4.8 Article

Direct Measurement of Length Scale Dependence of the Hydrophobic Free Energy of a Single Collapsed Polymer Nanosphere

Journal

PHYSICAL REVIEW LETTERS
Volume 122, Issue 4, Pages -

Publisher

AMER PHYSICAL SOC
DOI: 10.1103/PhysRevLett.122.047801

Keywords

-

Funding

  1. NSFC [21522402, 21774057, 11674153, 11334004]
  2. Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions
  3. Fundamental Research Funds for the Central Universities [14380080, 14380098, 14380090]

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The physics underlying hydrophobicity at macroscopic and microscopic levels is fundamentally distinct. However, experimentally quantifying the length scale dependence of hydrophobicity is challenging. Here we show that the size-dependent hydrophobic free energy of a collapsed polymer nanosphere can be continuously monitored from its single-molecule force-extension curve using a novel theoretical framework. The hydrophobic free energy shows a change from cubic to square dependence of the radius of the polymer nanosphere at a radius of similar to 1 nm-this is consistent with Lum-Chandler-Weeks theory and simulations. We can also observe a large variation of the hydrophobic free energy of each polymer nanosphere implying the heterogeneity of the self-assembled structures and/or the fluctuation of the water-polymer interface. We expect that our approach can be used to address many fundamental questions about hydrophobic hydration, which are otherwise inaccessible by ensemble measurements.

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