Enhancement of Polypropylene 3D-Printed Structures via the Addition of SiC Whiskers and Microwave Irradiation.

We report on enhancing the mechanical and structural characteristics of polypropylene (PP) three-dimensional (3D)-printed structures fabricated via fused filament fabrication (FFF) by employing composite PP-based filament with subsequent microwave (MWV) treatment. The composite filament contained a minute (0.9 vol %) fraction of silicon carbide whiskers (SiCWs) and was prepared via melt blending of PP pellets with SiCW using an extruder. The surface of the whiskers was modified with trimethoxy(octadecyl) silane to improve compatibility between the polar SiCW and nonpolar PP matrix. We employed SiCWs in composite filament because of the whiskers' high thermal conductivity and ability to generate heat locally under MWV irradiation. Indeed, we were able to conduct the heating of printed parts by MWV without sacrificing the structural integrity and improving the overall adhesion between the 3D-printed polymer layers. Our modeling captures an extent of heating upon MWV irradiation observed in our experiments. In general, utilization of the composite PP/SiCW filament significantly improved the printed parts' mechanical characteristics and sintering level compared to those made from pure PP filament. Specifically, after the MWV treatment, the adjusted (for density) storage modulus of the PP/SiCW material was just ∼20% lower than that for the PP sample obtained by conventional compression molding. After the MWV irradiation, Young's modulus, yield stress, and toughness of the printed structures were increased by ∼65, 53, and 55%, respectively. We attribute the improvement of mechanical properties via MWV treatment to enhancing the entanglement level at the weld.

Photocontrol of pattern formation and hysteresis loops in polymer gels with host-guest interactions.

Patterns formed under external stresses are often critical for ensuring the functionality of soft materials. We focus on dynamic control of pattern formation and restructuring in hydrogels with host-guest interactions. We extend the three-dimensional gel Lattice Spring Model to capture the dynamics of photo-responsive hydrogels with pendant azobenzene moieties immersed in the α-cyclodextrin (α-CD) solution. While trans-azobenzene moieties are accommodated by the α-CD cavities forming inclusion complexes resulting in hydrogel swelling, exposure to UV irradiation induces trans-to-cis photoisomerization leading to decomplexation and matrix deswelling. We demonstrate swelling-induced patterns in confined samples upon adding the α-CD solution in the dark. Further, we show that spatiotemporal variations in UV irradiation effectively control patterns formed and hysteresis loops. We introduce soft confinements via illuminating specific regions of unconstrained samples with UV light. Our results indicate that features of patterns and hysteresis in systems' response to external conditions can be regulated via well-defined illumination patterns.

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.

Mesoscale Modeling of Agglomeration of Molecular Bottlebrushes: Focus on Conformations and Clustering Criteria.

Using dissipative particle dynamics, we characterize dynamics of aggregation of molecular bottlebrushes in solvents of various qualities by tracking the number of clusters, the size of the largest cluster, and an average aggregation number. We focus on a low volume fraction of bottlebrushes in a range of solvents and probe three different cutoff criteria to identify bottlebrushes belonging to the same cluster. We demonstrate that the cutoff criteria which depend on both the coordination number and the length of the side chain allows one to correlate the agglomeration status with the structural characteristics of bottlebrushes in solvents of various qualities. We characterize conformational changes of the bottlebrush within the agglomerates with respect to those of an isolated bottlebrush in the same solvents. The characterization of bottlebrush conformations within the agglomerates is an important step in understanding the relationship between the bottlebrush architecture and material properties. An analysis of three distinct cutoff criteria to identify bottlebrushes belonging to the same cluster introduces a framework to identify both short-lived transient and long-lived agglomerates; the same approach could be further extended to characterize agglomerates of various macromolecules with complex architectures beyond the specific bottlebrush architecture considered herein.

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.

Polyethylene Glycol Crowder's Effect on Enzyme Aggregation, Thermal Stability, and Residual Catalytic Activity.

Protein stability and performance in various natural and artificial systems incorporating many other macromolecules for therapeutic, diagnostic, sensor, and biotechnological applications attract increasing interest with the expansion of these technologies. Here we address the catalytic activity of lysozyme protein (LYZ) in the presence of a polyethylene glycol (PEG) crowder in a broad range of concentrations and temperatures in aqueous solutions of two different molecular mass PEG samples (Mw = 3350 and 10000 g/mol). The phase behavior of PEG-protein solutions is examined by using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), while the enzyme denaturing is monitored by using an activity assay (AS) and circular dichroism (CD) spectroscopy. Molecular dynamic (MD) simulations are used to illustrate the effect of PEG concentration on protein stability at high temperatures. The results demonstrate that LYZ residual activity after 1 h incubation at 80 °C is improved from 15% up to 55% with the addition of PEG. The improvement is attributed to two underlying mechanisms. (i) Primarily, the stabilizing effect is due to the suppression of the enzyme aggregation because of the stronger PEG-protein interactions caused by the increased hydrophobicity of PEG and lysozyme at elevated temperatures. (ii) The MD simulations showed that the addition of PEG to some degree stabilizes the secondary structures of the enzyme by delaying unfolding at elevated temperatures. The more pronounced effect is observed with an increase in PEG concentration. This trend is consistent with CD and AS experimental results, where the thermal stability is strengthened with increasing of PEG concentration and molecular mass. The results show that the highest stabilizing effect is approached at the critical overlap concentration of PEG.

Mechanical Adaptability of Patterns in Constrained Hydrogel Membranes.

Pattern formation and dynamic restructuring play a vital role in a plethora of natural processes. Understanding and controlling pattern formation in soft synthetic materials is important for imparting a range of biomimetic functionalities. Using a three-dimensional gel Lattice spring model, we focus on the dynamics of pattern formation and restructuring in thin thermoresponsive poly(N-isopropylacrylamide) membranes under mechanical forcing via stretching and compression. A mechanical instability due to the constrained swelling of a polymer network in response to the temperature quench results in out-of-plane buckling of these membranes. The depth of the temperature quench and applied mechanical forcing affect the onset of buckling and postbuckling dynamics. We characterize formation and restructuring of buckling patterns under the stretching and compression by calculating the wavelength and the amplitude of these patterns. We demonstrate dynamic restructuring of the patterns under mechanical forcing and characterize the hysteresis behavior. Our findings show that in the range of the strain rates probed, the wavelength prescribed during the compression remains constant and independent of the sample widths, while the amplitude is regulated dynamically. We demonstrate that significantly smaller wavelengths can be prescribed and sustained dynamically than those achieved in equilibrium in the same systems. We show that an effective membrane thickness may decrease upon compression due to the out-of-plane deformations and pattern restructuring. Our findings point out that mechanical forcing can be harnessed to control the onset of buckling, postbuckling dynamics, and hysteresis phenomena in gel-based systems, introducing novel means of tailoring the functionality of soft structured surfaces and interfaces.

Native-Based Dissipative Particle Dynamics Approach for α-Helical Folding.

We developed a dissipative particle dynamics (DPD) approach that captures polyalanine folding into a stable helical conformation. Within the proposed native-based approach, the DPD parameters are derived based on the contact map constructed from the molecular dynamics (MD) simulations. We show that the proposed approach reproduces the folding of polypeptides of various lengths, including bundle formation for sufficiently long polypeptides. The proposed approach also allows one to capture the folding of the helical segments of the lysozyme. With further development of computationally efficient native-based DPD approaches for folding, modeling of a range of biomaterials incorporating α-helical segments could be extended to time and length scales far beyond those accessible in molecular dynamics simulations.

Highly Oil-Repellent Thermoplastic Boundaries via Surface Delivery of CF3 Groups by Molecular Bottlebrush Additives.

We fabricated thermoplastic surfaces possessing extremely limited water and oil wettability without employment of long-chain perfluoroalkyl (LCPFA) substances. Namely, by taking advantage of the structure and behavior of original oleophobic perfluoropolyether (PFPE) methacrylate (PFM) molecular bottlebrush (MBB) additive we obtained polymeric surfaces with oil contact angles well above 80° and surface energy on the level of 10 mN/m. Those angles and surface energies are the highest and the lowest respective values reported to date for any bulk solid flat organic surface not containing LCPFA. We show experimentally and computationally that this remarkable oil repellency is attributed to migration of small quantities of the oleophobic MBB additives to the surface of the thermoplastics. Severe mismatch in the affinity between the densely grafted long side chains of MBB and a host matrix promotes stretching and densification of mobile side chains delivering the lowest surface energy functionalities (CF3) to the materials' boundary. Our studies demonstrate that PFM can be utilized as an effective low surface energy additive to conventional thermoplastic polymers, such as poly(methyl methacrylate) and Nylon-6. We show that films containing PFM achieve the level of oil repellency significantly higher than that of polytetrafluoroethylene (PTFE), a fully perfluorinated thermoplastic. The surface energy of the films is also significantly lower than that of PTFE, even at low concentrations of PFM additives.

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.

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.

Controlling deformations of gel-based composites by electromagnetic signals within the GHz frequency range.

Using theoretical and computational modeling, we focus on dynamics of gels filled with uniformly dispersed ferromagnetic nanoparticles subjected to electromagnetic (EM) irradiation within the GHz frequency range. As a polymer matrix, we choose poly(N-isopropylacrylamide) gel, which has a low critical solution temperature and shrinks upon heating. When these composites are irradiated with a frequency close to the Ferro-Magnetic Resonance (FMR) frequency, the heating rate increases dramatically. The energy dissipation of EM signals within the magnetic nanoparticles results in the heating of the gel matrix. We show that the EM signal causes volume phase transitions, leading to large deformations of the sample for a range of system parameters. We propose a model that accounts for the dynamic coupling between the elastodynamics of the polymer gel and the FMR heating of magnetic nanoparticles. This coupling is nonlinear: when the system is heated, the gel shrinks during the volume phase transition, and the particle concentration increases, which in turn results in an increase of the heating rates as long as the concentration of nanoparticles does not exceed a critical value. We show that the system exhibits high selectivity to the frequency of the incident EM signal and can result in a large mechanical feedback in response to a small change in the applied signal. These results suggest the design of a new class of soft active gel-based materials remotely controlled by low power EM signals within the GHz frequency range.

Designing Highly Thermostable Lysozyme-Copolymer Conjugates: Focus on Effect of Polymer Concentration.

Designing biomaterials capable of functioning in harsh environments is vital for a range of applications. Using molecular dynamics simulations, we show that conjugating lysozymes with a copolymer [poly(GMA- stat-OEGMA)] comprising glycidyl methacrylate (GMA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA) results in a dramatic increase of stability of these enzymes at high temperatures provided that the concentration of the copolymer in the close vicinity of the enzyme exceeds a critical value. In our simulations, we use triads containing the same ratio of GMA to OEGMA units as in our recent experiments (N. S. Yadavalli et al., ACS Catalysis, 2017, 7, 8675). We focus on the dynamics of the conjugate at high temperatures and on its structural stability as a function of the copolymer/water content in the vicinity of the enzyme. We show that the dynamics of phase separation in the water-copolymer mixture surrounding the enzyme is critical for the structural stability of the enzyme. Specifically, restricting water access promotes the structural stability of the lysozyme at high temperatures. We identified critical water concentration below which we observe a robust stabilization; the phase separation is no longer observed at this low fraction of water so that the water domains promoting unfolding are no longer formed in the vicinity of the enzyme. This understanding provides a basis for future studies on designing a range of enzyme-copolymer conjugates with improved stability.

Designing polymer gels and composites that undergo bio-inspired phototactic reconfiguration and motion.

Inspired by the adaptive behavior of photo-responsive biological organisms, we develop analytical and computational models to design polymer gels and composites that can be dynamically reconfigured and driven to move with the application of light. We focus on gels formed from poly(N-isopropylacrylamide) and functionalized with spirobenzopyran (SP) chromophores, which become hydrophobic under blue light in acidic aqueous solution. Using our modeling approaches, we irradiate the gels through photomasks and demonstrate that the shapes of the samples can be reversibly and remotely 'remolded' by varying the apertures in the masks. By simulating the effect of repeatedly moving the light across the sample, we also show that the gel can undergo directed motion. We then examine gels that contain both SP chromophores and the ruthenium catalysts that drive the oscillatory Belousov-Zhabotinsky reaction. These dual-functionalized gels undergo spontaneous, self-sustained motion even when the lights are held stationary. We also simulate the behavior of composites formed from SP-functionalized fibers embedded in the poly(N-isopropylacrylamide) gel. With the SP-functionalization confined to the fibers, light and heat act as orthogonal stimuli and thus the composites display distinctly different modes of movement when the different cues are applied to the samples. Overall, our findings provide guidelines for using light to controllably reconfigure the shape and drive the movement of gel-based materials and thus, tailor the material to display different functionalities.

Photo-regeneration of severed gel with iniferter-mediated photo-growth.

Using dissipative particle dynamics (DPD), we developed a computational approach to model the light-induced regeneration of a gel matrix when a significant portion of the material is severed. We considered photo-controlled radical polymerization (photo-CRP) within polymer networks with embedded iniferter groups: the "photo-growth" strategy. Absorption of light by the iniferter groups turns on the polymerization process, which inserts monomers and cross-linkers into the network strands. Photo-growth allows us to effectively regenerate a severed gel under the application of light even when the severed parts are not in direct contact. The growth process can be turned off once the polymerization is near completion to yield a new cross-linked gel that resembles the uncut material.

Embedding flexible fibers into responsive gels to create composites with controllable dexterity.

Using computational modeling, we design a composite that encompasses a thermo-responsive gel and photo-responsive fibers that extend from the surface of the gel. By simulating the effect of light and heat on the sample, we isolate scenarios where cooperative interactions within the system allow the gel to actuate the "finger-like" motion of the embedded fibers. To achieve this distinctive behavior, we consider a gel formed from poly(N-isopropylacrylamide) (PNIPAAm), which shrinks when heated above the lower critical solution temperature (LCST). The fibers are functionalized with spirobenzopyran (SP) chromophores that extend a finite region into the polymer network. The application of heat causes the entire gel to shrink, while the application of light causes the regions around the functionalized fibers to collapse. With the fibers arranged in a square or circular pattern in the center of the gel, heating the non-illuminated samples drives the fibers to move apart as they bend outward (away from the center). With the application of light, the tips of fibers come together as the fibers bend inward. In this configuration, the fibers could act as grippers that bind objects in the presence of light. With the illumination turned off, the grippers could controllably release the objects. By placing the fibers closer to the edge of the sample, the combination of heat and light could be harnessed to bind and release larger objects. We also show that by illuminating the fibers separately, we can manipulate the motion of the individual finger-like objects, and thus, potentially expand the utility of the system. Overall, our findings provide guidelines for controllably reconfiguring the shape of soft materials and thus, tailoring the material to display different functionalities in different environments.

Harnessing Cooperative Interactions between Thermoresponsive Aptamers and Gels To Trap and Release Nanoparticles.

We use computational modeling to design a device that can controllably trap and release particles in solution in response to variations in temperature. The system exploits the thermoresponsive properties of end-grafted fibers and the underlying gel substrate. The fibers mimic the temperature-dependent behavior of biological aptamers, which form a hairpin structure at low temperatures (T) and unfold at higher T, consequently losing their binding affinity. The gel substrate exhibits a lower critical solution temperature and thus, expands at low temperatures and contracts at higher T. By developing a new dissipative particle dynamics simulation, we examine the behavior of this hybrid system in a flowing fluid that contains buoyant nanoparticles. At low T, the expansion of the gel causes the hairpin-shaped fibers to extend into the path of the fluid-driven particle. Exhibiting a high binding affinity for these particles at low temperature, the fibers effectively trap and extract the particles from the surrounding solution. When the temperature is increased, the unfolding of the fiber and collapse of the supporting gel layer cause the particles to be released and transported away from the layer by the applied shear flow. Since the temperature-induced conformational changes of the fiber and polymer gel are reversible, the system can be used repeatedly to "catch and release" particles in solution. Our findings provide guidelines for creating fluidic devices that are effective at purifying contaminated solutions or trapping cells for biological assays.

Computational modeling of oscillating fins that "catch and release" targeted nanoparticles in bilayer flows.

A number of physiological processes in living organisms involve the selective "catch and release" of biomolecules. Inspired by these biological processes, we use computational modeling to design synthetic systems that can controllably catch, transport, and release specific molecules within the surrounding solution, and, thus, could be harnessed for effective separation processes within microfluidic devices. Our system consists of an array of oscillating, microscopic fins that are anchored onto the floor of a microchannel and immersed in a flowing bilayer fluid. The oscillations drive the fins to repeatedly extend into the upper fluid and then tilt into the lower stream. The fins exhibit a specified wetting interaction with the fluids and specific adhesive interactions with nanoparticles in the solution. With this setup, we determine conditions where the oscillating fins can selectively bind, and thus, "catch" target nanoparticles within the upper fluid stream and then release these particles into the lower stream. We isolate the effects of varying the wetting interaction and the fins' oscillation modes on the effective extraction of target species from the upper stream. Our findings provide fundamental insights into the system's complex dynamics and yield guidelines for fabricating devices for the detection and separation of target molecules from complex fluids.

Designing a gel-fiber composite to extract nanoparticles from solution.

The extraction of nanoscopic particulates from flowing fluids is a vital step in filtration processes, as well as the fabrication of nanocomposites. Inspired by the ability of carnivorous plants to use hair-like filaments to entrap species, we use computational modeling to design a multi-component system that integrates compliant fibers and thermo-responsive gels to extract particles from the surrounding solution. In particular, hydrophobic fibers are embedded in a gel that exhibits a lower critical solution temperature (LCST). With an increase in temperature, the gel collapses to expose fibers that self-assemble into bundles, which act as nanoscale "grippers" that bind the particles and draw them into the underlying gel. By varying the relative stiffness of the fibers, the fiber-particle interaction strength and the shear rate in the solution, we identify optimal parameters where the particles are effectively drawn from the solution and remain firmly bound within the gel layer. Hence, the system can be harnessed in purifying fluids and creating novel hybrid materials that integrate nanoparticles with polymer gels.

Designing Composite Coatings That Provide a Dual Defense against Fouling.

Inspired by marine organisms that utilize spines and shape changes to prevent the biofouling of their surfaces, we use computational modeling to design a gel-based composite coating that provides a two-pronged defense mechanism against the fouling of the underlying substrate. Using dissipative particle dynamics (DPD) simulations, we construct a coating that encompasses rigid posts embedded in a thermoresponsive gel, which exhibits a lower critical solution temperature (LCST). When the gel is heated above its LCST, it collapses to expose the buried posts, which act as spines or spikes that prevent a solid particle from penetrating the layer. Moreover, we show that an imposed shear flow readily dislodges these particles and washes them away from the coated substrate. As the system dissipates heat and cools, the LCST gel expands, and this dynamic morphological change can also be harnessed to dislodge the adsorbed particles. Thus, both the exposed posts and the swelling gels can provide barriers to the penetration of particulates through the coating. In this manner, the coating provides a dual mechanism against the fouling of the substrate. This physical approach can be particularly beneficial because it does not require the release of any chemical substances that could have detrimental consequences to the environment.