DMREF: Collaborative Research: Interface-promoted Assembly and Disassembly Processes for Rapid Manufacture and Transport of Complex Hybrid Nanomaterials, NSF DMREF #1629094 ($552,901), #1629156 ($713,281), #1629078 ($320,001); Karen L. Wooley (TAMU), Arthi Jayaraman (UD), Darrin J. Pochan (UD), and William Johnson (UU), 10/01/2016 - 09/30/2020 (with 1 year no cost extension)

Intellectual Merit: This DMREF project focused on developing and applying integrated computational and experimental approaches to rapidly design and manufacture hybrid inorganic-organic nanostructured objects (HIONs) possessing complex compositions, structures, and transport properties, with an emphasis on their use for purification of contaminated water in porous media (e.g., water in contaminated soil).  On the fundamental side, synergistic coarse-grained molecular dynamics simulations and experiments (Figure 1) elucidated the complex interplay of chemistry (e.g., hydrophobic, hydrophilic, charged groups) and architecture within non-linear amphiphilic polymers (e.g., comb-coil, brush-coil, bottlebrush, star) in bulk solutions and near chemically-heterogeneous interfaces that led to assembled organic polymers and HIONs of different shapes, sizes, and morphologies.  Theoretical and experimental studies of model colloidal particles and synthesized realistic HIONs near surfaces (Figure 2) with discrete nanoscale heterogeneity further provided mechanistic prediction of nanoparticle retention and release from these surfaces in response to perturbations in solution conditions and fluid flow.

Besides improved fundamental understanding of these complex polymer materials and deployment of model materials during field trips to developing countries, we accomplished unique methodological advances in synthesis, soft materials characterization, computational methods for predicting molecular structure and morphology (e.g., CREASE) as well as transport at the colloidal level. In terms of technological broader impact value, the DMREF project combined the functions of inorganic and organic components within nanostructured assemblies specifically for deployment in environmental cleanup, however, these materials have potential use in many fields involved in complex nanoparticle loading, delivery, and retention, such as environmental remediation, biomedicine, and energy.

Broader Impacts: In terms of workforce development, the training of researchers was enhanced through participation in our DMREF program, with integration of theory, simulation and experiments across multiple length and time scales, and combination of the disciplines of chemistry, geosciences, chemical and materials science and engineering:  13 graduate students (9 women, 1 URM), 4 postdocs (2 women, 1 URM), and several undergraduates were mentored and trained on this project, with partial or full support. All DMREF researchers met in-person at UD, TAMU and UU for three annual in-person meetings that were comprised of research presentations and discussions about current and future research, education, outreach, and data sharing endeavors (Figure 3).  These meetings provided further training opportunities for students and postdocs to develop communication skills for conveying research to interdisciplinary groups.  Key outcomes included the identification of specific data, images, and figures, together with drafting of detailed outlines and timelines for completion of joint publications of research accomplished across laboratories, and also the development of strategies and goals to continue to evolve the combined computational and experimental works to predictive levels.

Last Modified: 01/04/2022
Modified by: Karen L Wooley