Evolution of Aggregate Structure in Solutions of Anionic Monorhamnolipids: Experimental and Computational Results

Ryan J. Eismin, Elango Munusamy, Laurel L. Kegel, David E. Hogan, Raina M. Maier, Steven D. Schwartz, Jeanne E. Pemberton

Research output: Research - peer-reviewArticle

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Abstract

The evolution of solution aggregates of the anionic form of the native monorhamnolipid (mRL) mixture produced by Pseudomonas aeruginosa ATCC 9027 is explored at pH 8.0 using both experimental and computational approaches. Experiments utilizing surface tension measurements, dynamic light scattering, and both steady-state and time-resolved fluorescence spectroscopy reveal solution aggregation properties. All-atom molecular dynamics simulations on self-assemblies of the most abundant monorhamnolipid molecule, l-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (Rha-C10-C10), in its anionic state explore the formation of aggregates and the role of hydrogen bonding, substantiating the experimental results. At pH 8.0, at concentrations above the critical aggregation concentration of 201 μM but below ∼7.5 mM, small premicelles exist in solution; above ∼7.5 mM, micelles with hydrodynamic radii of ∼2.5 nm dominate, although two discrete populations of larger lamellar aggregates (hydrodynamic radii of ∼10 and 90 nm) are also present in solution in much smaller number densities. The critical aggregation number for the micelles is determined to be ∼26 monomers/micelle using fluorescence quenching measurements, with micelles gradually increasing in size with monorhamnolipid concentration. Molecular dynamics simulations on systems with between 10 and 100 molecules of Rha-C10-C10 indicate the presence of stable premicelles of seven monomers with the most prevalent micelle being ∼25 monomers and relatively spherical. A range of slightly larger micelles of comparable stability can also exist that become increasing elliptical with increasing monomer number. Intermolecular hydrogen bonding is shown to play a significant role in stabilization of these aggregates. In total, the computational results are in excellent agreement with the experimental results.

LanguageEnglish (US)
Pages7412-7424
Number of pages13
JournalLangmuir
Volume33
Issue number30
DOIs
StatePublished - Aug 1 2017

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micelles
Micelles
monomers
Monomers
Agglomeration
hydrodynamics
molecular dynamics
fluorescence
radii
hydrogen
molecules
simulation
Molecular dynamics
Hydrogen bonds
Hydrodynamics
Molecules
Computer simulation
pseudomonas
self assembly
interfacial tension

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

Cite this

Evolution of Aggregate Structure in Solutions of Anionic Monorhamnolipids : Experimental and Computational Results. / Eismin, Ryan J.; Munusamy, Elango; Kegel, Laurel L.; Hogan, David E.; Maier, Raina M.; Schwartz, Steven D.; Pemberton, Jeanne E.

In: Langmuir, Vol. 33, No. 30, 01.08.2017, p. 7412-7424.

Research output: Research - peer-reviewArticle

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