜. 测定氨基酸浓度和对映体组成的手性荧光探针[J]. 有机化学, doi: 10.6023/cjoc202401022.

Fei-Fan Li, Kang Yu, Chuan-Zhi Ni, Yuan-Yuan Zhu, Jie Zeng, Shuang-Xi Gu. Chiral Fluorescent Probes for Determination of Both Concentration and Enantiomeric Composition of Amino Acids[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202401022.

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[1] (a) Vellai, T. Nature, 2021, 596, 192-194.
(b) Oh, S. F.; Praveena, T.; Song, H.; Yoo, J. S.; Jung, D. J.; Erturk-Hasdemi, D.; Hwang, Y. S. ; Lee, C. C.; Le Nours, J.; Kim, H.; Lee, J.; Blumberg, R. S.; Rossjohn, J.; Park, S. B.; Kasper, D.L. Nature, 2021, 600, 302-307.
(c) Gu, S.-X.; Wang, H.-F.; Zhu, Y.-Y.; Chen, F.-E. Pharm. Fronts, 2020, 02, e79-e87.
[2] (a) Cheng, X.; Shen, C.; Dong, X.-Q.; Wang, C.-J. Chem. Commun., 2022, 58, 3142.
(b) Li, K.; Wang, L.; Zhen, S.; Zhu, L.; Yu, S.; Wu, Y.; Guo, H. Org. Chem. Front., 2023, 10, 5463-5469.
(c) Nie, F.; Wang, K.-Z.; Yan, D. Nat. Commun., 2023, 14, 1654.
(d) Cai, J.;Liu, A.-A.; Shi, X.-H.; Fu, H.; Zhao,W.; Xu, L.; Kuang, H.; Xu, C.; Pang, D.-W. J. Am. Chem. Soc., 2023, 145, 24375-24385.
[3] Reviews on the determination of concentration and enantiomeric composition of amino acids by fluorescent probes: (a) Pu, L.; Acc. Chem. Res., 2017, 50, 1032-1040.
(b) Herrera, B. T.; Pilicer, S. L.; Anslyn, E. V.; Joyce, L. A.; Wolf, C. J. Am. Chem. Soc., 2018, 140, 10385-10401.
(c) Yu, F.; Chen, Y.; Jiang, H.; Wang, X. Analyst, 2020, 145, 6769-6812.
[4] Researches on the determination of concentration and enantiomeric composition of amino acids by fluorescent probes: (a) Wang, Q.; Wu X.; Pu, L. Org. Lett., 2019, 21, 9036-9039.
(b) Wen, K.; Yu, S.; Huang, Z.; Chen, L.; Xiao, M.; Yu, X.; Pu, L. J. Am. Chem. Soc., 2015, 137, 4517-4524.
(c) Iqbal, S.; Yu, S.; Jiang, L.; Wang, X.; Chen,Y.; Wang, Y.; Yu, X.; Pu, L. Chem. - Eur. J., 2019, 25, 9967-9972.
[5] Determination of concentration and enantiomeric composition of chiral amines by other methods: (a) Bentley, K. W.; Wolf, C. J. Am. Chem. Soc., 2013, 135, 12200-12203.
(b) Nieto, S.; Lynch, V. M.; Anslyn, E. V.; Kim, H.; Chin, J. J. Am. Chem. Soc., 2008, 130, 9232-9233.
(c) Nieto, S.; Dragna, J. M.; Anslyn, E. V. Chem. - Eur. J., 2010, 16, 227-232.
[6] Non-BINOL-based chiral fluorescence probes: (a) Mei, X. F.; Wolf, C. Chem. Commun., 2004, 18, 2078-2079.
(b) Upadhyay, S. P.; Pissurlenkar, R. R. S.; Coutinho, E. C.; Karnik, A. V. J. Org. Chem., 2007, 72, 5709-5714.
(c) Ghosn, M. W.; Wolf, C. J. Am. Chem. Soc., 2009, 131, 16360-16361.
[7] Huang, Z.; Yu,S.; Wen, K.; Yu, X.; Pu, L. Chem. Sci., 2014, 5, 3457-3462.
[8] Zhu, Y.-Y.; Wu, X.-D.; Gu, S.-X.; Pu, L. J. Am. Chem. Soc., 2019, 141, 175-181.
[9] Achiral fluorescent probes of Zn(II) with quinoline groups: (a) Hsieh, W. H.; Wan, C.-F.; Liao, D.-J.; Wu, A.-T. Tetrahedron Lett., 2012, 53, 5848-5851.
(b) Kimura, E.; Koike, T. Chem. Soc. Rev., 1998, 27, 179-184.
(c) Zalewski, P. D.; Forbes, I. J.; Seamark, R. F.; Borlinghaus, R.; Betts, W. H.; Lincoln, S. F.; Ward, A. D. Chem. Biol., 1994, 1, 153-161.
(d) Zalewski, P. D.; Forbes, I. J.; Betts, W. H. Biochem. J., 1993, 296, 403-408.
(e) Huang, S.; Yang, B.; Tu, S. Comput. Theor. Chem., 2022, 1210, 113647.
(f) Gao, L.-L.; Li, S.-P.; Wang, Y.; Wu, W.-N.; Zhao, X.-L.; Li, H.-J.; Xu, Z.-H. Spectrochim. Acta A, 2020, 230, 118025.

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测定氨基酸浓度和对映体组成的手性荧光探针

Chiral Fluorescent Probes for Determination of Both Concentration and Enantiomeric Composition of Amino Acids

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