The intrinsic role of nanoconfinement in chemical equilibrium: Evidence from DNA hybridization

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33 Scopus citations


Recently we predicted that when a reaction involving a small number of molecules occurs in a nanometric-scale domain entirely segregated from the surrounding media, the nanoconfinement can shift the position of equilibrium toward products via reactant-product reduced mixing. In this Letter, we demonstrate how most-recently reported single-molecule fluorescence measurements of partial hybridization of ssDNA confined within nanofabricated chambers provide the first experimental confirmation of this entropic nanoconfinement effect. Thus, focusing separately on each occupancy-specific equilibrium constant, quantitatively reveals extra stabilization of the product upon decreasing the chamber occupancy or size. Namely, the DNA hybridization under nanoconfined conditions is significantly favored over the identical reaction occurring in bulk media with the same reactant concentrations. This effect, now directly verified for DNA, can be relevant to actual biological processes, as well as to diverse reactions occurring within molecular capsules, nanotubes, and other functional nanospaces.

Original languageEnglish
Pages (from-to)2247-2251
Number of pages5
JournalNano Letters
Issue number5
StatePublished - 8 May 2013


  • DNA hybridization
  • Nanochemical equilibrium
  • equilibrium constant
  • mixing entropy
  • nanoconfinement

ASJC Scopus subject areas

  • Bioengineering
  • Chemistry (all)
  • Materials Science (all)
  • Condensed Matter Physics
  • Mechanical Engineering


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