Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Electrostatically gated membrane permeability in inorganic protocells

Nature Chemistry volume 5, pages 529–536 (2013)Cite this article

Subjects

Abstract

Although several strategies are now available to produce functional microcompartments analogous to primitive cell-like structures, little progress has been made in generating protocell constructs with self-controlled membrane permeability. Here we describe the preparation of water-dispersible colloidosomes based on silica nanoparticles and delineated by a continuous semipermeable inorganic membrane capable of self-activated, electrostatically gated permeability. We use crosslinking and covalent grafting of a pH-responsive copolymer to generate an ultrathin elastic membrane that exhibits selective release and uptake of small molecules. This behaviour, which depends on the charge of the copolymer coronal layer, serves to trigger enzymatic dephosphorylation reactions specifically within the protocell aqueous interior. This system represents a step towards the design and construction of alternative types of artificial chemical cells and protocell models based on spontaneous processes of inorganic self-organization.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Chemical construction of water-dispersible aqueous inorganic microcompartments with self-activated gated membrane permeability.
Figure 2: Optical micrographs of silica nanoparticle-stabilized aqueous microcompartments.
Figure 3: Release properties of inorganic cell-like microstructures.
Figure 4: Uptake properties of crosslinked copolymer-functionalized colloidosomes.
Figure 5: Enzyme-mediated dephosphorylation in inorganic protocells.

Similar content being viewed by others

References

  1. Stano, P., Carrara, P., Kuruma, Y., Souza, T & Luisi, P. L. Compartmentalized reactions as a case of soft-matter biotechnology: synthesis of proteins and nucleic acids inside lipid vesicles. J. Mater. Chem. 21, 18887–18902 (2011).

    Article  CAS  Google Scholar 

  2. Pohorille, A. & Deamer, D. Artificial cells: prospects for biotechnology. Trends Biotech. 20, 123–128 (2002).

    Article  CAS  Google Scholar 

  3. Städler, B. et al. Polymer hydrogel capsules: en route toward synthetic cellular systems. Nanoscale 1, 68–73 (2009).

    Article  Google Scholar 

  4. Szostak, J. W., Bartel, D. P. & Luisi, P. L. Synthesizing life. Nature 409, 387–390 (2001).

    Article  CAS  Google Scholar 

  5. Mann, S. Systems of creation: the emergence of life from non-living matter. Acc. Chem. Res. 45, 2131–2141 (2012).

    Article  CAS  Google Scholar 

  6. Stano, P. & Luisi, P. L. Achievements and open questions in the self-reproduction of vesicles and synthetic minimal cells. Chem. Commun. 46, 3639–3653 (2010).

    Article  CAS  Google Scholar 

  7. Dzieciol, A. & Mann, S. Designs for life: protocell models in the laboratory. Chem. Soc. Rev. 41, 79–85 (2012).

    Article  CAS  Google Scholar 

  8. Walde, P. Building artificial cells and protocell models: experimental approaches with lipid vesicles. Bioessays 32, 296–303 (2010).

    Article  CAS  Google Scholar 

  9. Koga, S., Williams, D. S., Perriman, A. W. & Mann, S. Peptide/nucleotide micro-droplets as a step towards a membrane-free protocell model. Nature Chem. 3, 720–724 (2011).

    Article  CAS  Google Scholar 

  10. Williams, D. S. et al. Polymer/nucleotide droplets as bio-inspired functional micro-compartments. Soft Matter 8, 6004–6014 (2012).

    Article  CAS  Google Scholar 

  11. Li, M., Green, D. C., Anderson, J. L. R., Binks, B. P. & Mann, S. In vitro gene expression and enzyme catalysis in bio-inorganic protocells. Chem. Sci. 2, 1739–1745 (2011).

    Article  CAS  Google Scholar 

  12. Cooper, G. J. T. et al. Modular redox-active inorganic chemical cells: iCHELLs. Angew. Chem. Int. Ed. 50, 10373–10376 (2011).

    Article  CAS  Google Scholar 

  13. Subramaniam, A. B., Wan, J., Gopinath, A. & Stone, H. A. Semi-permeable vesicles composed of natural clay. Soft Matter 7, 2600–2612 (2011).

    Article  CAS  Google Scholar 

  14. Dinsmore, A. D. et al. Colloidosomes: selectively permeable capsules composed of colloidal particles. Science 298, 1006–1008 (2002).

    Article  CAS  Google Scholar 

  15. Wu, C., Bai, S., Ansorge-Schumacher, M. B. & Wang, D. Nanoparticle cages for enzyme catalysis in organic media. Adv. Mater. 23, 5694–5699 (2011).

    Article  CAS  Google Scholar 

  16. Boker, A., He, J., Emrick, T. & Russell, T. P. Self-assembly of nanoparticles at interfaces. Soft Matter 3, 1231–1248 (2007).

    Article  Google Scholar 

  17. Wang, D. Y., Duan, H. W. & Mohwald, H. The water/oil interface: the emerging horizon for self-assembly of nanoparticles. Soft Matter 1, 412–416 (2005).

    Article  CAS  Google Scholar 

  18. Shah, R. K., Kim, J-W. & Weitz, D. A. Monodisperse stimuli-responsive colloidosomes by self-assembly of microgels in droplets. Langmuir 26, 1561–1565 (2010).

    Article  CAS  Google Scholar 

  19. Hsu, M. F. et al. Self-assembled shells composed of colloidal particles: fabrication and characterization. Langmuir 21, 2963–2970 (2005).

    Article  CAS  Google Scholar 

  20. Thompson, K. L. & Armes, S. P. From well-defined macromonomers to sterically-stabilized latexes to covalently cross-linkable colloidosomes: exerting control over multiple length scales. Chem. Commun. 46, 5274–5276 (2010).

    Article  CAS  Google Scholar 

  21. Subramaniam, A. B., Abkarian, M. & Stone, H. A. Controlled assembly of jammed colloidal shells on fluid droplets. Nature Mater. 4, 553–556 (2005).

    Article  CAS  Google Scholar 

  22. Kim, J-W. et al. Colloidal assembly route for responsive colloidosomes with tunable permeability. Nano Lett. 7, 2876–2880 (2007).

    Article  CAS  Google Scholar 

  23. Lee, D. & Weitz, D. A. Double emulsion-templated nanoparticle colloidosomes with selective permeability. Adv. Mater. 20, 3498–3503 (2008).

    Article  CAS  Google Scholar 

  24. Weaver, J. V. M. & Adams, D. J. Synthesis and application of pH-responsive branched copolymer nanoparticles (PRBNs): a comparison with pH-responsive shell cross-linked micelles. Soft Matter 6, 2575–2582 (2010).

    Article  CAS  Google Scholar 

  25. Harbron, R. L., McDonald, T. O., Rannard, S. P., Findlay, P. H. & Weaver J. V. M. One-pot, single-component synthesis of functional emulsion-templated hybrid inorganic–organic polymer capsules. Chem. Commun. 48, 1592–1594 (2012).

    Article  CAS  Google Scholar 

  26. Martin, W. & Russell, M. J. On the origins of cells: a hypothesis for the evolutionary transitions from abiotic geochemistry to chemoautotrophic prokaryotes, and from prokaryotyes to nucleated cells. Phil. Trans. R. Soc. Lond. B 358, 59–85 (2003).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank Parogle Technologies Ltd for a Collaborative Award in Science and Engineering (CASE) funded studentship for R.L.H, and A. Peacock (Centre for Materials Discovery, University of Liverpool) for running GPC samples. We thank the Engineering and Physical Sciences Research Council and the European Research Council (Advanced Grant scheme) for financial support. This paper is dedicated to the memory of J.V.M.W.

Author information

Authors and Affiliations

  1. Centre for Organized Matter Chemistry, School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK

    Mei Li & Stephen Mann

  2. Departments of Materials and Bioengineering, Imperial College London, London, SW2 7AZ, UK

    Rachel L. Harbron & Jonathan V. M. Weaver

  3. Department of Chemistry, Surfactant & Colloid Group, University of Hull, Hull, HU6 7RX, UK

    Bernard P. Binks

Authors
  1. Mei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rachel L. Harbron
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jonathan V. M. Weaver
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bernard P. Binks
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Stephen Mann
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

M.L. and S.M. conceived the concept, S.M. directed the research, M.L., R.L.H. and J.V.M.W. designed and performed the experiments and analysed the data, and B.P.B. contributed the surface-active nanoparticles and discussions on colloid science. All the authors participated in writing the paper.

Corresponding authors

Correspondence to Mei Li or Stephen Mann.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 6069 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Li, M., Harbron, R., Weaver, J. et al. Electrostatically gated membrane permeability in inorganic protocells. Nature Chem 5, 529–536 (2013). https://doi.org/10.1038/nchem.1644

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.1644

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing