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Construction of imprint sites in mesopores of SBA-15 via thiol-ene click reaction

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Abstract

This paper reports a new strategy for preparation of 2D molecularly imprinted materials (MIM) through the exploitation of thiol-ene click chemistry. 2D MIM for cholesterol was prepared using cholesterol as the template, acrolyl-modified β-cyclodextrin (acrolyl-β-CD) as the functional monomer, and thiol-modified SBA-15 (thiol-SBA-15) as the supporter. In this method, acrolyl-β-CD molecules were assembled around the templates by formation of template–monomer inclusion compounds. Then the acrolyl-β-CD molecules were anchored to the walls of the mesopores of SBA-15 via the thiol-ene click chemistry. After removal of the template molecules, the resulting recognition sites were formed in the mesopores of SBA-15. TEM, XRD, and N2 adsorption–desorption analysis results demonstrated that the synthesized MIM had a highly ordered mesoporous structure. Results from FT-IR revealed that acrolyl-β-CDs have been successfully conjugated to SBA-15. The density of β-CDs attached on the MIM is determined by EA and TGA. The equilibrium binding amounts of MIM and non-imprinted materials (NIM) for cholesterol are 53.50 and 25.24 μmol/g, respectively. The 2D MIM exhibited binding affinity and specificity for a group of analytes which have similar size and shape to those of template. The application of the prepared materials as stationary phases in thin layer chromatography was investigated preliminarily. The imprinted materials had higher retention ability for the template than the NIM. The retention factors (R f) of cholesterol on MIM and NIM are 0.62 and 0.81, respectively. The solid phase extraction of cholesterol using MIM as the adsorbent was further investigated. The recoveries of the molecularly imprinted solid phase extraction column for cholesterol were 77.1–94.7 % with relative standard deviations (RSD) of 2.25–6.78 %.

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References

  1. Zhao MY, Ma XD, Zhao FJ, Guo HW (2016) Molecularly imprinted polymer silica monolith for the selective extraction of alpha-cypermethrin from soil samples. J Mater Sci 51:3440–3447. doi:10.1007/s10853-015-9661-1

    Article  Google Scholar 

  2. Zhang Z, Li JH, Fu LW, Liu DY, Chen LX (2015) Magnetic molecularly imprinted microsensor for selective recognition and transport of fluorescent phycocyanin in seawater. J Mater Chem A 3:7437–7444

    Article  Google Scholar 

  3. Manzo V, Ulisse K, Rodríguez I, Pereira E, Richter P (2015) A molecularly imprinted polymer as the sorptive phase immobilized in a rotating disk extraction device for the determination of diclofenac and mefenamic acid in wastewater. Anal Chim Acta 889:130–137

    Article  Google Scholar 

  4. Whitcombe MJ, Chianella I, Larcombe L, Piletsky SA, Noble J, Porter R, Horgan A (2011) The rational development of molecularly imprinted polymer-based sensors for protein detection. Chem Soc Rev 40:1547–1571

    Article  Google Scholar 

  5. Fuchs Y, Soppera O, Mayes AG, Haupt K (2013) Holographic molecularly imprinted polymers for label-free chemical sensing. Adv Mater 25:566–570

    Article  Google Scholar 

  6. Ahmad R, Griffete N, Lamouri A, Felidj N, Chehimi MM, Mangeney C (2015) Nanocomposites of gold nanoparticles@molecularly imprinted polymers: chemistry, processing, and applications in sensors. Chem Mater 27:5464–5478

    Article  Google Scholar 

  7. Altintas Z, Gittens M, Guerreiro A, Thompson KA, Walker J, Piletsky S, Tothill IE (2015) Detection of waterborne viruses using high affinity molecularly imprinted polymers. Anal Chem 87:6801–6807

    Article  Google Scholar 

  8. Yun YH, Shon HK, Yoon SD (2009) Preparation and characterization of molecularly imprinted polymers for the selective separation of 2,4-dichlorophenoxyacetic acid. J Mater Sci 44:6206–6211. doi:10.1007/s10853-009-3863-3

    Article  Google Scholar 

  9. Liu BH, Han MY, Guan GJ, Wang SH, Liu RY, Zhang ZP (2011) Highly-controllable molecular imprinting at superparamagnetic iron oxide nanoparticles for ultrafast enrichment and separation. J Phys Chem C 115:17320–17327

    Article  Google Scholar 

  10. Chrzanowska AM, Poliwoda A, Wieczorek PP (2015) Surface molecularly imprinted silica for selective solid-phase extraction of biochanin A, daidzein and genistein from urine samples. J Chromatogr A 1392:1–9

    Article  Google Scholar 

  11. Wang X, Pan JM, Guan W, Dai JD, Zou XH, Yan YS, Li CX, Hu W (2011) Selective removal of 3-chlorophenol from aqueous solution using surface molecularly imprinted microspheres. J Chem Eng Data 56:2793–2801

    Article  Google Scholar 

  12. Chen W, Xue M, Xue F, Mu XR, Xu ZB, Meng ZH, Zhu GX, Shea KJ, Kunitake T, Lee S (2004) Molecularly imprinted hollow spheres for the solid phase extraction of estrogens, molecular imprinting in ultrathin titania gel films via surface sol-gel process. Anal Chim Acta 504:1–6

    Article  Google Scholar 

  13. Shi HG, Wang RY, Yang JX, Ren HQ, Liu S, Guo TY (2015) Novel imprinted nanocapsule with highly enhanced hydrolytic activity for organophosphorus pesticide degradation and elimination. Eur Polym J 72:190–201

    Article  Google Scholar 

  14. Pan JM, Yao H, Xu LC, Ou HX, Huo PW, Li XX, Yan YS (2011) Selective recognition of 2,4,6-trichlorophenol by molecularly imprinted polymers based on magnetic halloysite nanotubes composites. J Phys Chem C 115:5440–5449

    Article  Google Scholar 

  15. Embrecht A, Feng CYA, Mills C, Lee M, Bredebusch I, Schnekenburger J, Domschke W, Vancso GV, Schonherr H (2008) Inverted microcontact printing on polystyrene-block-poly(tert-butyl acrylate) films: a versatile approach to fabricate structured biointerfaces across the length scales. Langmuir 24:8841–8849

    Article  Google Scholar 

  16. Lua Q, Chen XM, Nie L, Luo J, Jiang HJ, Chen LN, Hua Q, Du SH, Zhang ZP (2010) Tuning of the vinyl groups’ spacing at surface of modified silica in preparation of high density imprinted layer-coated silica nanoparticles: a dispersive solid-phase extraction materials for chlorpyrifos. Talanta 81:959–966

    Article  Google Scholar 

  17. Altintas Z, Guerreiro A, Piletsky SA, Tothill IE (2015) NanoMIP based optical sensor for pharmaceuticals monitoring. Sensor Actuat B 213:305–313

    Article  Google Scholar 

  18. Zhang JW, Liu YL, Wu GL, Schönhoff M, Zhang X (2011) Bolaform supramolecular amphiphiles as a novel concept for the buildup of surface-imprinted films. Langmuir 27:10370–10375

    Article  Google Scholar 

  19. Zhang RR, Guo XQ, Shi XZ, Sun AL, Wang L, Xiao TT, Tang ZG, Pan DD, Li DX, Chen J (2014) Highly permselective membrane surface modification by cold plasma-induced grafting polymerization of molecularly imprinted polymer for recognition of pyrethroid insecticides in fish. Anal Chem 86:11705–11713

    Article  Google Scholar 

  20. Bi XY, Yang KL (2009) On-line monitoring imidacloprid and thiacloprid in celery juice using quartz crystal microbalance. Anal Chem 81:527–532

    Article  Google Scholar 

  21. Apodaca DC, Pernites RB, Del Mundo FR, Advincula RC (2011) Detection of 2,4-dinitrotoluene (DNT) as a model system for nitroaromatic compounds via molecularly imprinted short-alkyl-chain SAMs. Langmuir 27:6768–6779

    Article  Google Scholar 

  22. Nie DX, Jiang DW, Zhang D, Liang Y, Xue Y, Zhou TS, Jin LT, Shi GY (2011) Two-dimensional molecular imprinting approach for the electrochemical detection of trinitrotoluene. Sensor Actuat B 156:43–49

    Article  Google Scholar 

  23. Piletsky SY, Piletskaya EV, Sergeyeva TA, Panasyuk TL, El’skaya AV (1999) Molecularly imprinted self-assembled films with specificity to cholesterol. Sensor Actuat B 60:216–220

    Article  Google Scholar 

  24. Chou LCS, Liu CC (2005) Development of a molecular imprinting thick film electrochemical sensor for cholesterol detection. Sensor Actuat B 110:204–208

    Article  Google Scholar 

  25. Xu ZF, Deng PH, Tang SP, Kuang DZ, Zhang FX, Li JH (2014) Preparation of 2D molecularly imprinted materials based on mesoporous silicas via click reaction. J Mater Chem B 2:8418–8426

    Article  Google Scholar 

  26. McNair OD, Brent DP, Sparks BJ, Patton DL, Savin DA (2014) Sequential thiol click reactions: formation of ternary thiourethane/thiol–ene networks with enhanced thermal and mechanical properties. ACS Appl. Mater. Interfaces 6:6088–6097

    Article  Google Scholar 

  27. Ware TH, Perry ZP, Middleton CM, Iacono ST, White TJ (2015) Programmable liquid crystal elastomers prepared by thiol-ene photopolymerization. ACS Macro Lett 4:942–946

    Article  Google Scholar 

  28. Hishiya T, Shibata M, Kakazu M, Asanuma H, Komiyama M (1999) Molecularly imprinted cyclodextrins as selective receptors for steroids. Macromolecules 32:2265–2269

    Article  Google Scholar 

  29. Zhu QZ, Haupt K, Knopp D (2002) Molecularly imprinting polymer for metsulfuron-methyl and its binding characteristics for sulfonylurea herbicides. Anal Chim Acta 468:217–227

    Article  Google Scholar 

  30. Hishiya T, Akiyama T, Asanuma H, Komiyama M (2002) Molecular imprinting of cyclodextrins leading to synthetic antibodies. J Incl Phenom Macro 44:365–367

    Article  Google Scholar 

  31. Asanuma H, Akiyama T, Kajiya K, Hishiya T, Komiyama M (2001) Molecular imprinting of cyclodextrin in water for the recognition of nanometer-scaled guests. Anal Chim Acta 435:25–33

    Article  Google Scholar 

  32. Asanuma H, Kakazu M, Shibata M, Hishiya T, Komiyama M (1998) Synthesis of molecularly imprinted polymer of β-cyclodextrin for the efficient recognition of cholesterol. Supramol Sci 5:417–421

    Article  Google Scholar 

  33. Hishiya T, Asanuma H, Komiyama M (2002) Spectroscopic anatomy of molecular-imprinting of cyclodextrin: evidence for preferential formation of ordered cyclodextrin assemblies. J Am Chem Soc 124:570–575

    Article  Google Scholar 

  34. Matsui J, Miyoshi Y, Doblhoff-Dier O, Takeuchi T (1995) Molecularly imprinted synthetic polymer receptor selective for atrazine. Anal Chem 67:4404–4408

    Article  Google Scholar 

  35. Jing T, Wang Y, Dai Q, Xia H, Niu JW, Hao QL, Mei SR, Zhou YK (2010) Preparation of mixed-templates molecularly imprinted polymers and investigation of the recognition ability for tetracycline antibiotics. Biosens Bioelectron 25:2218–2224

    Article  Google Scholar 

  36. Shi XZ, Song SQ, Sun AL, Liu JH, Li DX, Chen J (2012) Characterisation and application of molecularly imprinted polymers for group-selective recognition of antibiotics in food samples. Analyst 137:3381–3389

    Article  Google Scholar 

  37. Su SF, Zhang M, Li BL, Zhang HY, Dong XC (2008) HPLC determination of sulfamethazine in milk using surface-imprinted silica synthesized with iniferter technique. Talanta 76:1141–1146

    Article  Google Scholar 

  38. Xu WJ, Su SF, Jiang P, Wang HS, Dong XC (2010) Determination of sulfonamides in bovine milk with column-switching high performance liquid chromatography using surface imprinted silica with hydrophilic external layer as restricted access and selective extraction material. J Chromatogr A 1217:7198–7207

    Article  Google Scholar 

  39. Fairhurst RE, Chassaing C, Venn RF, Mayes AG (2004) A direct comparison of the performance of ground, beaded and silica-grafted MIPs in HPLC and turbulent flow chromatography applications. Biosens Bioelectron 20:1098–1105

    Article  Google Scholar 

  40. Nematollahzadeh A, Shojaei A, Abdekhodaie MJ, Sellergren B (2013) Molecularly imprinted polydopamine nano-layer on the pore surface of porous particles for protein capture in HPLC column. J Colloid Interf Sci 404:117–126

    Article  Google Scholar 

  41. Suedee R, Songkram C, Petmoreekul A, Sangkunakup S, Sankasa S, Kongyarit N (1999) Direct enantioseparation of adrenergic drugs via thin-layer chromatography using molecularly imprinted polymers. J Pharm Biomed Anal 19:519–527

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank the National Natural Science Foundation of China (No. 21472038 and 21505035), the Project of Education Department of Hunan Province (No. 15A027), the Natural Science Foundation of Hunan Province (No. 2016JJ3028), the Aid programs for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, and the Key Discipline of Hunan Province for the financial support of the research.

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Authors and Affiliations

  1. College of Chemistry and Materials Science, Hengyang Normal University, Hengyang, 421008, People’s Republic of China

    Zhifeng Xu, Peihong Deng, Junhua Li, Siping Tang & Fuxing Zhang

  2. Key Laboratory of Functional Organometallic Materials of Hunan Province University, Hengyang, 421008, People’s Republic of China

    Zhifeng Xu, Peihong Deng, Junhua Li, Siping Tang & Fuxing Zhang

  3. Department of Applied Chemistry, College of Materials and Energy, South China Agricultural University, Guangzhou, 510642, People’s Republic of China

    Li Xu

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Correspondence to Zhifeng Xu.

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Xu, Z., Deng, P., Li, J. et al. Construction of imprint sites in mesopores of SBA-15 via thiol-ene click reaction. J Mater Sci 51, 6295–6308 (2016). https://doi.org/10.1007/s10853-016-9926-3

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