The Structure-Function Relationship of PAMAM Dendrimers as Robust Oil Dispersants

ORAL

Abstract

Dendrimers are well-defined fractal-like polymers with a hydrophilic surface and hydrophobic interior. Their encapsulation capacity enables biomedical applications such as drug or gene delivery. Recently, PAMAM (polyamidoamine) dendrimers have also been explored as efficient and biocompatible oil dispersants for oil spill remediation. However, their high cationic surface charge has been shown to be cytotoxic. It is therefore imperative to mitigate cationic charge-induced toxicity. Synergistic experimental approach was performed to examine the effects of varying terminal surface charge on the capacity of dendrimers to disperse model liner, polycyclic aromatic, and hybrid hydrocarbons. The discrete molecular dynamics (DMD) simulations with a new MEDUSA force field were also applied to study PAMAM structure and dynamics. We validated our DMD methods by benchmarking against previous experimental and computational results. Our study indicates that uncharged dendrimers collapse by forming intra-molecular hydrogen bonds, which reduce the hosting capability. On the other hand, changing the surface charges from positive to negative greatly shifts the pKa of tertiary amines of the PAMAM dendrimer interior. As a result, the negatively charged dendrimers have a significant percentage of tertiary amines protonated, $\sim$30{\%}. This unexpected change in interior protonation state cause electrostatic interactions with the anionic terminal groups, leading to contraction and a marked decrease in hydrocarbon hosting capacity.

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Authors

  • Bo Wang

    Clemson Univ

  • Brad Cox

    North Carolnia State University, Vanderbilt University, University of South Carolina, University of Virginia, Francis Marion Univ, Oak Ridge National Laboratory, Massachusetts Institute of Technology, Florida International University, Georgia College, JINR, Tsinghua University, LBNL, GANIL, Austin Peay State University, Lehigh University, University of Pardubice, Universit\'e de Rennes, Austin Peay State University Department of Physics and Astronomy, Oak Ridge National Laboratory, Oak Ridge TN 37831, American Superconductor Corp., Westborough MA 01581, University of North Georgia, Dahlonega GA 30597, Florida State University, Ecole Polytechnique, Space Telescope Science Institute, Fermi National Accelerator Lab, National Optical Astronomy Observatory, Austin Peay State Univerity, North Carolna State University, Florida Intl Univ, University of North Georgia, Clemson University, Clemson Univ, Vanderbilt University/ORNL, Vanderbilt University/Univ. of Kentucky, College of William and Mary, Louisiana State University, Presbyterian College, North Carolina State Univ, Department of Physics, Virginia Tech, Mathematical Institute, University of Oxford, Virginia Tech University, Hollins University, University of Tennessee Space Institute, Davidson College, University of Tennessee, American Superconductor Corporation, University of South Alabama, North Carolina State University, James Madison University, Lousiana State University, Korea Electrotechnology Research Institute, Changwon Korea

  • Brad Cox

    North Carolnia State University, Vanderbilt University, University of South Carolina, University of Virginia, Francis Marion Univ, Oak Ridge National Laboratory, Massachusetts Institute of Technology, Florida International University, Georgia College, JINR, Tsinghua University, LBNL, GANIL, Austin Peay State University, Lehigh University, University of Pardubice, Universit\'e de Rennes, Austin Peay State University Department of Physics and Astronomy, Oak Ridge National Laboratory, Oak Ridge TN 37831, American Superconductor Corp., Westborough MA 01581, University of North Georgia, Dahlonega GA 30597, Florida State University, Ecole Polytechnique, Space Telescope Science Institute, Fermi National Accelerator Lab, National Optical Astronomy Observatory, Austin Peay State Univerity, North Carolna State University, Florida Intl Univ, University of North Georgia, Clemson University, Clemson Univ, Vanderbilt University/ORNL, Vanderbilt University/Univ. of Kentucky, College of William and Mary, Louisiana State University, Presbyterian College, North Carolina State Univ, Department of Physics, Virginia Tech, Mathematical Institute, University of Oxford, Virginia Tech University, Hollins University, University of Tennessee Space Institute, Davidson College, University of Tennessee, American Superconductor Corporation, University of South Alabama, North Carolina State University, James Madison University, Lousiana State University, Korea Electrotechnology Research Institute, Changwon Korea

  • Brad Cox

    North Carolnia State University, Vanderbilt University, University of South Carolina, University of Virginia, Francis Marion Univ, Oak Ridge National Laboratory, Massachusetts Institute of Technology, Florida International University, Georgia College, JINR, Tsinghua University, LBNL, GANIL, Austin Peay State University, Lehigh University, University of Pardubice, Universit\'e de Rennes, Austin Peay State University Department of Physics and Astronomy, Oak Ridge National Laboratory, Oak Ridge TN 37831, American Superconductor Corp., Westborough MA 01581, University of North Georgia, Dahlonega GA 30597, Florida State University, Ecole Polytechnique, Space Telescope Science Institute, Fermi National Accelerator Lab, National Optical Astronomy Observatory, Austin Peay State Univerity, North Carolna State University, Florida Intl Univ, University of North Georgia, Clemson University, Clemson Univ, Vanderbilt University/ORNL, Vanderbilt University/Univ. of Kentucky, College of William and Mary, Louisiana State University, Presbyterian College, North Carolina State Univ, Department of Physics, Virginia Tech, Mathematical Institute, University of Oxford, Virginia Tech University, Hollins University, University of Tennessee Space Institute, Davidson College, University of Tennessee, American Superconductor Corporation, University of South Alabama, North Carolina State University, James Madison University, Lousiana State University, Korea Electrotechnology Research Institute, Changwon Korea

  • Brad Cox

    North Carolnia State University, Vanderbilt University, University of South Carolina, University of Virginia, Francis Marion Univ, Oak Ridge National Laboratory, Massachusetts Institute of Technology, Florida International University, Georgia College, JINR, Tsinghua University, LBNL, GANIL, Austin Peay State University, Lehigh University, University of Pardubice, Universit\'e de Rennes, Austin Peay State University Department of Physics and Astronomy, Oak Ridge National Laboratory, Oak Ridge TN 37831, American Superconductor Corp., Westborough MA 01581, University of North Georgia, Dahlonega GA 30597, Florida State University, Ecole Polytechnique, Space Telescope Science Institute, Fermi National Accelerator Lab, National Optical Astronomy Observatory, Austin Peay State Univerity, North Carolna State University, Florida Intl Univ, University of North Georgia, Clemson University, Clemson Univ, Vanderbilt University/ORNL, Vanderbilt University/Univ. of Kentucky, College of William and Mary, Louisiana State University, Presbyterian College, North Carolina State Univ, Department of Physics, Virginia Tech, Mathematical Institute, University of Oxford, Virginia Tech University, Hollins University, University of Tennessee Space Institute, Davidson College, University of Tennessee, American Superconductor Corporation, University of South Alabama, North Carolina State University, James Madison University, Lousiana State University, Korea Electrotechnology Research Institute, Changwon Korea

  • Brad Cox

    North Carolnia State University, Vanderbilt University, University of South Carolina, University of Virginia, Francis Marion Univ, Oak Ridge National Laboratory, Massachusetts Institute of Technology, Florida International University, Georgia College, JINR, Tsinghua University, LBNL, GANIL, Austin Peay State University, Lehigh University, University of Pardubice, Universit\'e de Rennes, Austin Peay State University Department of Physics and Astronomy, Oak Ridge National Laboratory, Oak Ridge TN 37831, American Superconductor Corp., Westborough MA 01581, University of North Georgia, Dahlonega GA 30597, Florida State University, Ecole Polytechnique, Space Telescope Science Institute, Fermi National Accelerator Lab, National Optical Astronomy Observatory, Austin Peay State Univerity, North Carolna State University, Florida Intl Univ, University of North Georgia, Clemson University, Clemson Univ, Vanderbilt University/ORNL, Vanderbilt University/Univ. of Kentucky, College of William and Mary, Louisiana State University, Presbyterian College, North Carolina State Univ, Department of Physics, Virginia Tech, Mathematical Institute, University of Oxford, Virginia Tech University, Hollins University, University of Tennessee Space Institute, Davidson College, University of Tennessee, American Superconductor Corporation, University of South Alabama, North Carolina State University, James Madison University, Lousiana State University, Korea Electrotechnology Research Institute, Changwon Korea