Letter | Published:

Gold nanocages covered by smart polymers for controlled release with near-infrared light

Nature Materials volume 8, pages 935939 (2009) | Download Citation

Subjects

Abstract

Photosensitive caged compounds have enhanced our ability to address the complexity of biological systems by generating effectors with remarkable spatial/temporal resolutions1,2,3. The caging effect is typically removed by photolysis with ultraviolet light to liberate the bioactive species. Although this technique has been successfully applied to many biological problems, it suffers from a number of intrinsic drawbacks. For example, it requires dedicated efforts to design and synthesize a precursor compound for each effector. The ultraviolet light may cause damage to biological samples and is suitable only for in vitro studies because of its quick attenuation in tissue4. Here we address these issues by developing a platform based on the photothermal effect of gold nanocages. Gold nanocages represent a class of nanostructures with hollow interiors and porous walls5. They can have strong absorption (for the photothermal effect) in the near-infrared while maintaining a compact size. When the surface of a gold nanocage is covered with a smart polymer, the pre-loaded effector can be released in a controllable fashion using a near-infrared laser. This system works well with various effectors without involving sophisticated syntheses, and is well suited for in vivo studies owing to the high transparency of soft tissue in the near-infrared region6.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    & Controlling cell chemistry with caged compounds. Annu. Rev. Physiol. 55, 755–784 (1993).

  2. 2.

    , & Photochemical tools for remote control of ion channels in excitable cells. Nature Chem. Bio. 7, 360–365 (2005).

  3. 3.

    & Biologically active molecules with a light switch. Angew. Chem. Int. Ed. 45, 4900–4921 (2006).

  4. 4.

    et al. Interleukin-12 suppresses ultraviolet radiation-induced apoptosis by inducing DNA repair. Nature Cell Bio. 4, 26–31 (2002).

  5. 5.

    et al. Facile synthesis of gold-silver nanocages with controllable pores on the surface. J. Am. Chem. Soc. 128, 14776–14777 (2006).

  6. 6.

    A clearer vision for in vivo imaging. Nature Biotechnol. 19, 316–317 (2001).

  7. 7.

    et al. Gold nanocages: Synthesis, properties, and applications. Acc. Chem. Res. 41, 1587–1595 (2008).

  8. 8.

    Hydrogels for biomedical applications. Adv. Drug Deliv. Rev. 43, 3–12 (2002).

  9. 9.

    et al. A quantitative study on the photothermal effect of immuno gold nanocages targeted to breast cancer cells. ACS Nano 2, 1645–1652 (2008).

  10. 10.

    , , & Optofluidic control using photothermal nanoparticles. Nature Mater. 5, 27–32 (2005).

  11. 11.

    , , & Effect of nanoconfinement on the collapse transition of responsive polymer brushes. Nano Lett. 8, 3819–3824 (2008).

  12. 12.

    & Combining atom transfer radical polymerization and disulphide/thiol redox chemistry: A route to well-defined (bio)degradable polymeric materials. Macromolecules 38, 3087–3092 (2005).

  13. 13.

    , & Amphiphilic sun-shaped polymers by grafting macrocyclic copolyesters with PEO. Macromolecules 41, 650–654 (2008).

  14. 14.

    et al. Ultrafast laser studies of the photothermal properties of gold nanocages. J. Phys. Chem. B 110, 1520–1524 (2006).

  15. 15.

    , & How does a gold nanorod melt? J. Phys. Chem. B 104, 7867–7870 (2000).

  16. 16.

    et al. Remotely triggered liposome release by near-infrared light absorption via hollow gold nanoshells. J. Am. Chem. Soc. 130, 8175–8177 (2008).

  17. 17.

    et al. Oxidation-triggered release of fluorescent molecules or drugs from mesoporous Si microparticles. ACS Nano 2, 2401–2409 (2008).

  18. 18.

    et al. Immuno gold nanocages with tailored optical properties for targeted photothermal destruction of cancer cells. Nano Lett. 7, 1318–1322 (2007).

  19. 19.

    & Biological activity of lysozyme after entrapment in poly(d,l-lactide-co-glycolide) microspheres. Pharm. Res. 14, 1556–1562 (1997).

  20. 20.

    & Encapsulation of proteins in biodegradable polymeric microparticles using electrospray in the taylor cone-jet mode. Biotechnol. Bioeng. 97, 1278–1290 (2007).

  21. 21.

    , , , & Lysozyme stability in primary emulsion for PLGA microsphere preparation: Effect of recovery methods and stabilizing excipients. Pharm. Res. 19, 629–633 (2002).

  22. 22.

    , , & Effect of additives on encapsulation efficiency, stability, and bioactivity of entrapped lysozyme from biodegradable polymer particles. J. Microencapsul. 22, 127–138 (2005).

  23. 23.

    , , & The effect of a water/organic solvent interface on the structural stability of lysozyme. J. Controlled Release 68, 351–359 (2000).

  24. 24.

    , , & Expanding the optical trapping range of gold nanoparticles. Nano Lett. 5, 1937–1942 (2005).

  25. 25.

    , , , & Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem. Rev. 105, 1103–1170 (2005).

  26. 26.

    et al. Gold nanocages: Bioconjugation and their potential use as optical imaging contrast agents. Nano Lett. 5, 473–477 (2005).

  27. 27.

    , , & Facile synthesis of Ag nanocubes and Au nanocages. Nature Protocols 2, 2182–2190 (2007).

  28. 28.

    , , & Rapid synthesis of small silver nanocubes by mediating polyol reduction with a trace amount of sodium sulfide or sodium hydrosulfide. Chem. Phys. Lett. 432, 491–496 (2006).

Download references

Acknowledgements

This work was supported by a 2006 Director’s Pioneer Award from the NIH (DP1 OD000798). Part of the work was carried out at the Nano Research Facility (NRF), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the NSF under award no. ECS-0335765. NRF is part of School of Engineering and Applied Science at Washington University in St Louis.

Author information

Author notes

    • Mustafa S. Yavuz
    • , Yiyun Cheng
    •  & Jingyi Chen

    These three authors contributed equally to this project

Affiliations

  1. Department of Biomedical Engineering, Washington University, St Louis, Missouri 63130, USA

    • Mustafa S. Yavuz
    • , Yiyun Cheng
    • , Jingyi Chen
    • , Claire M. Cobley
    • , Qiang Zhang
    • , Matthew Rycenga
    • , Jingwei Xie
    • , Chulhong Kim
    • , Kwang H. Song
    • , Andrea G. Schwartz
    • , Lihong V. Wang
    •  & Younan Xia

Authors

  1. Search for Mustafa S. Yavuz in:

  2. Search for Yiyun Cheng in:

  3. Search for Jingyi Chen in:

  4. Search for Claire M. Cobley in:

  5. Search for Qiang Zhang in:

  6. Search for Matthew Rycenga in:

  7. Search for Jingwei Xie in:

  8. Search for Chulhong Kim in:

  9. Search for Kwang H. Song in:

  10. Search for Andrea G. Schwartz in:

  11. Search for Lihong V. Wang in:

  12. Search for Younan Xia in:

Contributions

M.S.Y. and Y.C. synthesized the alizarin-PEG dye and polymers, carried out the loading and controlled-release experiments and did data analysis. J.C., C.M.C. and A.G.S. carried out the synthesis, surface modification and characterization of Au nanocages. C.M.C. and Q.Z. synthesized the Ag nanocubes. M.R. analysed the mechanism for laser-triggered release. C.K., K.H.S. and L.V.W. were involved in the planning of laser-triggered release experiments and helped with the analysis on Au nanocage melting. J.C. and J.X. conducted the cell viability, protein assay and enzyme activity assays. Y.X. conceived the strategy, supervised the experiments and prepared different versions of the manuscript.

Corresponding author

Correspondence to Younan Xia.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    Supplementary Information

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nmat2564

Further reading