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Microsystem Technologies

, Volume 20, Issue 10–11, pp 2037–2043 | Cite as

Photo-lithographic patterning of biomimetic molecularly imprinted polymer thin films onto silicon wafers

  • Reinhard I. Boysen
  • Lachlan J. Schwarz
  • Shuyan Li
  • Jamil Chowdhury
  • Milton T. W. Hearn
Technical Paper

Abstract

This investigation describes the design and synthesis of molecularly imprinted polymers (MIPs) as patterned thin films, based on molecular modelling of functional monomer-template interactions and validation by NMR-spectroscopy. Several MIP thin films were prepared from a solution containing the template N-boc-l-phenylalanine and functional acrylic monomers at varying ratios with a cross-linker and initiator in a porogenic solvent. This solution was then spin-coated onto 3-(trimethoxysilyl)propyl methacrylate-functionalised silicon wafers and subsequently the film was photo-polymerised. After template extraction, the film thickness and topography of a methacrylic acid MIP was characterised with atomic force microscopy. A 4-vinylpyridine-MIP thin film was then made by depositing the pre-polymerisation solution on top of the methacrylic acid MIP by spin-coating. Photo-lithographic etching through a gold grid and extraction of non-polymerised solution from under the gold mask yielded a grid-patterned surface, in which two different MIPs alternate with dimensionality at the micro- or submicro-meter scale. Selectivity differences between the two MIP surfaces towards fluorescent template analogue N-dansyl-l-phenylalanine were documented using fluorescence microscopy. This side-by-side comparison on the same thin film allows fast and cost-effective assessment of the two very different MIP selectivities towards various biomolecules.

Keywords

Silicon Wafer Functional Monomer Template Molecule Trimethoxysilyl Diglyme 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgments

This project was supported by the Commonwealth of Australia through funding from the Australian Research Council, Department of Industry, Innovation, Science and Research (International Science Linkages) program and was part of the Australian-European integrated FP7 project ‘Bio-Inspired Self-assembled Nano-Enabled Surfaces’ (BISNES).

References

  1. Belmont A-S, Jaeger S, Knopp D, Niessner R, Gauglitz G, Haupt K (2007) Molecularly imprinted polymer films for reflectometric interference spectroscopic sensors. Biosens Bioelectron 22:3267–3272. doi: 10.1016/j.bios.2007.01.023 CrossRefGoogle Scholar
  2. Boysen RI, Li S, Chowdhury J, Schwarz LJ, Hearn MTW (2012) Selectivity optimisation of biomimetic molecularly imprinted polymer thin films. Microelectron Eng 97:81–84. doi: 10.1016/j.mee.2012.03.026 CrossRefGoogle Scholar
  3. Campbell SE, Collins M, Xie L, BelBruno JJ (2009) Surface morphology of spin-coated molecularly imprinted polymer films. Surf Interface Anal 41:347–356. doi: 10.1002/sia.3030 CrossRefGoogle Scholar
  4. Detsi A, Afantitis A, Athanasellis G, Markopoulos J, Igglessi-Markopoulou O, Skylaris C-K (2003) Cyclisation of novel amino oxo esters to tetramic acids−density functional theory study of the reaction mechanism. Eur J Org Chem 2003:4593–4600. doi: 10.1002/ejoc.200300422 CrossRefGoogle Scholar
  5. Guillon S, Lemaire R, Linares AV, Haupt K, Ayela C (2009) Single step patterning of molecularly imprinted polymers for large scale fabrication of microbiochips. Lab Chip 9:2987–2991. doi: 10.1039/b905608d CrossRefGoogle Scholar
  6. Holdsworth CI, Bowyer MC, Lennard C, McCluskey A (2005) Formulation of cocaine-imprinted polymers utilizing molecular modelling and NMR analysis. Aust J Chem 58:315–320CrossRefGoogle Scholar
  7. Huang HC, Lin CI, Joseph AK, Lee YD (2004) Photo-lithographically impregnated and molecularly imprinted polymer thin film for biosensor applications. J Chromatogr A 1027:263–268. doi: 10.1016/j.chroma.2003.08.106 CrossRefGoogle Scholar
  8. Kantarovich K, Tsarfati I, Gheber LA, Haupt K, Bar I (2009) Writing droplets of molecularly imprinted polymers by nano fountain pen and detecting their molecular interactions by surface-enhanced Raman scattering. Anal Chem 81:5686–5690. doi: 10.1021/ac900418x CrossRefGoogle Scholar
  9. Lalo H, Ayela C, Dague E, Vieu C, Haupt K (2010) Nanopatterning molecularly imprinted polymers by soft lithography: a hierarchical approach. Lab Chip 10:1316–1318. doi: 10.1039/b924315a CrossRefGoogle Scholar
  10. Linares AV, Vandevelde F, Pantigny J, Falcimaigne-Cordin A, Haupt K (2009) Polymer films composed of surface-bound nanofilaments with a high aspect ratio, molecularly imprinted with small molecules and proteins. Adv Funct Mater 19:1299–1303. doi: 10.1002/adfm.200801222 CrossRefGoogle Scholar
  11. Ma J, Yuan L, Ding M, Wang S, Ren F, Zhang J, Du S, Li F, Zhou X (2011) The study of core-shell molecularly imprinted polymers of 17β-estradiol on the surface of silica nanoparticles. Biosens Bioelectron 26:2791–2795. doi: 10.1016/j.bios.2010.10.045 CrossRefGoogle Scholar
  12. Piletsky SA, Karim K, Piletska EV, Day CJ, Freebairn KW, Legge C, Turner APF (2001) Recognition of ephedrine enantiomers by molecularly imprinted polymers designed using a computational approach. Analyst 126:1826–1830. doi: 10.1039/b102426b CrossRefGoogle Scholar
  13. Schwarz L, Holdsworth CI, McCluskey A, Bowyer MC (2004) Synthesis and evaluation of a molecularly imprinted polymer selective to 2,4,6-trichlorophenol. Aust J Chem 57:759–764CrossRefGoogle Scholar
  14. Schwarz LJ, Danylec B, Harris SJ, Boysen RI, Hearn MTW (2011) Preparation of molecularly imprinted polymers for selective recognition of bioactive polyphenol, (E)-resveratrol. J Chromatogr A 1218:2189–2195. doi: 10.1016/j.chroma.2011.02.043 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Reinhard I. Boysen
    • 1
  • Lachlan J. Schwarz
    • 1
  • Shuyan Li
    • 1
  • Jamil Chowdhury
    • 1
  • Milton T. W. Hearn
    • 1
  1. 1.Victorian Centre for Sustainable Chemical Manufacturing, Centre for Green Chemistry, School of ChemistryMonash UniversityMelbourneAustralia

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