Computational Design of Nanostructured Soft Interfaces: Focus on Shape Changes and Spreading of Cubic Nanogels.

Understanding the dynamics of gels at soft interfaces is vital for a range of applications, from biocatalysis and drug delivery to enhanced oil recovery applications. Herein, we use dissipative particle dynamics simulations to focus on the shape changes of a cubic nanogel as it adsorbs from the aqueous phase onto the oil-water interface, effectively acting as a compatibilizer. Upon adsorption at the interface, the hydrogel spreads over the interface, adopting various shapes depending on its size and cross-link density. We characterize these shapes by the shape anisotropy and an effective extent of spreading. We highlight the differences between these characteristics for cubic and spherical nanogels and show that the choice of the cubic shape over the spherical one results in a wider range of topographies that could be dynamically prescribed onto the soft interface due to the gels' adsorption. We first validate our model parameters with respect to the known experimental values for polyacrylamide (PAAm) gels and focus on spreading and shape changes of PAAm nanogels onto the oil-water interfaces. We then probe the behavior of active gels by changing an affinity of the polymer matrix for the solvent, which can be caused by the application of an external stimulus (light, temperature, or change in the chemical composition of solvent). Furthermore, we focus on the interactions between multiple gels placed at the liquid-liquid interface. We show that controlling the shapes and the clustering of the gels at the interfaces via variations in solvent quality result in tailoring the dynamics and topography of soft nanostructured interfaces. Hence, our findings provide insights into the design of soft active nanostructured interfaces with topographies controlled externally via solvent quality.

Controlling Degradation and Erosion of Polymer Networks: Insights from Mesoscale Modeling.

Understanding and controlling degradation of polymer networks on the mesoscale is critical for a range of applications. We utilize dissipative particle dynamics to capture photocontrolled degradation and erosion processes in hydrogels formed by end-linking of four-arm polyethylene glycol precursors. We demonstrate that the polydispersity and the fraction of broken-off fragments scale with the relative extent of reaction. The reverse gel point measured is close to the value predicted by the bond percolation theory on a diamond lattice. We characterize the erosion process via tracking the mass loss that accounts for the fragments remaining in contact with the percolated network. We quantify the dependence of the mass loss on the extent of reaction and on the properties of the film prior to degradation. These results elucidate the main features of degradation and erosion on the mesoscale and could provide guidelines for future design of degrading materials with dynamically controlled properties.

Mesoscale Modeling of Phase Separation Controlled by Hydrosilylation in Polyhydromethylsiloxane (PHMS)-Containing Blends.

Controlling morphology of polysiloxane blends crosslinked by the hydrosilylation reaction followed by pyrolysis constitutes a robust strategy to fabricate polymer-derived ceramics (PDCs) for a number of applications, from water purification to hydrogen storage. Herein, we introduce a dissipative particle dynamics (DPD) approach that captures the phase separation in binary and ternary polymer blends undergoing hydrosilylation. Linear polyhydromethylsiloxane (PHMS) chains are chosen as preceramic precursors and linear vinyl-terminated polydimethylsiloxane (v-PDMS) chains constitute the reactive sacrificial component. Hydrosilylation of carbon-carbon unsaturated double bonds results in the formation of carbon-silicon bonds and is widely utilized in the synthesis of organosilicons. We characterize the dynamics of binary PHMS/v-PDMS blends undergoing hydrosilylation and ternary blends in which a fraction of the reactive sacrificial component (v-PDMS) is replaced with the non-reactive sacrificial component (methyl-terminated PDMS (m-PDMS), polyacrylonitrile (PAN), or poly(methyl methacrylate) (PMMA)). Our results clearly demonstrate that the morphology of the sacrificial domains in the nanostructured polymer network formed can be tailored by tunning the composition, chemical nature, and the degree of polymerization of the sacrificial component. We also show that the addition of a non-reactive sacrificial component introduces facile means to control the self-assembly and morphology of these nanostructured materials by varying the fraction, degree of polymerization, or the chemical nature of this component.

Rotating magnetic nanorods detect minute fluctuations of magnetic field.

Magnetic nanorods rotating in a viscous liquid are very sensitive to any ambient magnetic field. We theoretically predicted and experimentally validated the conditions for two-dimensional synchronous and asynchronous rotation as well as three-dimensional precession and tumbling of nanorods in an ambient field superimposed on a planar rotating magnetic field. We discovered that any ambient field stabilizes the synchronous precession of the nanorod so that the nanorod precession can be completely controlled. This effect opens up different applications of magnetic nanorods as sensors of weak magnetic fields, for microrheology, and generally for magnetic levitation.