Biomimetic Mineralization at a Dilute Concentration and Application in Enantioseparation†

doi:10.7503/cjcu20180394

Abstract

Abstract:

The morphologies and pore architectures of silicas were controlled by tuning the pH value, aging time and the concentration of tetraethoxysilane(TEOS) using the self-assemblies of an L-phenylalanine derivative(L-18Phe6PyBr) at a concentration of 0.30 mmol/L. The obtained samples were characterized using field-emission scanning electron microscopy and transmission electron microscopy. The results indicated that left-handed twisted nanoribbons were obtained at pH=10.01, while straight nanoribbons were obtained at pH=7.15 and 12.34. The increasing of the aging time was beneficial to the formation of straight nanoribbons which should follow a dynamic templating approach. With increasing the mass ratio of TEOS/L-18Phe6PyBr from 2:1 to 15:1, the width of the twisted nanoribbons increased and the helical pitch became longer. Silica tubular nanoribbons were obtained after removing the organic template by calcination. Silica prepared from TEOS/L-18Phe6PyBr(2:1, mass ratio) was used as the stationary phase of the gas chromatography for enantioseparation. The results indicated that 1-phenyl-1-propanol, 1-(4-chlorophenyl)ethanol and 2-methylpentanoic acid enantiomers were able to be separated. Chiral supramolecular imprinting was proposed to drive this enantiosepartion ability of the silica. The results not only gave us a better understanding of the cooperation self-assembly behavior of the silica oligomer and the low-molecular-weight gelator, but also brought out a chiral inorganic stationary phase for enantioseparation.

Key words: Self-assembly, Biomimetic mineralization, Silica, Enantioseparation, Gas chromatography

CLC Number:

O631

TrendMD:

HE Yangyang,LI Yi,LI Baozong,YANG Yonggang. Biomimetic Mineralization at a Dilute Concentration and Application in Enantioseparation^†[J]. Chem. J. Chinese Universities, 2019, 40(2): 393.

Figures/Tables 10

Fig.1 Molecular structure of L-18Phe6PyBr

Fig.2 FE-SEM images of the samples prepared at different L-18Phe6PyBr concentrationsc(L-18Phe6PyBr)/(mmol·L-1): (A) 0.074; (B) 0.15; (C) 0.30; (D) 0.74.

Fig.3 FE-SEM images of the samples prepared at different pH values after 7 d(A—C) and 6 months(D—F)pH: (A, D) 7.15; (B, E) 10.01; (C, F) 12.34.

Fig.4 FE-SEM and TEM images of the samples prepared at different TEOS/L-18Phe6PyBr ratios before(A—H) and after(I—P) calcinationm(TEOS)/m(L-18Phe6PyBr): (A, E, I, M) 2:1; (B, F, J, N) 6:1; (C, G, K, O) 9:1; (D, H, L, P) 15:1.

Fig.5 WAXRD patterns of samples prepared at different TEOS/L-18Phe6PyBr ratios before(A) and after(B) template removal by calcinationm(TEOS):m(L-18Phe6PyBr): a. 2:1; b. 6:1; c. 9:1; d. 15:1.

Fig.6 N2 adsorption-desorption measurements of silica prepared at different TEOS/L-18Phe6PyBr ratios(A) Sorption isotherms; (B) BJH pore-size distribution plot from the adsorption branch. m(TEOS):m(L-18Phe6PyBr): a. 2:1; b. 6:1; c. 9:1; d. 15:1.

Fig.7 FE-SEM images of M1 deposited on the inner wall of the capillary column(A) and the thickness of M1 coating in part of the capillary column(B)

Fig.8 GC chromatograms on the M1-coated open tubular column(15 m × 0.25 mm i. d.) using temperature program for the separation of n-alkanes(A) and aromatic hydrocarbon mixture(benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene)(B)(A) 60 ℃ for 0.5 min, the 40 ℃/min to 200 ℃under a N2 linear velocity of 10.6 cm/s;(B) 80 ℃ for 0.5 min, then 60 ℃/min to 200 ℃ under a N2 linear velocity of 10.0 cm/s.

Table 1 Separations of racemates on the M1-coated column*

Racemate	Temperature/℃	$V N 2$ /(cm·s^-1)	α	R
1-Phenyl-1-propanol	180	10.2	1.18	0.93
1-(4-Chlorophenyl) ethanol	200	10.0	1.39	1.07
2-Methylpentanoic acid	180	12.1	1.22	0.94

Table 1 Separations of racemates on the M1-coated column*

Racemate	Temperature/℃	$V N 2$ /(cm·s^-1)	α	R
1-Phenyl-1-propanol	180	10.2	1.18	0.93
1-(4-Chlorophenyl) ethanol	200	10.0	1.39	1.07
2-Methylpentanoic acid	180	12.1	1.22	0.94

Fig.9 GC chromatograms on the M1-coated open tubular column(15 m×0.25 mm i. d.) for the separation of racemates(A) 1-Phenyl-1-propanol at 180 ℃ under a N2 linear velocity of 10.2 cm/s; (B) 1-(4-chlorophenyl) ethanol at 200 ℃ under a N2 linear velocity of 10.0 cm/s; (C) 2-methylpentanoic acid at 180 ℃ under a N2 linear velocity of 12.1 cm/s.

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