title: Switchable enantioseparation based on macromolecular memory of a helical polyacetylene in the solid state.
abstract: In the chromatographic separation of enantiomers the order of elution is determined by the strength of diasteromeric interactions between the components of the mixture and a chiral stationary phase. For analytical purposes, it is ideal to have the minor component elute first, whereas in the preparative mode a faster elution of the major component is desirable. Here we describe a stationary phase constructed from a polyacetylene that bears 2,2'-bisphenol-derived side chains in which chirality can be switched in the solid state prior to use. Both the macromolecular helicity of the polymer backbone and the axial chirality of the side chains can be switched in the solid state by interaction with a chiral alcohol, but importantly are maintained after removal of the chiral alcohol because of a memory effect. The chiral stationary phase thus prepared was used to separate the enantiomers of trans-stilbene oxide with the enantiomer elution order determined by the preseparation treatment.
authors.affiliation: Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
authors.forename: Kouhei
authors.initials: K
authors.lastname: Shimomura
authors.affiliation: Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
authors.forename: Tomoyuki
authors.initials: T
authors.lastname: Ikai
authors.affiliation: Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
authors.forename: Shigeyoshi
authors.initials: S
authors.lastname: Kanoh
authors.affiliation: Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan.
authors.forename: Eiji
authors.initials: E
authors.lastname: Yashima
authors.affiliation: Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
authors.forename: Katsuhiro
authors.initials: K
authors.lastname: Maeda
mesh_terms: D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010636:Phenols / Q000737:chemistry; D053279:Polyynes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013267:Stilbenes / Q000737:chemistry* / Q000302:isolation & purification*
chemical_list: D046911:Macromolecular Substances; D010636:Phenols; D013267:Stilbenes; D053279:Polyynes; C025906:stilbene oxide
references.citation: J Am Chem Soc. 2001 Dec 19;123(50):12700-1
references.pmid: 11741444
references.citation: J Am Chem Soc. 2005 Jan 19;127(2):534-5
references.pmid: 15643872
references.citation: Acc Chem Res. 2008 Dec;41(12):1641-52
references.pmid: 18605742
references.citation: Chem Rev. 2001 Dec;101(12):4013-38
references.pmid: 11740925
references.citation: Angew Chem Int Ed Engl. 2008;47(51):9879-82
references.pmid: 19016279
references.citation: J Am Chem Soc. 2013 Jul 17;135(28):10282-5
references.pmid: 23808906
references.citation: J Pharm Biomed Anal. 2002 Jan 15;27(3-4):401-7
references.pmid: 11755741
references.citation: Chem Asian J. 2008 Mar 7;3(3):614-624
references.pmid: 18278780
references.citation: J Am Chem Soc. 2010 Dec 1;132(47):16753-5
references.pmid: 21053898
references.citation: Angew Chem Int Ed Engl. 2006 Feb 13;45(8):1245-8
references.pmid: 16411264
references.citation: Angew Chem Int Ed Engl. 1999 Nov 2;38(21):3138-3154
references.pmid: 10556885
references.citation: J Am Chem Soc. 2008 Sep 17;130(37):12266-7
references.pmid: 18722436
references.citation: J Am Chem Soc. 2005 Apr 13;127(14):5018-9
references.pmid: 15810826
references.citation: J Am Chem Soc. 2007 Sep 12;129(36):10992-3
references.pmid: 17705489
references.citation: Acc Chem Res. 2005 Sep;38(9):745-54
references.pmid: 16171317
references.citation: Angew Chem Int Ed Engl. 2005 Apr 8;44(15):2275-9
references.pmid: 15812796
references.citation: Chem Rev. 2001 Dec;101(12):3893-4012
references.pmid: 11740924
references.citation: J Am Chem Soc. 2013 Jan 9;135(1):114-7
references.pmid: 23252447
references.citation: J Am Chem Soc. 2006 May 3;128(17):5650-1
references.pmid: 16637628
references.citation: J Am Chem Soc. 2004 Apr 7;126(13):4329-42
references.pmid: 15053623
references.citation: Chem Rev. 2009 Nov;109(11):6102-211
references.pmid: 19905011
references.citation: Nature. 2000 Nov 9;408(6809):181-4
references.pmid: 11089967
references.citation: Chem Rev. 2001 Dec;101(12):4039-70
references.pmid: 11740926