基于Co-BDC-NH2的二维手性金属有机框架纳米片用作气相色谱固定相

doi:10.3724/SP.J.1123.2024.06004

摘要/Abstract

摘要： 二维金属有机框架材料(2D-MOFs)具有易于衍生化、孔隙率高、活性位点充足等特点,目前,鲜有将2D-MOFs应用于色谱分离的研究报道,在气相色谱手性分离分析领域的报道更为罕见。本文通过表面活性剂辅助溶剂热法制备了2D-MOFs纳米片,即Co-BDC-NH₂,采用扫描电子显微镜、X射线粉末衍射对其进行表征。通过后修饰法分别将手性配体甘氨酰-L-天冬氨酸、甘氨酰-L-谷氨酸引入到Co-BDC-NH₂中,得到两种具有手性的2D-MOFs纳米片材料,采用傅里叶红外光谱(FT-IR)、圆二色谱(CD)、热重分析(TGA)对其进行表征。将两种2D-MOFs纳米片材料用作气相色谱手性固定相,采用动态涂覆法分别将其涂覆到石英毛细管柱中,通过扫描电子显微镜分析,确定制备得到两根手性柱,并进行气相色谱分离测试。结果表明:两根色谱柱的理论塔板数各为3538和3108 N/m,柱效优良;两根柱子的麦氏常数依次为181与208,说明两种手性2D-MOFs纳米片是中等极性。两根色谱柱对位置异构体、外消旋化合物(尤其是氨基酸衍生物类)表现出较好的分离能力,其中,Co-BDC-NH₂-甘氨酰-L-天冬氨酸与Co-BDC-NH₂-甘氨酰-L-谷氨酸色谱柱分别对7种与8种外消旋化合物表现出手性识别能力。此外,Co-BDC-NH₂-甘氨酰-L-天冬氨酸色谱柱对正构烷烃混合物、正构醇混合物及Grob试剂也表现出较好的分离效果。本研究在2D-MOFs纳米片上引入了手性功能团,验证其作为气相色谱固定相的可行性,也拓展了其在手性分离分析领域的应用。

关键词: 二维手性金属有机框架纳米片, 手性固定相, 气相色谱, 手性分离

Abstract:

Two-dimensional metal-organic-framework (2D-MOF) materials have emerged as a new class of functional 2D material. Compared to bulk crystals, 2D-MOFs are easily derivatized, highly porous, and have sufficient active sites. While 2D-MOFs are of considerable research interest, they are also efficient candidates for multiple applications in a variety of fields owing to their numerous advantages. The ability to separate and analyze chiral compounds is greatly significant for progressing human society, and chromatographic separation is widely used in this regard owing to its high resolution and sensitivity. Few reports on the use of 2D-MOFs in chromatographic-separation applications currently exist, and those use gas chromatography to analyze and separate enantiomers are even rarer. Unsurprisingly, the development of novel stationary phases has become a popular topic in the chiral-chromatography field. In this study, 2D-MOF nanosheets (Co-BDC-NH₂) were synthesized using a surfactant-assisted solvothermal method. The nanosheets were subsequently characterized by scanning electron microscopy and X-ray diffractometry. MOFs can be post-synthetically modified without affecting their frameworks, and such modifications can lead to the construction of chiral MOFs. Accordingly, Co-BDC-NH₂ was post-synthetically modified with glycyl-L-aspartic acid and glycyl-L-glutamic acid as chiral ligands to afford two chiral 2D-MOF nanosheets, namely Co-BDC-NH₂-glycyl-L-aspartic acid and Co-BDC-NH₂-glycyl-L-glutamic acid. These chiral 2D-MOF nanosheets were characterized by Fourier-transform infrared spectroscopy, circular dichroism, and thermogravimetric analysis. The two 2D-MOF nanosheet materials were used as chiral stationary phases in gas chromatography by coating them onto prepared capillary columns using a dynamic coating method; this process leaves a homogeneous coating layer on the inner wall of the column. Scanning electron microscopy confirmed that the two chiral columns had been successfully prepared. The columns were finally tested through gas-chromatography-separation experiments. Theoretical plates can be used to evaluate column efficiency. The Co-BDC-NH₂-glycyl-L-aspartic acid and Co-BDC-NH₂-glycyl-L-glutamic acid columns were determined to have 3538 and 3108 N/m theoretical plates, respectively, which implies that these columns are highly efficient. The McReynolds constant can be used to determine the polarity of the stationary phase in a chromatographic column; the two capillary columns exhibited McReynolds constants of 181 and 208, consistent with materials of medium polarity. The two chromatographic columns exhibited good abilities to resolve positional isomers and racemates (especially amino-acid derivatives), with seven racemates identified using the Co-BDC-NH₂-glycyl-L-aspartic acid column, and eight identified using the Co-BDC-NH₂-glycyl-L-glutamic acid column. In addition, the former column also separated mixed n-alkanes, mixed n-alcohols, and Grob mixtures. In this study, we augmented 2D-MOF nanosheets with chiral functional groups and confirmed that they are effective stationary phases for use in gas-chromatography applications. The study also expands the applicability of 2D-MOF nanosheets to chiral separation.

Key words: two-dimensional chiral metal-organic-framework nanosheets, chiral stationary phase, gas chromatography (GC), chiral separation

中图分类号:

O658

杨梅芳, 郑康妮, 龙怡幸, 李毅洁, 王雪萍, 章俊辉, 袁黎明. 基于Co-BDC-NH₂的二维手性金属有机框架纳米片用作气相色谱固定相[J]. 色谱, 2025, 43(4): 335-344.

YANG Meifang, ZHENG Kangni, LONG Yixing, LI Yijie, WANG Xueping, ZHANG Junhui, YUAN Liming. Two-dimensional chiral metal-organic-framework nanosheets based on Co-BDC-NH₂ used as stationary phases for gas chromatography[J]. Chinese Journal of Chromatography, 2025, 43(4): 335-344.

图/表 19

图1 Co-BDC-NH2的扫描电镜图

Fig. 1 Scanning electron microscope (SEM) images of Co-BDC-NH2 Co-BDC-NH2: co-2-aminoterephthalic acid.

图2 CMOF1和CMOF2的X射线衍射图谱

Fig. 2 X-ray diffraction patterns of CMOF1 and CMOF2 CMOF1: 2-aminoterephthalic acid-glycyl-L-aspartic acid; CMOF2: 2-aminoterephthalic acid-glycyl-L-glutamic acid.

图3 CMOF1和CMOF2的红外光谱图

Fig. 3 Fourier transform-infrared (FT-IR) spectra of CMOF1 and CMOF2

图4 (a) CMOF1和(b) CMOF2的圆二色谱分析

Fig. 4 Circular dichroism (CD) analysis of (a) CMOF1 and (b) CMOF2

图5 (a) CMOF1和(b) CMOF2的热重分析曲线

Fig. 5 Thermogravimetric analysis (TGA) curves of (a) CMOF1 and (b) CMOF2

图6 (a)空柱、(b) CMOF1色谱柱和(c) CMOF2色谱柱的扫描电镜图

Fig. 6 Scanning electron microscope (SEM) images of (a) empty column, (b) CMOF1 column and (c) CMOF2 column

表1 CMOF1、CMOF2色谱柱的性能

Table 1 Properties of the CMOF1 column and CMOF2 column

Column	Temperature/ ℃	Retention factor (k)	Linear velocity/ (cm/s)	Column efficiency/ (N/m)
CMOF1	120	1.43	14.5	3538
CMOF2	120	1.34	13.3	3108

表2 CMOF1、CMOF2色谱柱的麦氏常数

Table 2 McReynolds constants of the CMOF1 column and CMOF2 column

Column	Benzene	2-Pentanone	1-Butanol	1-Nitropropane	Pyridine	Average polarity
CMOF1	102	157	195	238	211	181
CMOF2	168	179	225	213	254	208

表3 正构烷烃在CMOF1色谱柱上的分离数据

Table 3 Separation data of n-alkanes on the CMOF1 column

n-Alkane	Separation factor (α)^*	Resolution (R_s)^*
n-Hexane	-	-
n-Heptane	1.73	1.52
n-Octane	1.89	2.46
n-Nonane	1.97	3.44
n-Decane	1.72	4.14

表4 正构醇在CMOF1色谱柱上的分离数据

Table 4 Separation data of n-alcohols on the CMOF1 column

n-Alcohol	α
Methanol	-	-
Ethanol	4.28	1.03
1-Propanol	2.36	1.28
1-Butanol	2.34	2.04
1-Pentanol	1.61	1.90
1-Hexanol	1.36	1.90
1-Heptanol	1.24	1.98
1-Octanol	1.29	4.37
1-Nonanol	1.10	1.64

表5 Grob试剂在CMOF1色谱柱上的分离数据

Table 5 Separation data of Grob mixtures on the CMOF1 column

Grob	α	R_s	Grob	α	R_s	Grob	α	R_s
2,3-Butanediol	-	-	2,6-Xylidine	1.21	1.65	Dicyclohexylamine	1.11	1.78
n-Decane	3.66	2.50	2,6-Xylenol	1.10	0.76	Methyl undecanoate	1.09	1.57
n-Undecane	1.98	3.03	1-Nonanal	1.08	0.57	Methyl laurate	1.10	1.33
1-Octanol	1.95	5.79	Methyl caprate	1.06	0.73

表6 位置异构体在CMOF1色谱柱上的分离数据

Table 6 Separation data of positional isomers on the CMOF1 column

Positional isomers	T/℃	k₁	k₂	α₁	α₂	R_s1	R_s2	v/(cm/s)
α,β-Ionone	150	1.26	1.32	1.04	-	0.59	-	13.9
cis-/trans-Citral	125	1.13	1.19	1.05	-	0.62	-	15.6
o,m,p-Nitrobromobenzene	125	0.69	0.81	1.17	1.03	2.31	0.67	12.5

表7 位置异构体在CMOF2色谱柱上的分离数据

Table 7 Separation data of positional isomers on the CMOF2 column

Positional isomers	T/℃	k₁	k₂	α₁	α₂	R_s1	R_s2	v/(cm/s)
α,β-Ionone	128	1.23	1.33	1.08	-	0.89	-	12.6
o,m,p-Dinitrobenzene	135	0.73	0.77	1.06	1.10	0.75	0.97	12.2
o,m,p-Chlorophenol	110	0.86	0.91	1.06	1.53	0.63	2.82	15.1
o,m,p-Nitrobromobenzene	110	0.93	1.12	1.20	1.04	3.52	0.66	14.2

图7 位置异构体在CMOF1柱上的色谱图

Fig. 7 Chromatograms of positional isomers on the CMOF1 column

图8 位置异构体在CMOF2柱上的色谱图

Fig. 8 Chromatograms of positional isomers on the CMOF2 column

表8 外消旋体在CMOF1色谱柱上的分离

Table 8 Separation data of racemates on the CMOF1 column

Racemate	T/℃	k₁	α	R_s	v/(cm/s)
DL-Alanine^a	150	0.72	2.59	4.93	13.0
2-Methylpentanoic acid	178	0.91	1.06	0.79	14.0
2-Methylvaleraldehyde	178	0.90	1.24	1.84	13.1
Menthol	155	1.01	1.09	1.29	15.0
DL-Lysine^a	162	1.25	1.06	0.99	13.5
DL-Methionine^a	172	1.57	1.16	1.15	15.6
Butyl glycidyl ether	133	0.99	1.14	1.67	14.2

图9 外消旋体在CMOF1柱上的色谱图

Fig. 9 Chromatograms of racemates on the CMOF1 column

表9 外消旋体在CMOF2色谱柱上的分离

Table 9 Separation data of racemates on the CMOF2 column

Racemate	T/℃	k₁	α	R_s	v/(cm/s)
Butyl glycidyl ether	110	0.70	2.17	3.92	14.4
1,2-Epoxybutane	100	1.02	1.04	0.58	14.7
Styrene oxide	100	1.29	1.08	0.74	13.9
Methyl phenyl sulfoxide	127	0.76	1.23	1.36	14.1
Menthol	129	0.63	1.73	4.74	14.5
Limonene	150	1.06	1.06	0.71	14.9
DL-Methionine^a	185	1.06	1.13	0.99	13.5
DL-Isoleucine^a	145	0.96	1.11	0.68	15.5

图10 外消旋体在CMOF2柱上的色谱图

Fig. 10 Chromatograms of racemates on the CMOF2 column

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基于Co-BDC-NH₂的二维手性金属有机框架纳米片用作气相色谱固定相

Two-dimensional chiral metal-organic-framework nanosheets based on Co-BDC-NH₂ used as stationary phases for gas chromatography

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