手性有序无机介孔硅用作气相色谱固定相

doi:10.3724/SP.J.1123.2019.07032

摘要/Abstract

摘要：

手性介孔材料在手性分离、不对称催化、手性传感等领域具有广泛的应用价值。手性有序无机介孔硅是一类介孔结构高度有序、不含有机成分的手性材料。该文采用D-苯丙氨酸为手性源合成手性有序无机介孔硅(COIMS),将其用聚硅氧烷(OV-1701)稀释后用作固定相制备毛细管气相色谱手性柱,并对该手性柱的分离性能进行了考察,8种手性化合物在该手性柱上得到了拆分。COIMS柱对直链烷烃、醇的分离也表现出良好的选择性。该柱还具有分析时间短、在较高温度下测定稳定等优点,其具有开发成高温手性固定相的潜力。

关键词: 气相色谱, 手性介孔材料, 固定相, 手性分离

Abstract:

Chiral mesoporous materials have widely applications in chiral separation, asymmetric catalysis, and chiral sensing. Chiral order inorganic mesoporous silica (COIMS) is a kind of chiral materials with high order mesoporous structure not containing organic component. Here we report that a COIMS diluted with a polysiloxane OV-1701 was explored as a novel stationary phase for capillary gas chromatography. The COIMS was synthesized from D-phenylalanine chiral source, and its separation properties of the chiral column were investigated. Eight enantiomers including chiral alcohols, dialcohols, esters and amino acid derivative have been resolved on the coated capillary column. In addition, COIMS chiral column also exhibits good selectivity for the separations of linear alkanes and alcohols. This work indicates that the column has the advantages of high temperature resistance and short analysis time, so it has great potential to develop it as a chiral stationary phase at high temperature.

Key words: gas chromatography (GC), chiral mesoporous materials, stationary phase, chiral separation

中图分类号:

O658

普青, 何宇雨, 袁黎明. 手性有序无机介孔硅用作气相色谱固定相[J]. 色谱, 2020, 38(4): 484-489.

PU Qing, HE Yuyu, YUAN Liming. Chiral order inorganic mesoporous silica used as stationary phase in gas chromatography[J]. Chinese Journal of Chromatography, 2020, 38(4): 484-489.

图/表 8

图1 COIMS的(a)CD图、(b)XRD图和(c)TGA曲线

Fig. 1 (a) Circular dichroism (CD) pattern, (b) small- angle X-ray powder diffraction (SA-XRD) pattern and (c) thermogravimetric analysis (TGA) curve of chiral order inorganic mesoporous silica (COIMS)

图2 COIMS涂敷柱截面以及COIMS的SEM图和TEM图

Fig. 2 SEM and TEM images of the cross-section of COIMS coated column and COIMS a. SEM image of the cross-section of COIMS coated capillary column; b. SEM image of COIMS deposited on the inner wall of the capillary column; c. SEM image of COIMS; d. TEM image of the COIMS.

表1 COIMS涂敷柱在120 ℃下的保留因子及柱效

Table 1 Retention factor and column efficiency of the COIMS coated column at 120 ℃

Content	Column size/(μm×m)	Temperature/ ℃	Retention factor	N₂ linear velocity (cm/s)	n/(plate/m)
n-Dodecane	250×15	120	1.19	16.8	2105

表2 COIMS涂敷柱在120 ℃下的麦氏常数及其平均值

Table 2 McReynolds constants and its average value of the COIMS coated column at 120 ℃

2-Pentanone	1-Nitropropane	Benzene	Pyridine	1-Butanol	Average value
286	635	743	845	848	671

图3 在COIMS涂敷柱上进行的程序升温分离色谱图

Fig. 3 Chromatograms of the separation on COIMS coated column using temperature programs a. n-Alkanes at a N2 linear velocity of 17.2 cm/s using a temperature program: 60 ℃ for 0.5 min, then 40 ℃/min to 150 ℃; b. n-alcohols (C1-OH to C8-OH) at a N2 linear velocity of 16.4 cm/s using a temperature program: 60 ℃ for 1 min, then 60 ℃/min to 180 ℃.

表3 外消旋体化合物在COIMS涂敷柱上的分离

Table 3 Separation of racemates on COIMS coated column

Racemates	T/℃	k	α	R_s	v/(cm/s)
Valine^*	120	1.38	1.62	8.53	13.80
Methionine^#	90	1.12	1.25	1.46	17.60
Tryptophan^#	95	1.03	1.06	0.27	16.80
Threonine^#	100	1.04	1.09	0.29	18.70
1,3-Butanediol	180	1.19	1.28	1.59	12.40
1-Amino-2-propyl alcohol	180	1.02	1.02	0.24	12.80
Dihydrocarvyl acetate	120	1.12	1.23	1.96	16.50
Ethyl lactate	200	1.08	1.14	1.85	15.20

图4 手性化合物在COIMS涂敷柱上的拆分色谱图

Fig. 4 Chromatograms of the separation of chiral compounds on COIMS coated column

图5 COIMS涂敷柱的重现性色谱图

Fig. 5 Reproducible chromatograms on COIMS coated column a. 1,3-butanediol at a N2 linear velocity of 12.4 cm/s under 180 ℃; b. valine derivative at a N2 linear velocity of 13.8 cm/s under 120 ℃. Line 1: the column was first used; lines 2-4: after the column subjected to 100, 200 and more than 300 injections, respectively. +: dextrorotation; -: levogyration.

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