Skip to main content
SpringerLink
Log in

Fabrication of free-standing multilayer films by using pH-responsive microgels as sacrificial layers

  • Short Communication
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

A facile way to prepare free-standing polyelectrolyte multilayer films of poly(sodium 4-styrenesulfonate)(PSS)/poly(diallyldimethylammonium)(PDDA) was developed by applying a new pH-dependent sacrificial system based on cross-linked poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) microgels. The tertiary amine groups of PDMAEMA microgels can be protonated in acidic environment, and the protonated microgels were deposited by layer-by-layer (LbL) technique with PSS. PSS/PDDA multilayer films were constructed on the top of the PSS/microgels sacrificial layers. The LbL assembly process was investigated by UV–vis spectroscopy. Further study shows that the free-standing PSS/PDDA multilayer films can be obtained within 3 min by treating the as-prepared films in alkali aqueous solution with a pH of 12.0. The pH-triggered exfoliation of PSS/PDDA multilayer films provides a simple and facile way to prepare LbL assembled free-standing multilayer films.

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

References

  1. Decher G, Schlenoff JB (2003) Multilayer thin films: sequential assembly of nanocomposite materials. Wiley-VCH, Weinheim, Germany

    Google Scholar 

  2. Such GS, Johnston APR, Caruso F (2011) Engineered hydrogen-bonded polymer multilayers: from assembly to biomedical applications. Chem Soc Rev 40:19–29

    Article  CAS  Google Scholar 

  3. Zhang X (2007) Surface molecular engineering of polymer multilayer films. Acta Polym Sin 10:905–912

    Google Scholar 

  4. Zhang X, Chen H, Zhang HY (2007) Layer-by-layer assembly: from conventional to unconventional methods. Chem Commun 14:1395–1405

    Article  Google Scholar 

  5. Li Y, Wang X, Sun JQ (2012) Layer-by-layer assembly for rapid fabrication of thick polymeric films. Chem Soc Rev 41:5998–6009

    Article  CAS  Google Scholar 

  6. Decher G, Hong JD (1991) Buildup of ultrathin multilayer films by a self-assembly process: 1 consecutive adsorption of anionic and cationic bipolar amphiphiles on charged surfaces. Makromol Chem Macromol Symp 46:321–327

    Article  CAS  Google Scholar 

  7. Schmitt J, Decher G, Dressick WJ, Brandow SL, Geer RE, Shashidhar R, Calvert JM (1997) Metal nanoparticle/polymer superlattice films: fabrication and control of layer structure. Adv Mater 9:61–65

    Article  CAS  Google Scholar 

  8. Crespo-Biel O, Dordi B, Reinhoudt DN, Huskens J (2005) Supramolecular layer-by-layer assembly: alternating adsorptions of guest- and host-functionalized molecules and particles using multivalent supramolecular interactions. J Am Chem Soc 127:7594–7600

    Article  CAS  Google Scholar 

  9. Shimazaki Y, Mitsuishi M, Ito S, Yamamoto M (1997) Preparation of the layer-by-layer deposited ultrathin film based on the charge-transfer interaction. Langmuir 13:1385–1387

    Article  CAS  Google Scholar 

  10. Stockton WB, Rubner MF (1997) Molecular-level processing of conjugated polymers. 4. Layer-by-layer manipulation of polyaniline via hydrogen-bonding interactions. Macromolecules 30:2717–2725

    Article  CAS  Google Scholar 

  11. Suzuki I, Egawa Y, Mizukawa Y, Hoshi T, Anzai J (2002) Construction of positively-charged layered assemblies assisted by cyclodextrin complexation. Chem Commun 2:164–165

    Article  Google Scholar 

  12. Wang LY, Wang ZQ, Zhang X, Shen JC, Chi LF, Fuchs H (1997) A new approach for the fabrication of an alternating multilayer film of poly(4-vinylpyridine) and poly(acry1ic acid) based on hydrogen bonding. Macromol Rapid Commun 18:509–514

    Article  CAS  Google Scholar 

  13. Artyukhin AB, Bakajin O, Stroeve P, Noy A (2004) Layer-by-layer electrostatic self-assembly of polyelectrolyte nanoshells on individual carbon nanotube templates. Langmuir 20:1442–1448

    Article  CAS  Google Scholar 

  14. Shi F, Liu ZH, Wu GL, Zhang M, Chen H, Wang ZQ, Zhang X, Willner I (2007) Surface imprinting in layer-by-layer nanostructured films. Adv Funct Mater 17:1821–1827

    Article  CAS  Google Scholar 

  15. Chen H, Zeng GH, Wang ZQ, Zhang X, Peng ML, Wu LZ, Tung CH (2005) To combine precursor assembly and layer-by-layer deposition for incorporation of single-charged species: nanocontainers with charge-selectivity and nanoreactors. Chem Mater 17:6679–6685

    Article  CAS  Google Scholar 

  16. Fabianowski W, Roszko M, Brodziñska W (1998) Optical sensor with active matrix built from polyelectrolytes–smart molecules mixture. Thin Solid Films 327–329:743–743

    Article  Google Scholar 

  17. Ikeda A, Hatano T, Shinkai S, Akiyama T, Yamada S (2001) Efficient photocurrent generation in novel self-assembled multilayers comprised of [60]fullerene-cationic homooxacalix[3]arene inclusion complex and anionic porphyrin polymer. J Am Chem Soc 123:4855–4856

    Article  CAS  Google Scholar 

  18. Schütte M, Kurth DG, Linford MR, Cölfen H, Möhwald H (1998) Metallosupramolecular thin polyelectrolyte films. Angew Chem Int Ed 37:2891–2893

    Article  Google Scholar 

  19. 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  CAS  Google Scholar 

  20. Zhang JW, Liu YL, Yuan B, Wang ZQ, Schönhoff M, Zhang X (2012) Multilayer films with nanocontainers: redox-controlled reversible encapsulation of guest molecules. Chem Eur J 18:14968–14973

    Article  CAS  Google Scholar 

  21. Zhang JW, Li F, Yuan B, Song Q, Wang ZQ, Zhang X (2013) Layer-by-Layer assembly of azulene-based supra-amphiphiles: reversible encapsulation of organic molecules in water by charge-transfer interaction. Langmuir 29:6348–6353

    Article  CAS  Google Scholar 

  22. Ono SS, Decher G (2006) Preparation of ultrathin self-standing polyelectrolyte multilayer membranes at physiological conditions using pH-responsive film segments as sacrificial layers. Nano Lett 6:592–598

    Article  CAS  Google Scholar 

  23. Jiang CY, Tsukruk VV (2006) Freestanding nanostructures via layer-by-layer assembly. Adv Mater 18:829–840

    Article  CAS  Google Scholar 

  24. Delcea M, Möhwald H, Skirtach AG (2011) Stimuli-responsive LbL capsules and nanoshells for drug delivery. Adv Drug Deliv Rev 63:730–747

    Article  CAS  Google Scholar 

  25. Johnston APR, Cortez C, Angelatos AS, Caruso F (2006) Layer-by-layer engineered capsules and their applications. Curr Opin Colloid Interface Sci 11:203–209

    Article  CAS  Google Scholar 

  26. Peyratout CS, Dähne L (2004) Tailor-made polyelectrolyte microcapsules: from multilayers to smart containers. Angew Chem Int Ed 43:3762–3783

    Article  CAS  Google Scholar 

  27. Mamedov AA, Kotov NA (2000) Free-standing layer-by-layer assembled films of magnetite nanoparticles. Langmuir 16:5530–5533

    Article  CAS  Google Scholar 

  28. Mamedov AA, Kotov NA, Prato M, Guldi DM, Wicksted JP, Hirsch A (2002) Molecular design of strong single-wall carbon nanotube/polyelectrolyte multilayer composites. Nat Mater 1:190–194

    Article  CAS  Google Scholar 

  29. Lutkenhaus JL, Hrabak KD, McEnnis K, Hammond PT (2005) Elastomeric flexible free-standing hydrogen-bonded nanoscale assemblies. J Am Chem Soc 127:17228–17234

    Article  CAS  Google Scholar 

  30. Ma Y, Sun JQ, Shen JC (2007) Ion-triggered exfoliation of layer-by-layer assembled poly(acrylic acid)/poly(allylamine hydrochloride) films from substrates: a facile way to prepare free-standing multilayer films. Chem Mater 19:5058–5062

    Article  CAS  Google Scholar 

  31. Wu JJ, Wang YX, Long YH, Gao H, Zhang XL, Zhao N, Cai YL, Xu J (2011) Mussel-inspired chemistry for robust and surface-modifiable multilayer films. Langmuir 27:13684–13691

    Article  CAS  Google Scholar 

  32. Dubas ST, Farhat TR, Schlenoff JB (2001) Multiple membranes from “true” polyelectrolyte multilayers. J Am Chem Soc 123:5368–5369

    Article  CAS  Google Scholar 

  33. Jiang CY, Markutsya S, Pikus Y, Tsukruk VV (2004) Freely suspended nanocomposite membranes as highly sensitive sensors. Nat Mater 3:721–728

    Article  CAS  Google Scholar 

  34. Zhuk A, Pavlukhina S, Sukhishvili SA (2009) Hydrogen-bonded layer-by-layer temperature-triggered release films. Langmuir 25:14025–14029

    Article  CAS  Google Scholar 

  35. Zhao CZ, Zhang JW, Yuan GC, Han CC (2013) CO2-triggered liquid–solid switching through a jamming mechanism. RSC Adv 3:9645–9648

    Article  CAS  Google Scholar 

  36. Han DH, Tong X, Boissière O, Zhao Y (2012) General strategy for making CO2-switchable polymers. ACS Macro Lett 1:57–61

    Article  CAS  Google Scholar 

  37. Zhao Q, Qian JW, An QF, Du BY (2009) Speedy fabrication of free-standing layer-by-layer multilayer films by using polyelectrolyte complex particles as building blocks. J Mater Chem 19:8448–8455

    Article  CAS  Google Scholar 

  38. Gui ZL, Qian JW, Du BY, Yin MJ, An QF (2009) Fabrication of free-standing polyelectrolyte multilayer films: a method using polysulfobetaine-containing films as sacrificial layers. J Colloid Interface Sci 340:35–41

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Basic Research Program of China (2013CB834502), the Germany-China Joint Project TRR61 (DFG-NSFC Transregio Project), and the National Natural Science Foundation of China (51303195, 21304105). We thank Mr. Jun Xu at Tsinghua University for his kind help with AFM imaging. We thank Prof. Xi Zhang of Tsinghua University for the useful discussions.

Author information

Authors and Affiliations

  1. Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, People’s Republic of China

    Jiawei Zhang, Bin Yuan & Zhiqiang Wang

  2. Division of Polymer and Composite Materials, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, People’s Republic of China

    Jiawei Zhang & Tao Chen

Authors
  1. Jiawei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bin Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhiqiang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tao Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jiawei Zhang.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 1,744 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, J., Yuan, B., Wang, Z. et al. Fabrication of free-standing multilayer films by using pH-responsive microgels as sacrificial layers. Colloid Polym Sci 292, 1235–1240 (2014). https://doi.org/10.1007/s00396-014-3188-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-014-3188-x

Keywords

Search

Navigation