Complex Förster energy transfer interactions between semiconductor quantum dots and a redox-active osmium assembly

Michael H. Stewart, Alan L. Huston, Amy M. Scott, Alexander L. Efros, Joseph S. Melinger, Kelly Boeneman Gemmill, Scott A. Trammell, Juan B. Blanco-Canosa, Philip E. Dawson, Igor L. Medintz

Research output: Contribution to journalArticle

43 Scopus citations

Abstract

The ability of luminescent semiconductor quantum dots (QDs) to engage in diverse energy transfer processes with organic dyes, light-harvesting proteins, metal complexes, and redox-active labels continues to stimulate interest in developing them for biosensing and light-harvesting applications. Within biosensing configurations, changes in the rate of energy transfer between the QD and the proximal donor, or acceptor, based upon some external (biological) event form the principle basis for signal transduction. However, designing QD sensors to function optimally is predicated on a full understanding of all relevant energy transfer mechanisms. In this report, we examine energy transfer between a range of CdSe-ZnS core-shell QDs and a redox-active osmium(II) polypyridyl complex. To facilitate this, the Os complex was synthesized as a reactive isothiocyanate and used to label a hexahistidine-terminated peptide. The Os-labeled peptide was ratiometrically self-assembled to the QDs via metal affinity coordination, bringing the Os complex into close proximity of the nanocrystal surface. QDs displaying different emission maxima were assembled with increasing ratios of Os-peptide complex and subjected to detailed steady-state, ultrafast transient absorption, and luminescence lifetime decay analyses. Although the possibility exists for charge transfer quenching interactions, we find that the QD donors engage in relatively efficient Förster resonance energy transfer with the Os complex acceptor despite relatively low overall spectral overlap. These results are in contrast to other similar QD donor-redox-active acceptor systems with similar separation distances, but displaying far higher spectral overlap, where charge transfer processes were reported to be the dominant QD quenching mechanism.

Original languageEnglish (US)
Pages (from-to)5330-5347
Number of pages18
JournalACS Nano
Volume6
Issue number6
DOIs
StatePublished - Jun 26 2012
Externally publishedYes

Keywords

  • FRET
  • charge transfer
  • coordination
  • electron transfer
  • metal affinity
  • metal complex
  • osmium
  • peptide
  • polypyridyl
  • quantum dot
  • redox
  • semiconductor

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

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  • Cite this

    Stewart, M. H., Huston, A. L., Scott, A. M., Efros, A. L., Melinger, J. S., Gemmill, K. B., Trammell, S. A., Blanco-Canosa, J. B., Dawson, P. E., & Medintz, I. L. (2012). Complex Förster energy transfer interactions between semiconductor quantum dots and a redox-active osmium assembly. ACS Nano, 6(6), 5330-5347. https://doi.org/10.1021/nn301177h