碳硼烷基苯并咪唑鎓环蕃的合成及核苷酸识别性质研究

doi:10.6023/cjoc202203005

摘要/Abstract

以1,2-双(4-苄溴苯基)-邻碳硼烷为原料合成了两种新型的碳硼烷基苯并咪唑鎓类荧光探针4a和4b, 通过IR, ¹H NMR, ¹³C NMR, ¹¹B NMR和ESI-MS对其结构进行表征, 并通过荧光、紫外光谱研究了探针4a和4b对核苷酸的识别性能. 荧光滴定结果表明: 探针4a和4b可以对单磷酸尿苷(UMP)实现on-off型响应, 并具有良好的选择性和灵敏度, 其中探针4b对于UMP的检测限可以达到3.41×10^–8 mol/L. 通过Job’s曲线和¹H NMR滴定对探针4b的识别机理进行了初步的研究.

关键词: 碳硼烷, 苯并咪唑, 识别, 荧光淬灭, 单磷酸尿苷

Two novel carborane-based benzimidazolium fluorescent probes 4a and 4b were synthesized using 1,2-bis(4-benzylbromophenyl)-o-carborane as starting materials. The structures were characterized by IR, ¹H NMR, ¹³C NMR, ¹¹B NMR and ESI-MS, and the recognition properties of probes 4a and 4b for nucleotides were studied by fluorescence and ultraviolet spectroscopy. The results of fluorescence titration showed that probes 4a and 4b could achieve on-off response to uridine monophosphate (UMP), and had good selectivity and sensitivity. The detection limit of probe 4b for UMP could reach 3.41×10^–8 mol/L. The recognition mechanism of the probe 4b was studied by Jobʼs curve and ¹H NMR titration.

Key words: carborane, benzimidazole, recognition, fluorescence quenching, uridine monophosphate

引用此文

林炳涵, 卓继斌, 林彩霞, 高勇, 袁耀锋. 碳硼烷基苯并咪唑鎓环蕃的合成及核苷酸识别性质研究[J]. 有机化学, 2022, 42(8): 2551-2558.

Binghan Lin, Jibin Zhuo, Caixia Lin, Yong Gao, Yaofeng Yuan. Synthesis and Nucleotide Recognition Properties of Carborane-Based Benzoimidazolium Cyclophane[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2551-2558.

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

分享此文

图/表 8

图式1. 探针4a和4b的合成路线

Scheme 1. Synthesis of probes 4a and 4b

图1. 不同核苷酸(100 μmol/L)存在下探针4a和4b (10 μmol/L)的荧光发射谱图(a, b); 在没有和存在单磷酸核苷酸(100 μmol/L)的情况下4a和4b (10 μmol/L)在最大发射波长367nm处的荧光强度对比图(c, d)

Figure 1. Fluorescence emission spectra of probes 4a and 4b (10 μmol/L) in the presence of different nucleotdes (100 μmol/L) (a, b); Comparison of fluorescence intensity of 4a and 4b (10 μmol/L) at the maximum emission wavelength of 367 nm in the absence and presence of single nucleotides (100 μmol/L) (c, d)

图2. (a)不同浓度的UMP (100 μmol/L)加入到探针4a溶液(10 μmol/L)中的荧光发射谱图(插图: 4a与UMP络合的B-H方程和254 nm下的荧光淬灭); (b)不同浓度的UMP (80 μmol/L)加入到探针4b溶液(10 μmol/L)中的荧光发射谱图(插图: 4b与UMP络合的B-H方程和254 nm下的荧光淬灭)

Figure 2. (a) Fluorescence emission spectra of different concentration of UMP (100 μmol/L) added to the solution of probe 4a (10 μmol/L) (Inset: the B-H equation of 4a complexed with UMP and fluorescence quenching exposed to 254 nm light); (b) Fluorescence emission spectra of different concentration of UMP (80 μmol/L) added to the solution of probe 4b (10 μmol/L) (Inset: the B-H equation of 4b complexed with UMP and fluorescence quenching exposed to 254 nm light)

图3. (a)不同单磷酸核苷酸或阴离子存在下探针4a对UMP识别的抗干扰能力; (b)不同单磷酸核苷酸或阴离子存在下探针4b对UMP识别的抗干扰能力

Figure 3. (a) Anti-interference ability of probe 4a to UMP in the presence of different monophosphate nucleotides or anions; (b) anti-interference ability of probe 4b to UMP in the presence of different monophosphate nucleotides or anions

图4. 探针4a和4b与UMP作用的Job’s曲线

Figure 4. Job’s plot between the probe 4a or 4b and UMP

图5. 不同浓度的UMP加入到4b溶液中的核磁变化谱图

Figure 5. 1H NMR spectra of different concentration of UMP added to 4b solution

Scheme 2. 探针4b与UMP作用机理图

Scheme 2. Proposed mechanism of probe 4b interacted with UMP

主体	客体	K/(L•mol^–1)	检测限/(mol•L^–1)
4a	UMP	2.87×10³	7.62×10^–7
4b	UMP	2.81×10⁴	3.41×10^–8

表1. 探针4a和4b对UMP的识别性能

Table1. Recognition performance of probes 4a and 4b for UMP

参考文献 16

[1]	Gella, A.; Ponce, J.; Cusso, R. and Durany, N. J. Physiol. Biochem. 2008, 64, 9. doi: 10.1007/BF03168230 pmid: 18663991
[2]	Zhang, L. M.; Guo, L. E.; Li, X. M.; Shi, Y. G.; Wu, G. F.; Xie, X. G.; Zhou, Y.; Zhao, Q. H.; Zhang, J. F. Tetrahedron Lett. 2014, 55, 6131. doi: 10.1016/j.tetlet.2014.09.074
[3]	Tumir, L. M.; Grabar, M.; Tomic, S.; Piantanida, I. Tetrahedron 2010, 66, 2501. doi: 10.1016/j.tet.2010.01.063
[4]	(a) Olivari, M.; Montis, R.; Karagiannidis, L. E.; Horton, P. N.; Mapp, L. K.; Coles, S. J.; Light, M. E.; Gale, P. A.; Caltagirone, C. Dalton Trans. 2015, 44, 2138. doi: 10.1039/C4DT02893G pmid: 26207611
	(b) Qiao, B.; Sengupta, A.; Liu, Y.; McDonald, K. P.; Pink, M.; Anderson, J. R.; Raghavachari, K.; Flood, A. H. J. Am. Chem. Soc. 2015, 137, 9746. doi: 10.1021/jacs.5b05839 pmid: 26207611
	(c) Toure, M.; Charles, L.; Chendo, C.; Viel, S.; Chuzel, O.; Parrain, J. L. Chem.-Eur. J. 2016, 22, 8937. doi: 10.1002/chem.201601174 pmid: 26207611
[5]	(a) Lin, J. H.; Tseng, W. B.; Lin, K. C.; Lee, C. Y.; Chandirasekar, S.; Tseng, W. L.; Hsieh, M. M. ACS Sensors 2016, 1, 1132. doi: 10.1021/acssensors.6b00425
	(b) Lu, S. H.; Phang, R. P.; Fang, J. M. Org. Lett. 2016, 18, 1724. doi: 10.1021/acs.orglett.6b00311
[6]	Li, X. Y.; Zhao, Z. X.; Hu, L. H.; Wei, D. C.; Liu, Q. X. Chin. J. Org. Chem. 2021, 41, 3608. (in Chinese) doi: 10.6023/cjoc202103011
	(李芯颖, 赵志翔, 胡林海, 魏登澈, 柳清湘, 有机化学, 2021, 41, 3608 ) doi: 10.6023/cjoc202103011
[7]	Zhou, J.; Yuan, Y. F.; Zhuo, J. B.; Lin, C. X. Tetrahedron Lett. 2018, 59, 1059.
[8]	Fuentes, I.; Garcia-Mendiola, T.; Sato, S.; Pita, M.; Nakamura, H.; Lorenzo, E.; Teixidor, F.; Marques, F.; Vinas, C. Chem.-Eur. J. 2018, 24, 17239. doi: 10.1002/chem.201803178 pmid: 30222214
[9]	Ahmed, N.; Shirinfar, B.; Youn, I. S.; Bist, A.; Suresh, V.; Kim, K. S. Chem. Commun. 2012, 48, 2662. doi: 10.1039/c2cc17145g
[10]	Liu, K.; Zhang, J.; Xu, L.; Liu, J.; Ding, L. P.; Liu, T. H.; Fang, Y. Chem. Commun. 2019, 55, 12679. doi: 10.1039/C9CC06771J
[11]	Cao.; Xinxin Zhao.; Wenge Yang. Dyes Pigm. 2019, 160, 48. (a) Huace Sheng.; Yonghong Hu.; Yi Zhou.; Shimin Fan.; Yang Cao.; Xinxin Zhao.; Wenge Yang. Dyes Pigm. 2019, 160, 48. doi: 10.1016/j.dyepig.2018.07.036
	(b) Dai, Y. P.; Xu, K. X.; Wang, C. Y.; Liu, X. Y.; Wang, P. Supramol. Chem. 2017, 29, 315. doi: 10.1080/10610278.2016.1228935
	(c) Wang, P.; Fu, J. X.; Yao, K.; Chang, Y. X.; Xu, K. X.; Xu, Y. Q. Sens. Actuators, B 2018, 273, 1070. doi: 10.1016/j.snb.2018.07.028
[12]	(a) Dai, Y. P.; Xu, K. X.; Wang, C. Y.; Liu, X. Y.; Wang, P. Supramol. Chem. 2017, 29, 315. doi: 10.1080/10610278.2016.1228935
	(b) Wang, P.; Fu, J. X.; Yao, K.; Chang, Y. X.; Xu, K. X.; Xu, Y. Q. Sens. Actuators, B 2018, 273, 1070. doi: 10.1016/j.snb.2018.07.028
[13]	Bitter, I.; Torok, Z.; Csokai, V.; Grun, A.; Balazs, B.; Toth, G.; Keseru, G. M.; Kovari, Z.; Czugler, M. Eur. J. Org. Chem. 2001, 2001, 2861. doi: 10.1002/1099-0690(200108)2001:15＜2861::AID-EJOC2861＞3.0.CO;2-S
[14]	(a) Adam, A.; Haberhauer, G. Chem.-Eur. J. 2017, 23, 12190. doi: 10.1002/chem.201701096 pmid: 16018672
	(b) Hausner, S. H.; Striley, C. A. F.; Krause-Bauer, J. A.; Zimmer, H. J. Org. Chem. 2005, 70, 5804. pmid: 16018672
[15]	Wang, J. C.; Yuan, Y. F.; Zhuo, J. B.; Yang, S. H.; Lin, F. Chem. J. Chin. Univ. 2018, 39, 889. (in Chinese)
	(王吉成, 袁耀锋, 卓继斌, 杨思涵, 林芬, 高等学校化学学报, 2018, 39, 889.)
[16]	Dong, L. R.; Wang, S. Y.; Zhang, X. M.; Cheng, J. J.; Yuan, Y. F. Chem. J. Chin. Univ. 2019, 40, 927. (in Chinese)
	(董丽蓉, 王思雨, 张小媚, 成佳佳, 袁耀锋, 高等学校化学学报, 2019, 40, 927.)