title: A comparison of covalent and non-covalent imprinting strategies for the synthesis of stigmasterol imprinted polymers.
abstract: Non-covalent and covalent imprinting strategies have been investigated for the synthesis of stigmasterol imprinted polymers. The synthesized molecularly imprinted polymers (MIPs) were then evaluated for their recognition and selectivity towards stigmasterol via static and dynamic batch-binding assays and their performance measured against control non-imprinted polymers (NIPs). MIPs prepared using the conventional non-covalent imprinting method displayed little to no binding affinity for stigmasterol under various conditions. In contrast, the application of a covalent imprinting approach using the novel post-synthetically cleavable monomer-template composite stigmasteryl-3-O-methacrylate resulted in the fabrication of a MIP that successfully recognized stigmasterol in both organic and partially aqueous environments. The affinity and selectivity of the covalently prepared MIP was enhanced when undertaken in a partially aqueous environment consisting of an acetonitrile/water (9:1, v/v) solvent mixture. These features have been exploited in a molecularly imprinted solid-phase extraction (MISPE) format, wherein the preferential retention of stigmasterol (with an imprint factor of 12) was demonstrated with 99% recovery in comparison to cholesterol (imprint factor of 6) and ergosterol (imprint factor of 4) while in the presence of several closely related steryl analogues.
authors.affiliation: Centre for Green Chemistry, Monash University, Monash 3800 Victoria, Australia.
authors.forename: Shima N N S
authors.initials: SN
authors.lastname: Hashim
authors.affiliation: Centre for Green Chemistry, Monash University, Monash 3800 Victoria, Australia.
authors.forename: Reinhard I
authors.initials: RI
authors.lastname: Boysen
authors.affiliation: Centre for Green Chemistry, Monash University, Monash 3800 Victoria, Australia.
authors.forename: Lachlan J
authors.initials: LJ
authors.lastname: Schwarz
authors.affiliation: Centre for Green Chemistry, Monash University, Monash 3800 Victoria, Australia.
authors.forename: Basil
authors.initials: B
authors.lastname: Danylec
authors.affiliation: Centre for Green Chemistry, Monash University, Monash 3800 Victoria, Australia. Electronic address: milton.hearn@monash.edu.
authors.forename: Milton T W
authors.initials: MT
authors.lastname: Hearn
mesh_terms: D054802:Molecular Imprinting / Q000379:methods*; D011108:Polymers / Q000138:chemical synthesis*; D052616:Solid Phase Extraction / Q000295:instrumentation* / Q000379:methods; D013265:Stigmasterol / Q000737:chemistry* / Q000302:isolation & purification; D014874:Water Pollutants, Chemical / Q000737:chemistry / Q000302:isolation & purification
chemical_list: D011108:Polymers; D014874:Water Pollutants, Chemical; D013265:Stigmasterol
keywords: Covalent and non-covalent imprinting; Molecularly imprinted polymers; Phytosterols; Solid-phase extraction; Stigmasterol