Skip to main content
SpringerLink
Log in

Molecularly imprinted polymers fabricated via Pickering emulsions stabilized solely by food-grade casein colloidal nanoparticles for selective protein recognition

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Novel molecularly imprinted polymers (MIPs) based on denatured casein nanoparticle (DCP)-stabilized Pickering emulsions were developed for the first time. Casein, a phosphoprotein, is the main protein in milk. In this work, DCPs were solely used as Pickering-type interfacial emulsifiers for fabrication of MIPs for the selective recognition of proteins for the first time. DCPs were prepared by acidification and heat denaturation (at 80 °C) of casein. Their dispersions have satisfactory colloidal stability over a wide pH range. The DCPs acted as natural, food-grade, and edible interfacial emulsifiers, and adsorbed at the oil–water interface to form Pickering emulsions. After the polymerization of monomers, the template protein was removed by elution. During the elution, the interfacial DCPs were also removed, allowing more imprinted cavities to become exposed. The interfacial imprinting technology causes nearly all the imprinted sites to locate on the surface of the polymeric material. Therefore, the MIPs obtained exhibit fast rebinding and excellent specific recognition ability toward the analytes. Overall, this work provides a promising method for designing and fabricating natural-protein-based structured emulsions to prepare MIPs and thus offers new insight into protein separation and purification.

Pickering emulsions stabilized by denatured casein particles.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Lv YQ, Tan TW, Svec F. Molecular imprinting of proteins in polymers attached to the surface of nanomaterials for selective recognition of biomacromolecules. Biotechnol Adv. 2013;31:1172–86.

    Article  CAS  Google Scholar 

  2. Mirata F, Resmini M. Molecularly imprinted polymers for catalysis and synthesis. Adv Biochem Eng Biotechnol. 2015;150:107–29.

    CAS  Google Scholar 

  3. Haupt K, Mosbach K. Molecularly imprinted polymers and their use in biomimetic sensors. Chem Rev. 2000;100:2495–504.

    Article  CAS  Google Scholar 

  4. Chen L, Xu S, Li J. Recent advances in molecular imprinted technology: current status, challenges and highlighted applications. Chem Soc Rev. 2011;40:2922–42.

    Article  CAS  Google Scholar 

  5. Luo J, Ma Q, Wei W, Zhu Y, Liu R, Liu X. Synthesis of water-dispersible molecularly imprinted electroactive nanoparticles for the sensitive and selective paracetamol detection. ACS Appl Mater Interfaces. 2016;8:21028–38.

    Article  CAS  Google Scholar 

  6. Chunta S, Suedee R, Lieberzeit PA. Low-density lipoprotein sensor based on molecularly imprinted polymer. Anal Chem. 2016;88:1419–25.

    Article  CAS  Google Scholar 

  7. Hussain M, Kotoya K, Lieberzeit PA. Molecularly imprinted polymer nanoparticles for formaldehyde sensing with QCM. Sensors. 2016;16:1011-11.

  8. Wulff G. Enzyme-like catalysis by molecularly imprinted polymers. Chem Rev. 2002;102:1–28.

    Article  CAS  Google Scholar 

  9. Sun Y, Chen J, Li Y, Li H, Zhu X, Hu Y, et al. Bio-inspired magnetic molecularly imprinted polymers based on Pickering emulsion for selective protein recognition. New J Chem. 2016;40:8745–52.

    Article  CAS  Google Scholar 

  10. Dai J, He J, Xie A, Gao L, Pan J, Chen X, et al. Novel pitaya-inspired well-defined core-shell nanospheres with ultrathin surface imprinted nanofilm for magnetic mesoporous nanosilica for highly efficient chloramphenicol removal. Chem Eng J. 2016;284:812–22.

    Article  CAS  Google Scholar 

  11. Pellizzoni E, Tommasini M, Marangon E, Rizzolio F, Saito G, Benedetti F, et al. Fluorescent molecularly imprinted nanogels for the detection of anticancer drugs in human plasma. Biosens Bioelectron. 2016;86:913–9.

    Article  CAS  Google Scholar 

  12. Ray JV, Mirata F, Perollier C, Arotcarena M, Bayoudh S, Resmini M. Smart coumarin-tagged imprinted polymers for the rapid detection of tamoxifem. Anal Bioanal Chem. 2016;408:1855–61.

    Article  CAS  Google Scholar 

  13. Urraca JL, Aureliano CSA, Schillinger E, Esselmann H, Wiltfang J, Sellergren B. Polymeric complements to the Alzheimer’s disease biomarker β–amyloid isoforms Aβ1-40 and Aβ1-42 for blood serum analysis under denaturing conditions. J Am Chem Soc. 2011;33:9220–3.

    Article  Google Scholar 

  14. Chunta S, Singsanan S, Suedee R, Lieberzeit PA. Sensor array based on molecularly imprinted polymers for simultaneous detection of lipoproteins. Proceedings. 2017;1:510-10

  15. Li S, Cao S, Whitcombe MJ, Piletsky SA. Size matters: challenges in imprinting macromolecules. Prog Polym Sci. 2014;39:145–63.

    Article  CAS  Google Scholar 

  16. Luo J, Huang J, Cong J, Wei W, Liu X. Double recognition and selective extraction of glycoprotein based on the molecular imprinted graphene oxide and boronate affinity. ACS Appl Mater Interfaces. 2017;9:7735–44.

    Article  CAS  Google Scholar 

  17. Verheyen E, Schillemans JP, van Wijk M, Demenies MA, Hennink WE, van Nostrum CF. Challenges for the effective molecular imprinting of proteins. Biomaterials. 2011;32:3008–20.

    Article  CAS  Google Scholar 

  18. Zhou T, Zhang K, Kamra T, Bulow L, Ye L. Preparation of protein imprinted polymer beads by Pickering emulsion polymerization. J Mater Chem. 2015;3:1254–60.

    Article  CAS  Google Scholar 

  19. Shen X, Zhou T, Ye L. Molecular imprinting of protein in Pickering emulsion. Chem Commun. 2012;48:8198–200.

    Article  CAS  Google Scholar 

  20. Hoshino Y, Koide H, Urakami T, Kanazawa H, Kodama T, Oku N, et al. Recognition, neutralization, and clearance of target peptides in the bloodstream of living mice by molecularly imprinted polymer nanoparticles: a plastic antibody. J Am Chem Soc. 2010;132:6644–5.

    Article  CAS  Google Scholar 

  21. Ramsden W. Separation of solids in the surface-layers of solutions and ‘suspensions’ (Observations on surface-membranes bubbles, emulsions, and mechanical coagulation)–Preliminary account. Proc R Soc Lond. 1903;72:156–64.

    Article  CAS  Google Scholar 

  22. Pickering SU. Emulsions. J Chem Soc Trans. 1907;81:2001–21.

    Article  Google Scholar 

  23. Pan J, Liu J, Ma Y, Huang X, Zhang T, Chen X, et al. Wulff-type boronic acids suspended hierarchical porous polymeric monolith for the specific capture of cis-diol-containing flavone under neutral condition. Chem Eng J. 2017;317:317–30.

    Article  CAS  Google Scholar 

  24. Tang J, Quinlan PJ, Tam KC. Stimuli-responsive Pickering emulsions: recent advances and potential application. Soft Matter. 2015;11:3512–29.

    Article  CAS  Google Scholar 

  25. Tang J, Berry RM, Tam KC. Stimuli-responsive cellulose nanocrystals for surfactant-free oil harvesting. Biomacromolecules. 2016;17:1748–56.

    Article  CAS  Google Scholar 

  26. Schrade A, Landfester K, Ziener U. Pickering-type stabilized nanoparticles by heterophase polymerization. Chem Soc Rev. 2013;42:6823–39.

    Article  CAS  Google Scholar 

  27. Berton-Carabin CC, Schroen K. Pickering emulsions for food applications: background, trends, and challenges. Annu Rev Food Sci Technol. 2015;6:263–97.

    Article  CAS  Google Scholar 

  28. Hussain MA, Liu H, Wang Q, Zhong F, Guo Q, Balamurugan S. Use of encapsulated bacteriophages to enhance farm to fork food safety. Crit Rev Food Sci Nutr. 2017;57:2801–10.

    Article  CAS  Google Scholar 

  29. Zhou H, Shi T, Zhou X. Preparation of polystyrene/SiO2 microsphere via Pickering emulsion polymerization: Synergistic effect of SiO2 concentrations and initiators sorts. Appl Surf Sci. 2013;66:33–8.

    Article  Google Scholar 

  30. Li Y, Sun Y, Chen J, Zhu X, Li H, Huang S, et al. Graphene oxide as a sacrificial material for fabricating molecularly imprinted polymers via Pickering emulsion polymerization. RSC Adv. 2016;6:74654–61.

    Article  CAS  Google Scholar 

  31. Bon SAF, Colver PJ. Pickering miniemulsion polymerization using laponite clay as a stabilizer. Langmuir. 2007;23:8316–22.

    Article  CAS  Google Scholar 

  32. Teixeira RFA, McKenzie HS, Boyd AA, Bon SAF. Pickering emulsion polymerization using laponite clay as stabilizer to prepare armored “soft” polymer latexes. Macromolecules. 2011;44:7415–22.

    Article  CAS  Google Scholar 

  33. Sun Y, Li Y, Xu J, Huang L, Qiu T. Interconnectivity of macroporous molecularly imprinted polymers fabricated by hydroxyapatite-stabilized Pickering high internal phase emulsions-hydrogels for the selective recognition of protein. Colloids Surf B. 2017;155:142–9.

    Article  CAS  Google Scholar 

  34. Wang X, Li J, Li Y, Liu L, Guan W. Emulsion-templated fully three-dimensional interconnected porous titania ceramics with excellent humidity sensing properties. Sensors Actuators B Chem. 2016;237:894–8.

    Article  CAS  Google Scholar 

  35. Huo J, Marcello M, Garai A, Bradshaw D. MOF-polymer composite microcapsules derived from Pickering emulsions. Adv Mater. 2013;25:2717–22.

    Article  CAS  Google Scholar 

  36. Luo ZY, Lyu SS, Fu YX, Heng Y, Mo DC. The Janus effect on superhydrophilic Cu mesh decorated with Ni-NiO/Ni(OH)2 core-shell nanoparticles for oil/water separation. Appl Surf Sci. 2017;409:431–7.

    Article  CAS  Google Scholar 

  37. Liu X, Yi C, Zhu Y, Yang Y, Jiang J, Cui Z. Pickering emulsions stabilized by self-assembled colloidal particles of copolymers of P(St-alt-Man)-co-P(VM-alt-Man). J Colloid Interface Sci. 2010;351:315–22.

    Article  CAS  Google Scholar 

  38. Sun Y, Zhong S. Nanoscale trifunctional bovine hemoglobin for fabricating molecularly imprinted polydopamine via Pickering emulsions-hydrogels polymerization. Colloids Surf B. 2017;159:131–8.

    Article  CAS  Google Scholar 

  39. Lin Q, Liang R, Ye A, Singh H, Zhong F. Effects of calcium on lipid digestion in nanoemulsions stabilized by modified starch: implications for bioaccessibility of β-carotene. Food Hydrocoll. 2017;73:184–93.

    Article  CAS  Google Scholar 

  40. Zhu W, Ma W, Li C, Pan J, Dai X, Gan M, et al. Magnetic molecularly imprinted microspheres via yeast stabilized Pickering emulsion polymerization for selective recognition of λ-cyhalothrin. Colloids Surf A Physicochem Eng Asp. 2014;453:27–36.

    Article  CAS  Google Scholar 

  41. Wongkongkatep P, Manopwisedjaroen K, Tiposoth P, Archakunakorn S, Pongtharangkul T, Suphantharika M, et al. Bacteria interface Pickering emulsions stabilized by self-assembled bacteria-chitosan network. Langmuir. 2012;28:5729–36.

    Article  CAS  Google Scholar 

  42. Qiu Y, Ma Z, Hu P. Environmentally benign magnetic chitosan/Fe3O4 composites as reductant and stabilizer for anchoring Au NPs and their catalytic reduction of 4-nitrophenol. J Mater Chem A. 2014;2:13471–8.

    Article  CAS  Google Scholar 

  43. Tang J, Sisler J, Grishkewich N, Tam KC. Functionalization of cellulose nanocrystals for advanced applications. J Colloid Interface Sci. 2017;495:397–409.

    Article  Google Scholar 

  44. Han S, Zhang H, Xie Y, Liu L, Shan C, Li X, et al. Application of cow milk-derived carbon dots/Ag NPs composite as the antibacterial agent. Appl Surf Sci. 2015;328:368–73.

    Article  CAS  Google Scholar 

  45. Dalgleish DG. On the structural models of bovine casein micelles – review and possible improvements. Soft Matter. 2011;7:2265–72.

    Article  CAS  Google Scholar 

  46. Liu F, Tang CH. Soy protein nanoparticle aggregates as Pickering stabilizers for oil-in-water emulsions. J Agric Food Chem. 2013;61:8888–98.

    Article  CAS  Google Scholar 

  47. Feng Y, Lee Y. Surface modification of zein colloidal particles with sodium caseinate to stabilize oil-in-water Pickering emulsion. Food Hydrocoll. 2016;56:292–302.

    Article  CAS  Google Scholar 

  48. Donato L, Alexander M, Dalgleish DG. Acid gelation in heated and unheated milks: interactions between serum protein complexes and the surfaces of casein micelles. J Agric Food Chem. 2007;55:4160–8.

    Article  CAS  Google Scholar 

  49. Yaginuma Y, Kijima T. Effect of pH on rheological properties of microcrystalline cellulose dispersions. J Dispers Sci Technol. 2006;27:365–70.

    Article  CAS  Google Scholar 

  50. de Folter JW, van Ruijven MWM, Velikov KP. Oil-in-water Pickering emulsions stabilized by colloidal particles from the water-insoluble protein zein. Soft Matter. 2012;8:6807–15.

    Article  Google Scholar 

  51. Vignati E, Piazza R, Lockhart TP. Pickering emulsions: Interfacial tension, colloidal layer morphology, and trapped-particle motion. Langmuir. 2003;19:6650–6.

    Article  CAS  Google Scholar 

  52. Fan X, Niu L, Wu Y, Cheng J, Yang Z. Assembly route toward raspberry-like composite particles and their controlled surface wettability through varied dual-size binary roughness. Appl Surf Sci. 2015;332:393–402.

    Article  CAS  Google Scholar 

  53. Gao R, Zhang L, Hao Y, Cui X, Liu D, Zhang M, et al. One-step preparation of magnetic imprinted nanoparticles adopting dopamine-cupric ion as a co-monomer for the specific recognition of bovine hemoglobin. J Sep Sci. 2015;38:3568.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (no. 21576295) and Hunan Provincial Innovation Foundation for Postgraduate (CX2017B043).

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan, 410083, China

    Yanhua Sun & Shian Zhong

Authors
  1. Yanhua Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shian Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shian Zhong.

Ethics declarations

This article does not contain any studies with human participants or animals performed by any of the authors.

Conflict of interest

The authors declare that they have no competing interests.

Electronic supplementary material

ESM 1

(PDF 237 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sun, Y., Zhong, S. Molecularly imprinted polymers fabricated via Pickering emulsions stabilized solely by food-grade casein colloidal nanoparticles for selective protein recognition. Anal Bioanal Chem 410, 3133–3143 (2018). https://doi.org/10.1007/s00216-018-1006-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1006-x

Keywords

Search

Navigation