Skip to main content
SpringerLink
Log in

Polyelectrolyte exchange and diffusion in microgel multilayer thin films

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

Abstract

The exchange of the polycation, poly-l-lysine (PLL), within polymeric multi-layer films constructed with anionic poly(N-isopropylacrylamide)–co-acrylic acid (pNIPAm-co-AAc) microgels was explored. Via incorporation of a fluorescent tag on PLL, the incorporation and distribution of PLL was visualized by fluorescence microscopy and optical extinction techniques. Using UV-vis spectrophotometry, the absorbance of PLL during multi-layer film formation was monitored. Distinctive “in” and “out” diffusive properties of the polycation with limited exchange was observed. Additionally, mechanical deformation was used to probe the influence of self-healing on PLL redistribution across an entire multi-layer film depth; CLSM was utilized to compare the fluorescence profile of these films before and after healing, and a lack of polycation exchange throughout the entire microgel-polyelectrolyte film depth was revealed. Importantly, these results stand in contrast to those observed previously in purely linear polyelectrolyte films, which suggests polycation-microgel interactions that are somewhat unique as compared to the interactions observed for purely linear polyelectrolyte complexation.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

References

  1. Nolan CM, Serpe MJ, Lyon LA (2004) Thermally modulated insulin release from microgel thin films. Biomacromolecules 5:1940–1946

    Article  CAS  Google Scholar 

  2. Serpe MJ, Yarmey KA, Nolan CM, Lyon LA (2004) Doxorubicin uptake and release from microgel thin films. Biomacromolecules 6:408–413

    Article  Google Scholar 

  3. Stuart MAC, Huck WTS, Genzer J, Muller M, Ober C, Stamm M, Sukhorukov GB, Szleifer I, Tsukruk VV, Urban M, Winnik F, Zauscher S, Luzinov I, Minko S (2010) Emerging applications of stimuli-responsive polymer materials. Nat Mater 9:101–113

    Article  Google Scholar 

  4. Tokarev I, Minko S (2009) Stimuli-responsive hydrogel thin films. Soft Matter 5:511–524

    Article  CAS  Google Scholar 

  5. White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Sriram SR, Brown EN, Viswanathan S (2001) Autonomic healing of polymer composites. Nature 409:794–797

    Article  CAS  Google Scholar 

  6. Cho SH, White SR, Braun PV (2009) Self-healing polymer coatings. Adv Mater 21:645–649

    Article  CAS  Google Scholar 

  7. Hammond PT (2004) Form and function in multilayer assembly: new applications at the nanoscale. Adv Mater 16:1271–1293

    Article  CAS  Google Scholar 

  8. Decher G (1997) Fuzzy nanoassemblies: toward layered polymeric multicomposites. Science 277:1232–1237

    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. 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 

  12. Iler RK (1966) Multilayers of colloidal particles. J Colloid Interface Sci 21:569–594

    Article  CAS  Google Scholar 

  13. Decher G, Hong JD, Schmitt J (1992) Buildup of ultrathin multilayer films by self-assembly process.3. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces. Thin Solid Films 210:831–835

    Article  Google Scholar 

  14. Kotov NA, Dekany I, Fendler JH (1995) Layer-by-layer self-assembly of polyelectrolyte-semiconductor nanoparticle composite films. J Phys Chem 99:13065–13069

    Article  CAS  Google Scholar 

  15. Lvov Y, Decher G, Sukhorukov G (1993) Assembly of thin-films by means of successive deposition of alternate layers of DNA and poly(allylamine). Macromolecules 26:5396–5399

    Article  CAS  Google Scholar 

  16. Saurer EM, Flessner RM, Sullivan SP, Prausnitz MR, Lynn DM (2010) Layer-by-layer assembly of DNA- and protein-containing films on microneedles for drug delivery to the skin. Biomacromolecules 11:3136–3143

    Article  CAS  Google Scholar 

  17. Schonhoff M (2003) Self-assembled polyelectrolyte multilayers. Curr Opin Colloid Interface Sci 8:86–95

    Article  CAS  Google Scholar 

  18. Lvov Y, Decher G, Mohwald H (1993) Assembly, structural characterization, and thermal-behavior of layer-by-layer deposited ultrathin films of poly(vinyl sulfate) and poly(allylamine). Langmuir 9:481–486

    Article  CAS  Google Scholar 

  19. Picart C, Ladam G, Senger B, Voegel JC, Schaaf P, Cuisinier FJG, Gergely C (2001) Determination of structural parameters characterizing thin films by optical methods: a comparison between scanning angle reflectometry and optical waveguide lightmode spectroscopy. J Chem Phys 115:1086–1094

    Article  CAS  Google Scholar 

  20. Caruso F, Niikura K, Furlong DN, Okahata Y (1997) Ultrathin multilayer polyelectrolyte films on gold: construction and thickness determination.1. Langmuir 13:3422–3426

    Article  CAS  Google Scholar 

  21. Picart C (2008) Polyelectrolyte multilayer films: from physico-chemical properties to the control of cellular processes. Curr Med Chem 15:685–697

    Article  CAS  Google Scholar 

  22. Picart C, Lavalle P, Hubert P, Cuisinier FJG, Decher G, Schaaf P, Voegel JC (2001) Buildup mechanism for poly(l-lysine)/hyaluronic acid films onto a solid surface. Langmuir 17:7414–7424

    Article  CAS  Google Scholar 

  23. Porcel C, Lavalle P, Ball V, Decher G, Senger B, Voegel JC, Schaaf P (2006) From exponential to linear growth in polyelectrolyte multilayers. Langmuir 22:4376–4383

    Article  CAS  Google Scholar 

  24. Lavalle P, Voegel JC, Vautier D, Senger B, Schaaf P, Ball V (2011) Dynamic aspects of films prepared by a sequential deposition of species: perspectives for smart and responsive materials. Adv Mater 23:1191–1221

    Article  CAS  Google Scholar 

  25. Picart C, Mutterer J, Richert L, Luo Y, Prestwich GD, Schaaf P, Voegel JC, Lavalle P (2002) Molecular basis for the explanation of the exponential growth of polyelectrolyte multilayers. Proc Natl Acad Sci U S A 99:12531–12535

    Article  CAS  Google Scholar 

  26. Lavalle P, Picart C, Mutterer J, Gergely C, Reiss H, Voegel JC, Senger B, Schaaf P (2004) Modeling the buildup of polyelectrolyte multilayer films having exponential growth. J Phys Chem B 108:635–648

    Article  CAS  Google Scholar 

  27. Lavalle P, Gergely C, Cuisinier FJG, Decher G, Schaaf P, Voegel JC, Picart C (2002) Comparison of the structure of polyelectrolyte multilayer films exhibiting a linear and an exponential growth regime: an in situ atomic force microscopy study. Macromolecules 35:4458–4465

    Article  CAS  Google Scholar 

  28. Lavalle P, Vivet V, Jessel N, Decher G, Voegel JC, Mesini PJ, Schaaf P (2004) Direct evidence for vertical diffusion and exchange processes of polyanions and polycations in polyelectrolyte multilayer films. Macromolecules 37:1159–1162

    Article  CAS  Google Scholar 

  29. Hubsch E, Ball V, Senger B, Decher G, Voegel JC, Schaaf P (2004) Controlling the growth regime of polyelectrolyte multilayer films: changing from exponential to linear growth by adjusting the composition of polyelectrolyte mixtures. Langmuir 20:1980–1985

    Article  Google Scholar 

  30. Shiratori SS, Rubner MF (2000) Ph-dependent thickness behavior of sequentially adsorbed layers of weak polyelectrolytes. Macromolecules 33:4213–4219

    Article  CAS  Google Scholar 

  31. Dubas ST, Schlenoff JB (1999) Factors controlling the growth of polyelectrolyte multilayers. Macromolecules 32:8153–8160

    Article  CAS  Google Scholar 

  32. Buijs J, Lichtenbelt JWT, Norde W, Lyklema J (1995) Adsorption of monoclonal iggs and their f(ab')(2) fragments onto polymeric surfaces. Colloids Surf B:Biointerfaces 5:11–23

    Article  CAS  Google Scholar 

  33. Ostrander JW, Mamedov AA, Kotov NA (2001) Two modes of linear layer-by-layer growth of nanoparticle-polylectrolyte multilayers and different interactions in the layer-by-layer deposition. J Am Chem Soc 123:1101–1110

    Article  CAS  Google Scholar 

  34. Hendrickson GR, Smith MH, South AB, Lyon LA (2010) Design of multiresponsive hydrogel particles and assemblies. Adv Funct Mater 20:1697–1712

    Article  CAS  Google Scholar 

  35. Lyon LA, Fernandez-Nieves A (2012) The polymer/colloid duality of microgel suspensions. Annu Rev Phys Chem 63:25–43

    Article  CAS  Google Scholar 

  36. Smith MH, Lyon LA (2012) Multifunctional nanogels for siRNA delivery. Acc Chem Res 45:985–993

    Article  CAS  Google Scholar 

  37. South AB, Lyon LA (2010) Autonomic self-healing of hydrogel thin films. Angew Chem Int Ed 49:767–771

    Article  CAS  Google Scholar 

  38. South AB, Whitmire RE, Garcia AJ, Lyon LA (2009) Centrifugal deposition of microgels for the rapid assembly of nonfouling thin films. ACS Appl Mater Interfaces 1:2747–2754

    Article  CAS  Google Scholar 

  39. Clarke KC, Lyon LA (2013) Modulation of the deswelling temperature of thermoresponsive microgel films. Langmuir 29:12852–12857

    Article  CAS  Google Scholar 

  40. Wiedemair J, Serpe MJ, Kim J, Masson J-F, Lyon LA, Mizaikoff B, Kranz C (2006) In-situ AFM studies of the phase-transition behavior of single thermoresponsive hydrogel particles. Langmuir 23:130–137

    Article  Google Scholar 

  41. Gaulding JC, Spears MW, Lyon LA (2013) Plastic deformation, wrinkling, and recovery in microgel multilayers. Polym Chem 4:4890–4896

    Article  CAS  Google Scholar 

  42. Porcel C, Lavalle P, Decher G, Senger B, Voegel JC, Schaaf P (2007) Influence of the polyelectrolyte molecular weight on exponentially growing multilayer films in the linear regime. Langmuir 23:1898–1904

    Article  CAS  Google Scholar 

  43. Elbert DL, Herbert CB, Hubbell JA (1999) Thin polymer layers formed by polyelectrolyte multilayer techniques on biological surfaces. Langmuir 15:5355–5362

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Funding for E.S.H was provided by the Georgia Institute of Technology.

Author information

Authors and Affiliations

  1. School of Chemistry and Biochemistry and the Petit Institute for Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, GA, 30332, USA

    E. S. Herman & L. A. Lyon

  2. Schmid College of Science and Technology, Chapman University, Orange, CA, 92866, USA

    L. A. Lyon

Authors
  1. E. S. Herman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. A. Lyon
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to L. A. Lyon.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 503 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Herman, E.S., Lyon, L.A. Polyelectrolyte exchange and diffusion in microgel multilayer thin films. Colloid Polym Sci 293, 1535–1544 (2015). https://doi.org/10.1007/s00396-015-3547-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-015-3547-2

Keywords

Search

Navigation