Free-energy predictions and absorption spectra calculations for supramolecular nanocarriers and their photoactive cargo

Adriana Pietropaolo, Sicheng Tang, Francisco Raymo

Research output: Contribution to journalArticle

5 Scopus citations

Abstract

We reconstructed the free-energy landscape for supramolecular nanoparticles of amphiphilic methacrylated-based co-polymers. Their self-assembly in aqueous solution and encapsulation of borondipyrromethene (BODIPY) derivatives were enforced through atomistic free-energy simulations. The BODIPY binding modes detected in each of the free-energy basins were validated through a comparison of theoretical absorption spectra, calculated at the TD-DFT level, to their experimental counterparts. The nanoparticle distribution is controlled within a thermodynamic regime, with free-energy barriers approaching 8 kcal mol-1, enabling the existence of different-sized nanoparticles in aqueous solution at room temperature. Two types of supramolecular morphologies were identified. One is compact and spherical in shape and the other is large and donut-like, with the former more stable than the latter by 4 kcal mol-1. The morphology of the supramolecular host affects the binding mode of the BODIPY guests. Stacked BODIPY aggregates are encapsulated in the spherical nanocarriers, whereas isolated chromophores associate with the donut-shaped assemblies.

Original languageEnglish (US)
Pages (from-to)4989-4994
Number of pages6
JournalNanoscale
Volume9
Issue number15
DOIs
StatePublished - Apr 21 2017

ASJC Scopus subject areas

  • Materials Science(all)

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