Deciphering and Controlling Structural and Functional Parameters of the Shells in Vesicle-Templated Polymer Nanocapsules

Dergunov, Sergey A.; Richter, Andrew George; Kim, Mariya D.; Pingali, Sai Venkatesh; Urban, Volker S.; Pinkhassik, Eugene

doi:10.1021/acs.langmuir.9b01495

Title: Deciphering and Controlling Structural and Functional Parameters of the Shells in Vesicle-Templated Polymer Nanocapsules

Journal Article · Mon Aug 12 00:00:00 EDT 2019 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.9b01495· OSTI ID:1785618

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Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry
Valparaiso Univ., IN (United States). Dept. of Physics and Astronomy
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Structural Molecular Biology

Vesicle-templated nanocapsules are prepared by polymerization of hydrophobic acrylic monomers and crosslinkers in the hydrophobic interior of self-assembled bilayers. Understanding the mechanism of capsule formation and the influence of synthetic parameters on the structural features and functional performance of nanocapsules is critical for the rational design of functional nanodevices, an emerging trend of application of the nanocapsule platform. This study investigated the relationship between basic parameters of the formulation and synthesis of nanocapsules and structural and functional characteristics of the resulting structures. Variations in the monomer/surfactant ratio, temperature of polymerization, and the molar fraction of the free-radical initiators were investigated with a multipronged approach, including shell thickness measurements using small-angle neutron scattering, evaluation of the structural integrity of nanocapsules with scanning electron microscopy, and determination of the retention of entrapped molecules using absorbance and fluorescence spectroscopy. Surprisingly, the thickness of the shells did not correlate with the monomer/surfactant ratio, supporting the hypothesis of substantial stabilization of the surfactant bilayer with loaded monomers. Decreasing the temperature of polymerization had no effect on the spherical structure of nanocapsules but resulted in progressively lower retention of entrapped molecules, suggesting that a spherical skeleton of nanocapsule forms rapidly, followed by filling the gaps to create the structure without pinholes. Lower content of initiators resulted in slower reactions, outlining the baseline conditions for practical synthetic protocols. Taken together, these findings provide insights into the formation of nanocapsules and offer methods for controlling the properties of nanocapsules in viable synthetic methods.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; CHE-1709921; CHE-1012951; CHE-1522525; CHE-1316680

OSTI ID:: 1785618

Journal Information:: Langmuir, Vol. 35, Issue 40; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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