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Phys Rev Lett. 2007 Aug 10;99(6):066104. Epub 2007 Aug 8.

Charge regulation as a stabilization mechanism for shell-like assemblies of polyoxometalates.

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  • 1Van 't Hoff Laboratory for Physical and Colloid Chemistry, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.


We show that the equilibrium size of single-layer shells composed of polyoxometalate macroions is inversely proportional to the dielectric constant of the medium in which they are dispersed. This behavior is consistent with a stabilization mechanism based on Coulomb repulsion combined with charge regulation. We estimate the cohesive energy per bond between macroions on the shells to be approximately -6kT. This number is extracted from analysis based on a charge regulation model in combination with a model for defects on a sphere. The value of the cohesive bond energy is in agreement with the model-independent critical aggregate concentration. This observation points to a new class of thermodynamically stable shell-like objects. We point out the possible relevance our findings have for certain surfactant systems.

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