Tunable Enantioselective Adsorption of the As⁃synthesized Mesoporous Silica Through Chiral Imprinting

doi:10.7503/cjcu20210401

Abstract

Abstract:

Chiral mesoporous silica（CMS） has unique chiral structure and good enantioselective adsorption properties， which can be used for the separation of racemic mixtures. The preparation and applications of the CMS have received many attentions in recent years， while less research has been conducted on the origin for the chiral selective adsorption of the CMS. In this work， CMS was prepared using chiral anionic surfactants as supramolecular templates assisted by co?structure directing method. The enantioselective adsorption of racemic molecules and chirality for the CMS were measured using circular dichroism（CD）， and the effect of mesoporous surface modification with or without co?structure directing agent TMAPS（N?trimethoxysilylpropyl?N， N， N?trimethylammonium chloride） on the adsorption selectivity was compared. As a result， the as?synthesized CMS whose inner surface is grafted with TMAPS induced by supramolecular templates with opposite chirality can produce chiral imprinting with opposite helical arrangement and thus result in opposite adsorption selecti?vity. It has been confirmed that the enantioselective adsorption of the CMS for separating racemic mixtures is mainly caused by the chiral imprinting of TMAPS with helical arrangement grafted on the mesoporous surface. The chiral supramolecular templated TMAPS alignment to produce chiral imprinting is practical for some applications， which can in situ tune the enantioselective adsorption and separation property for the as?synthesized mesoporous materials. This work is thought to widen the applications of the CMS in many areas such as stereoselective recognition， asymmetric catalysis and drug delivery etc.

Key words: Chiral mesoporous silica, Chiral supramolecular template, Enantioselective adsorption, Chiral imprinting, co?Structure directing agent

CLC Number:

O647.3

TrendMD:

SONG Wenyao, ZHOU Zhanglang, YANG Xinli, CHEN Lan, GE Guanglu. Tunable Enantioselective Adsorption of the As⁃synthesized Mesoporous Silica Through Chiral Imprinting[J]. Chem. J. Chinese Universities, 2021, 42(10): 3144.

Figures/Tables 6

References 37

1	Liu K. S.， Tian D. L.， Jiang L.， Modern Inorganic Synthetic Chemistry， Elsevier， Amsterdam， 2017， 687—721
2	Wesley H. B.， Wayne C. G.， Kenyon G. D.， Curr. Top. Med. Chem.， 2011， 11（7）， 760—770
3	Geva M.， Frolow F.， Eisenstein M.， Addadi L.， J. Am. Chem. Soc.， 2003， 125（3）， 696—704
4	Somorjai G. A.， Frei H.， Park J. Y.， J. Am. Chem. Soc.， 2009， 131（46）， 16589—16605
5	Wang X.， Gan H.， Sun T. L.， Su B. L.， Fuchs H.， Vestweber D.， Butz S.， Soft Matter， 2010， 6（16）， 3851—3855
6	Zhou F.， Yuan L.， Li D.， Huang H.， Sun T. L.， Chen H.， Colloids Surf. B， 2012， 90（1）， 97—101
7	El‐Gindi J.， Benson K.， de Cola L.， Galla H. J.， Seda Kehr N.， Angew. Chem. Int. Ed.， 2012， 51（15）， 3716—3720
8	Zhang M. X.， Qing G. Y.， Sun T. L.， Chem. Soc. Rev.， 2012， 41（5）， 1972—1984
9	González⁃Campo A.， Amabilino D. B.， Biochirality，Springer， Berlin， 2013， 109—156
10	He Y. Y.， Li Y.， Li Z. B.， Yang Y. G.， Chem. J. Chinese Universities， 2019， 40（2）， 201—210 （贺洋洋，李艺，李宝宗，杨永刚. 高等学校化学学报，2019， 40（2）， 201—210）
11	Cao Y. Y.， Che S. A.， Chiral Nanomaterials： Preparation， Properties and Applications， Wiley⁃VCH Verlag GmbH & Co.， Weinheim， 2017， 121—177
12	Qiu H. B.， Che S. A.， Chem. Soc. Rev.， 2011， 40（3）， 1259—1268
13	Guo Y. Y.， Wu L. L.， Gou K. J.， Wang Y. M.， Hu B. C.， Pang Y.， Li S. M.， Li H. R.， Micropor. Mesopor. Mater.， 2020， 294（1）， 109862
14	Che S. A.， Liu Z.， Ohsuna T.， Sakamoto K.， Terasaki O.， Tatsumi T.， Nature， 2004， 429（6989）， 281—284
15	Wang Y.， Han L.， Che S. A.， Chem. J. Chinese Universities， 2011， 32（3）， 560—570 （王玉，韩璐，车顺爱. 高等学校化学学报， 2011， 32（3）， 560—570）
16	Gou K. J.， Wang Y. M.， Xie L. L.， Guo X. M.， Guo Y. Y.， Ke J.， Wu L. L.， Li S. M.， Li H. R.， Chem. Eng. J.， 2020， 421（2）， 127862
17	Care A.， Bergquist P. L.， Sunna A.， Trends Biotechnol.， 2015， 33（5）， 259—268
18	Paik P.， Gedanken A.， Mastai Y.， Micropor. Mesopor. Mater.， 2010， 129（1/2）， 82—89
19	Su M. X.， Liu Z. Y.， Chen J. L.， Cheng L. F.， Li B.， Yan F.， Di B.， RSC Adv.， 2014， 4（98）， 54998—55002
20	Di B.， Cheng L. F.， Jiang Q. L.， Su M. X.， Hao W. Q.， New J. Chem.， 2013， 37（5）， 1603—1609
21	Che S. A.， Garcia⁃Bennett A. E.， Yokoi T.， Sakamoto K.， Kunieda H.， Terasaki O.， Tatsumi T.， Nat. Mater.， 2003， 2（12）， 801—805
22	Ng E. P.， Bahaman N.， Mukti R. R.， Ling T. C.， Ng Y. H.， Adam F.， Mater. Res. Bull.， 2015， 62， 192—199
23	Min L.， Li T.， Tan Q.， Tan X. P.， Pan W.， He L.， Zhang J.， Ou E. C.， Xu W. J.， Dalton Trans.， 2016， 45（18）， 7912—7920
24	Yokoi T.， Yamataka Y.， Ara Y.， Sato S.， Kubota Y.， Tatsumi T.， Micropor. Mesopor. Mater.， 2007， 103（1—3）， 20—28
25	Han L.， Che S. A.， Chem. Soc. Rev.， 2013， 42（9）， 3740—3752
26	Xie J. J.， Duan Y. Y.， Che S. A.， Adv. Funct. Mater.， 2012， 22（18）， 3784—3792
27	Huang Y.， Vidal X.， Garcia‐Bennett A. E.， Angew. Chem. Int. Ed.， 2019， 58（32）， 10859—10862
28	Huang Y.， Garcia⁃Bennett A. E.， Molecules， 2021， 26（2）， 338
29	Wan Y.， Zhao D. Y.， Chem. Rev.， 2007， 107（7）， 2821—2860
30	Zhou Z. L.， Zhou J.， Chen L.， Zhao Q.， Zhang C.， Ge G. L.， ChemComm， 2020， 56（97）， 15345—15348
31	Jin H.， Wang L.， Bing N.， Mater. Chem. Phys.， 2011， 127（1/2）， 409—412
32	Wu X. W.， Jin H. Y.， Liu Z.， Ohsuna T.， Terasaki O.， Sakamoto K.， Che S. A.， Chem. Mater.， 2006， 18（2）， 241—243
33	Ravikovitch P. I.， Vishnyakov A.， Neimark A. V.， Ribeiro Carrott M. M.， Russo P. A.， Carrott P. J.， Langmuir， 2006， 22（2）， 513—516
34	Xavier V.， Ivan F.， Alex F. B.， Gabriel M.， Applied Physics Letters， 2015， 107（21）， 211107
35	Guo Y. Y.， Gou K. J.， Yang B. X.， Wang Y. M.， Pu X. Y.， Li S. M.， Li H. R.， Molecules， 2019， 24（19）， 3552
36	Wang X.， Li C.， Fan N.， Li J.， Zhang H. T.， Shang L.， He Z. G.， Sun J.， Asian J. Pharm.， 2019， 14（4）， 405—412
37	Li J.， Xu L.， Yang B. X.， Wang H. Y.， Bao Z. H.， Pan W. S.， Li S. M.， Int. J. Pharm.， 2015， 492（1/2）， 191—198

Adsorbent	Adsorbate	Adsorption capacity/（mg·g^-1）	Enantioselective adsorption factor
L?CMS	L?Ala	135	1.35
	D?Ala	100
D?CMS	D?Ala	127	1.34
	L?Ala	94.5

Adsorbent	Adsorbate	Adsorption capacity/（mg·g^-1）	Enantioselective adsorption factor
L?CMS	L?Ala	135	1.35
	D?Ala	100
D?CMS	D?Ala	127	1.34
	L?Ala	94.5

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