Chiral order inorganic mesoporous silica used as stationary phase in gas chromatography

doi:10.3724/SP.J.1123.2019.07032

Abstract

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

CLC Number:

O658

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.

Figures/Tables 8

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)

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.

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

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

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 ℃.

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

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

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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