Abstract
Selective cation-exchange membranes are placing a key role in separation processes. The application of selective cation-exchange membranes is wide since there are many kinds of mixtures needed to be separated for reuse. In this study, a facile and efficient one-pot approach was used to obtain monodispersed methyl methacrylate–N-isopropyl acrylamide (MMA–NIPAm) polymer by atom transfer radical precipitation polymerization (ATRPP) and then MMA–NIPAm chiral selective separation membranes were prepared for separating racemic equol. Firstly, using dodecylbenzenesulfonyl chloride (DBSC) as the initiator, bipyridine (bipy)/CuCl as the catalyst system, acetonitrile as the solvent, and S-equol as template molecule by which a MMA–NIPAm copolymer was synthesized and it was characterized by TEM, FTIR, TGA, UV–vis absorption spectrum, and dynamic layer scattering analysis. Lastly, MMA–NIPAm chiral separation membranes were prepared by casting 3 wt% of MMA–NIPAm copolymer dimethyl formamide (DMF) solution on a rimmed glass plate and evaporated the solvent completely at 100 °C under vacuum. Then, the PMMA–PNIPAm chiral selective cation-exchange membranes were prepared by immersing in methanol/acetic acid (95:5, v/v) to remove the template molecules. Most worthy of mention was that the prepared chiral selective separation membranes could separate S-equol and R-equol from the mixture of racemic equol. In application of a thermo-responsive monomer, the separation ability of the prepared PMMA–PNIPAm chiral separation membranes could be tunable according to environment temperature changes.
Similar content being viewed by others
References
Turner R, Baron T, Wolffram S, Minihane AM, Cassidy A, Rimbach G, Weinberg PD (2004) Effect of circulating forms of soy isoflavones on the oxidation of low density lipoprotein. Free Radic Res 382:209–216
Hedlund TE, Johannes WU, Miller GJ (2003) Soy isoflavonoid equol modulates the growth of benign and malignant prostatic epithelial cells in vitro. Prostate 54:68–78
Muthyala RS, Ju YH, Sheng S, Williams LD, Doerge DR, Katzenellenbogen BS, Helferich WG, Katzenellenbogen JA (2004) Equol, a natural estrogenic metabolite from soy isoflavones: convenient preparation and resolution of R- and S-equols and their differing binding and biological activity through estrogen receptors alpha and beta. Bioorg Med Chem 12:1559–1567
Kenny AK, Mangano KM, Abourizk RH, Bruno RS, Anamani DE, Kleppinger AS, Walsh J, Prestwood KM, Kerstetter JE (2009) Soy proteins and isoflavones affect bone mineral density in older women: a randomized controlled trial. Am J Clin Nutr 90:234–242
Alvira E, García JI, Mayoral JA (1998) Molecular modeling study for chiral separation of equol enantiomers by β-cyclodextrin. Chem Phys 240:101–108
Cheong WJ, Yang SH, Ali F (2013) Molecular imprinted polymers for separation science: a review of reviews. J Sep Sci 36:609–628
Firdaous F, Dhulster P, Amiot J, Gaudreau A, Lecouturier D, Kapel R, Lutin F, Vezina LP, Bazinet L (2009) Concentration and selective separation of bioactive peptides from an alfalfa white protein hydrolysate by electrodialysis with ultrafiltration membranes. J Membr Sci 329:60–67
Kan XW, Zhao Q, Shao DL, Geng ZR, Wang ZL, Zhu JJ (2010) Preparation and recognition properties of bovine hemoglobin magnetic molecularly imprinted polymers. J Phys Chem B 114:3999–4004
Piletsky SA, Matuschewski H, Schedler U, Wilpert A, Piletska EV, Thiele TA (2000) Surface functionalization of porous polypropylene membranes with molecularly imprinted polymers by photograft copolymerization in water. Macromolecules 33:3092–3098
Schild HG (1992) Poly(N-isopropylacrylamide): experiment, theory and application. Prog Polym Sci 17:163–249
Cao ZF, Jin Y, Zhang B, Miao Q (2010) A novel temperature- and pH-responsive polymer–biomolecule conjugate composed of casein and poly(N-isopropylacrylamide). Iran Polym J 19:689–698
Deng KL, Li Q, Bai LB, Gou YB, Dong LR, Huang CY, Wang SL, Gao T (2011) A pH/thermo-responsive injectable hydrogel system based on poly(N-acryloylglycine) as a drug carrier. Iran Polym J 20:185–194
Liu ZJ, Liang YL, Geng FF, Ge C, Ullah K, Lv F, Dai RJ, Zhang YK, Deng YL (2012) Separation of peptides with an aqueous mobile phase by temperature-responsive chromatographic column. J Sep Sci 35:2069–2074
Kiani GR, Arsalani N (2006) Synthesis and properties of some transition metal complexes with water soluble hydroxy functionalized polyacrylonitrile. Iran Polym J 15:727–735
Xu LC, Pan JM, Xia QF, Shi FF, Dai JD, Wei X, Yan YS (2012) Composites of silica and molecularly imprinted polymers for degradation of sulfadiazine. J Phys Chem C 116:25309–25318
Shanmugharaj AM, Ryu SH (2013) Synthesis of poly(styrene-co-acrylonitrile) copolymer brushes on silica nanoparticles through surface-initiated polymerization. Iran Polym J 22:227–236
Shim SE, Yang S, Choe S (2004) Mechanism of the formation of stable microspheres by precipitation copolymerization of styrene and divinylbenzene. J Polym Sci, Part A Polym Chem 42:3967–3974
Li K, Stöver HDH (1993) Synthesis of monodisperse poly(divinylbenzene) microspheres. J Polym Sci, Part A Polym Chem 31:3257–3263
Bai F, Yang X, Li R, Huang B, Huang W (2006) Monodisperse hydrophilic polymer microspheres having carboxylic acid groups prepared by distillation precipitation polymerization. Polymer 47:5775–5784
Limé F, Irgum K (2007) Monodisperse polymeric particles by photoinitiated precipitation polymerization. Macromolecules 40:1962–1968
Limé F, Irgum K (2009) Preparation of divinylbenzene and divinylbenzene-co-glycidyl methacrylate particles by photoinitiated precipitation polymerization in different solvent mixtures. Macromolecules 42:4436–4442
Liu LC, Wang GX, Lu M, Wu H (2013) Activators regenerated by electron transfer in ATRP of methyl methacrylate with alcohol as reducing agent in the presence of a base. Iran Polym J 22:890–896
Vaughan AD, Sizemore SP, Byrne ME (2007) Enhancing molecularly imprinted polymer binding properties via controlled/living radical polymerization and reaction analysis. Polymer 48:74–81
Inui K, Noguchi T, Miyata T, Uragami T (1999) Pervaporation characteristics of methyl methacrylate–methacrylic acid copolymer membranes ionically crosslinked with metal ions for a benzene/cyclohexane mixture. J Appl Polym Sci 71:233–241
Neel J, Huang RYM (1991) Elsevier. Amsterdam, Chapter 1:2–17
Kashiwagi T, Inaba A, Brown JE (1986) Effect of weak linkages on the thermal and oxidative degradation of poly(methyl methacrylates). Macromoleculres 19:2160–2168
Popovic IG, Katsikas L, Weller H, Schrötter S, Velickovic JS (1993) Polymerization studies: the application of the differential thermogravimetric analysis. J Appl Polym Sci 50:1475–1482
Chang C, Wei H, Feng J, Wang ZC, Wu XJ, Wu DQ, Cheng SX, Zhang XZ, Zhuo RX (2009) Temperature and pH double responsive hybrid cross-linked micelles based on p(NIPAAm-co-MPMA)-b-P(DEA): RAFT synthesis and “Schizophrenic” micellization. Macromolecules 42:4838–4844
Zhang XZ, Zhuo RX (2001) Dynamic properties of temperature-sensitive poly(N-isopropylacrylamide) gel cross-linked through siloxane linkage. Langmuir 17:12–16
Xu LC, Pan JM, Dai JD, Li XX, Hang H, Cao ZJ, Yan YS (2012) Preparation of thermal-responsive magnetic molecularly imprinted polymers for selective removal of antibiotics from aqueous solution. J Hazard Mater 233–234:48–56
Gajovic-Eichelmann N, Athikomrattanakul U, Dechtrirat D, Scheller FW (2013) Molecular imprinting technique for biosensing and diagnostics. Iran Polym J 14:143–170
Cowieson D, Piletska E, Moczko E, Piletsky S (2013) Grafting of molecularly imprinted polymer to porous polyethylene filtration membranes by plasma polymerization. Anal Bioanal Chem 405:6489–6496
Zhang T, Kientzy C, Franco P, Ohnishi A, Kagamihara Y, Kurosawa H (2005) Solvent versatility of immobilized 3,5-dimethylphenylcarbamate of amylose in enantiomeric separations by HPLC. J Chromatogr A 1075:65–75
Cheng ZY, Zhang LW, Li YZ (2004) Synthesis of an enzyme-like imprinted polymer with the substrate as the template, and its catalytic properties under aqueous conditions. Chem Eur J 10:3555–3561
Zhu XY, Zheng ZJ, Xie J, Wang P (2012) Selective separation of magnolol using molecularly imprinted membranes. J Sep Sci 35:315–319
Acknowledgments
This work was financially supported by Foundation of State Key Laboratory of Natural and Biomimetic Drugs (K20110105).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Lei, Y., Chen, F. & Luo, Y. Preparation and evaluation of chiral selective cation-exchange PMMA–PNIPAm thermal-sensitive membranes. Iran Polym J 23, 679–687 (2014). https://doi.org/10.1007/s13726-014-0262-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13726-014-0262-7