Chiral Metal-organic Framework{[Co(L-trp)(bpe)(H2O)]·H2O·NO3}n Used for High Performance Liquid Chromatographic Separation†

doi:10.7503/cjcu20120521

Abstract

Abstract:

A homochiral MOF {[Co(L-trp)(bpe)(H₂O)]·H₂O·NO₃}_n[L-trp=L-tryptophan, bpe=1,2-bis(4-pyridyl)ethylene] with 2D chiral layers was synthesized and used as a new chiral stationary phase for high-performance liquid chromatographic enantioseparation in this study. The chiral MOFs was characterized by powder X-ray diffraction(XRD) and scanning electron microscope(SEM). The experimental results showed that 3 isomers and 11 recemates were separated on {[Co(L-trp)(bpe)(H₂O)]·H₂O·NO₃}_n packed column. The chiral column also exhibited good reproducibility and stability.

Key words: Metal-organic framework, High-performance liquid chromatography, Chiral enantioseparation

CLC Number:

O657.7

TrendMD:

NONG Ruiyu, KONG Jiao, ZHANG Junhui, CHEN Ling, TANG Bo, XIE Shengming, YUAN Liming. Chiral Metal-organic Framework{[Co(L-trp)(bpe)(H₂O)]·H₂O·NO₃}_n Used for High Performance Liquid Chromatographic Separation^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 19.

Figures/Tables 8

Fig.1 Molecular structures of the positional isomers and racemates

Fig.2 XRD patterns of Co-MOF^a. Simulated; b. as-synthesized; c. after HPLC measurement for more than 60 d.

Fig.3 SEM image of the prepared Co-Trp-MOF

Table 1 Separations of the positional isomers on the Co-Trp-MOF-column

Positional isomer	Mobile phase V(Hexane)/V(Isopropanol)	Retention factor, k'			Separation factor, α
Positional isomer	Mobile phase V(Hexane)/V(Isopropanol)	o-			m-	p-
o,m,p-Nitroaniline	9∶1	1.75	2.07	5.60	1.11(m-/o-)	2.15(p-/m-)
o,m,p-Phenylenediamine	98∶2	0.97	1.11	7.39	1.12(m-/o-)	3.47(p-/m-)
o,m,p-Benzenediol	98∶2	2.02	1.03	3.77	2.87(o-/m-)	1.96(p-/o-)

Fig.4 HPLC chromatograms on the packed Co-Trp-MOF-column(250 mm×2.0 mm i.d.) for the separation of positional isomers^(A) o,m,p-Nitroaniline; (B) o,m,p-phenylenediamine; (C) o,m,p-benzenediol. Mobile phase: hexane and isopropanol; flow rate: 0.1 mL/min; UV: 254 nm.

Table 2 Separations of racemates on columns Aa, Bb, Cc and Dd

Racemate	Mobile phase V(Hexane)/V(Isopropanol)	Retention factor, k	Separation factor, α
Racemate	Mobile phase V(Hexane)/V(Isopropanol)	Retention factor, k	Column A	Column B	Column C	Column D
3-Benzylexy-1,2-propanediol	98∶2	1.07	4.68	3.72	1.36	2.69
3,5-Dinitro-N-(1-phenylethyl)benzamide	95∶5	5.08	1.66	1.49		2.26
Propranolol hydrochloride	95∶5	0.84	1.38
1-(9-Anthryl)-2,2,2-trifluoroethanol	90∶10	1.01	1.37		2.60
Pindolol	90∶10	0.78	1.47
DNB-(R,S)-Leucine	90∶10	0.82	2.12
Hydrobenzoin	80∶10	1.02	1.77	1.62
Warfarin sodium	80∶10	4.36	1.74	1.35
Omeprazole	80∶20	2.26	1.85
Chlorpheniramine maleate	80∶20	1.27	1.58
Alprenolol	80∶20	1.28	2.69

Fig.5 HPLC chromatograms on the Co-Trp-MOF-column(250 mm× 2.0 mm i.d.) for the separation of racemates^(A) 3,5-Dinitro-N-(1-phenylethyl)benzamide; (B) 1-(9-anthryl)-2,2,2-trifluoroethanol; (C) hydrobenzoin; (D) pindolol; (E) 3-benzylexy-1,2-propanediol; (F) warfarin sodium; (G) omeprazole; (H) chlorpheniramine maleate; (I) alprenolol. Mobile phase: hexane and isopropanol(Table 2); flow rate: 0.1 mL/min; UV: 254 nm.

Fig.6 Structure of {[Co(L-trp)(bpe)(H2O)]·H2O·NO3}n^(A) 1D chiral chain having L-trp units arranged in a syn-anti mode; (B) 2D homochiral metal-tryptophanate coordination (4,4)-layer structure along the a axis.

References 29

[1]	Wei W. Y., Fang J., Kong H. N., Han J. Y., Chang H. Y., Progress in Chemistry, 2005, 17(6), 1110—1114
	(魏文英, 方键, 孔海宁, 韩金玉, 常贺英. 化学进展, 2005, 17(6), 1110—1114)
[2]	Xie S.M., Yuan L. M.,Progress in Chemistry, 2013, 25(10), 1763—1770
	(谢生明, 袁黎明. 化学进展, 2013, 25(10), 1763—1770)
[3]	Ma S. Q., Sun D. F., Simmons J. M., Collier C. D., Yuan D. Q., Zhou H. C., J. Am. Chem. Soc., 2008, 130(3), 1012—1016
[4]	Allendorf M. D., Houk R. J. T., Andruszkiewicz L., Talin A. A., Pikarsky J., Choudhury A., Gall K. A., Hesketh P. J., J. Am. Chem. Soc., 2008, 130(44), 14404—14405
[5]	Yang C. X., Chen Y. J., Wang H. F., Yan X. P., Chem. Eur. J., 2011, 17(42), 1734—11737
[6]	Liu S. S., Yang C. X., Wang S. W., Yan X. P., Analyst,2012, 137(4), 816—818
[7]	Fu Y. Y., Yang C. X., Yan X. P., J. Chromatogr. A, 2013, 1274, 137—144
[8]	Yang B. C., Jiang Y. D., Qin X. J., Chen Z. L., Ren F., Chem. J. Chinese Universities, 2012, 33(1), 26—31
	(杨宝春, 姜耀东, 秦雪娟, 陈志良, 任非. 高等学校化学学报, 2012, 33(1), 26—31)
[9]	Li Z. Q., Wang A., Guo C. Y., Hu W. N., Tai Y. F., Chem. J. Chinese Universities, 2013, 34(11), 2470—2477
	(李宗群, 汪艾, 郭春燕, 胡文娜, 邰燕芳. 高等学校化学学报, 2013, 34(11), 2470—2477)
[10]	Aijaz A., Akita T., Tsumori N., Xu Q., J. Am. Chem. Soc., 2013, 135(44), 6356—16359
[11]	Li Y. X., Xue M., Guo L. J., Huang L., Chen S. R., Qiu S. L., Chem. Res. Chinese Universities, 2013, 29(2), 196—200
[12]	Yang C. X., Yan X. P., Chin. J. Anal. Chem., 2013, 41(9), 1297—1301
	(杨成雄, 严秀平. 分析化学, 2013, 41(9), 1297—1301)
[13]	Cheng B. P., Li L. S., Zhou R. D., Li L., Zhang H. F., Chem. J. Chinese Universities, 2015, 36(5), 872—880
	(程彪平, 李来生, 周仁丹, 李良, 张宏福. 高等学校化学学报, , 2015, 36(5), 872—880
[14]	Ezuhara T., Endo K., Aoyama Y., J. Am. Chem. Soc., 1999, 121, 3279—3283
[15]	Chelucci G., Thummel R. P., Chem. Rev., 2002, 102, 3129—3170
[16]	Bu X. H., Tong M. L., Kitagawa H. C. S., Batten S. R., Angew. Chem. Int. Ed., 2004, 43, 192—195
[17]	Cai Y. G., Bernasek S. L., Phys J. Chem. B, 2005, 109(10), 4514—4519
[18]	Dybtsev D. N., Nuzhdin A. L., Chun H., Bryliakov K. P., Talsi E. P., Fedin V. P., Kim K., Angew. Chem. Int. Ed., 2006, 45(6), 916—920
[19]	Zhang J., Chen S. M., Wu T., Feng P., Bu X. H., J. Am. Chem. Soc., 2008, 130, 12882—12883
[20]	Ma L. Q., Abney C., Lin W. B., Chem. Soc. Rev., 2009, 38(5), 1248—1256
[21]	Jiang W. J., Babarao R., Hu Z. Q., Chem. Soc. Rev., 2011, 40(7), 3599—3612
[22]	Nuzhdin A. L., Dybtsev D. N., Bryliakov K. P., Talsi E. P., Fedin V. P., J. Am. Chem. Soc., 2007, 129, 12958—12959
[23]	Padmanaban M., Muller P., Lieder C., Gedrich K., Grunker R., Bon V., Senkovska I., Baumgartner S., Opelt S., Paasch S., Brunner E., Glorius F., Klemm E., Kaskel S., Chem. Commun., 2011, 47, 12089—12091
[24]	Tanaka K., Muraoka T., Hirayama D., Ohnish A., Chem. Commun., 2012, 48, 8577—8579
[25]	Kuang X., Ma Y., Su H., Zhang J., Dong Y. B., Tang B., Anal. Chem., 2014, 86, 1277—1281
[26]	Zhang M., Pu Z. J., Chen X. L., Gong X. L., Zhu A. X., Yuan L. M., Chem. Commun., 2013, 49(45), 5201—5203
[27]	Zhang M., Zhang J. H., Zhang Y., Wang B. J., Xie S. M., Yuan L. M., J. Chromatogr. A, 2014, 1325, 163—170
[28]	Kong J., Zhang M., Duan A. H., Zhang J. H., Yang R., Yuan L. M., J. Sep. Sci., 2015, 38, 556—561
[29]	Mendiratta S., Usman M., Luo T. T., Chang B. C., Lee S. F., Lin Y. C., Lu K. L., Cryst. Growth Des., 2014, 14, 1572—1579

Chiral Metal-organic Framework{[Co(L-trp)(bpe)(H₂O)]·H₂O·NO₃}_n Used for High Performance Liquid Chromatographic Separation^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 29

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHAO Yingzhe, ZHANG Jianling. Applications of Metal-organic Framework-based Material in Carbon Dioxide Photocatalytic Conversion [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220223.
[2]	LU Cong, LI Zhenhua, LIU Jinlu, HUA Jia, LI Guanghua, SHI Zhan, FENG Shouhua. Synthesis， Structure and Fluorescence Detection Properties of a New Lanthanide Metal-Organic Framework Material [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220037.
[3]	TIAN Xueqin, MO Zheng, DING Xin, WU Pengyan, WANG Yu, WANG Jian. A Squaramide-containing Luminescent Metal-organic Framework as a High Selective Sensor for Histidine [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210589.
[4]	XING Peiqi, LU Tong, LI Guanghua, WANG Liyan. Controllable Syntheses of Two Cd（II） Metal-organic Frameworks Possessing Related Structures [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220218.
[5]	HAN Zongsu, YU Xiaoyong, MIN Hui, SHI Wei, CHENG Peng. A Rare Earth Metal-Organic Framework with H₆TTAB Ligand [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210342.
[6]	MO Zongwen, ZHANG Xuewen, ZHOU Haolong, ZHOU Dongdong, ZHANG Jiepeng. Guest-responses of A Porous Coordination Polymer Based on Synergistic Hydrogen Bonds [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210576.
[7]	LIU Xueguang, YANG Xiaoshan, MA Jingjing, LIU Weisheng. Separating Methyl Blue Selectively from the Mixture of Dyes by Europium Metal-organic Frameworks [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210715.
[8]	SHI Xiaofan, ZHU Jian, BAI Tianyu, FU Zixuan, ZHANG Jijie, BU Xianhe. Research Status and Progress of MOFs with Application in Photoelectrochemical Water-splitting [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210613.
[9]	WU Ji, ZHANG Hao, LUO Yuhui, GENG Wuyue, LAN Yaqian. A Microporous Cationic Ga（III）-MOF with Fluorescence Properties for Selective sensing Fe³⁺ Ion and Nitroaromatic Compounds [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210617.
[10]	LI Wen, QIAO Junyi, LIU Xinyao, LIU Yunling. Zirconium-based Metal-Organic Framework with Naphthalene for Fluorescent Detection of Nitroaromatic Explosives in Water [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210654.
[11]	WANG Jie, HUO Haiyan, WANG Yang, ZHANG Zhong, LIU Shuxia. General Strategy for In situ Synthesis of NENU-n Series Polyoxometalate-based MOFs on Copper Foil [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210557.
[12]	LI Shurong, WANG Lin, CHEN Yuzhen, JIANG Hailong. Research Progress of Metal⁃organic Frameworks on Liquid Phase Catalytic Chemical Hydrogen Production [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210575.
[13]	ZHANG Chi, SUN Fuxing, ZHU Guangshan. Synthesis， N₂ Adsorption and Mixed-matrix Membrane Performance of Bimetal Isostructural CAU-21 [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210578.
[14]	SHI Ge, XU Qian, DAI Xiao, ZHANG Jie, SHEN Jun, WAN Xinhua. Effect of Aromatic Substituent on Chiral Recognition of Helical Polyacetylene-based Chiral Stationary Phases for High-Performance Liquid Chromatography [J]. Chem. J. Chinese Universities, 2021, 42(8): 2673.
[15]	ZHAO Yangyang, LIU Qiyong, CHEN Boxin, ZHAO Bin, ZHOU Haimei, LI Xinxin, ZHENG Dan, FENG Fei. Silicon-based Micro Gas Chromatographic Column Using Metal-Organic Framework Material ZIF-8 as Stationary Phase [J]. Chem. J. Chinese Universities, 2021, 42(6): 1736.