Achieving controllable and reversible snap-through in pre-strained strips of liquid crystalline elastomers.

Deformable, elastic materials that buckle in response to external stimuli can display "snap-through", which involves a transition between different, stable buckled states. Snap-through produces a quick release of stored potential energy, and thus can provide fast actuation for soft robots and other flexible devices. Liquid crystalline elastomers (LCEs) exposed to light undergo a phase transition and a concomitant mechanical deformation, allowing control of snap-through for rapid, large amplitude actuation. Using both a semi-analytical model and finite element simulations, we focus on a thin LCE strip that is clamped at both ends and buckles due to an initially imposed strain. We show that when this clamped, strained sample is exposed to light, it produces controllable snap-through behavior, which can be regulated by varying the light intensity and the area of the sample targeted by light. In particular, this snap-through can be triggered in different directions, allowing the system to be reset and triggered multiple times. Removing the light source will cause the system to settle into one of two stable states, enabling the encoding and storage of information in the system. We also highlight a specific case where removing the light source removes the induced buckling and returns the material to an initially flat state. In this case, the system can be reset and form a new shape, allowing it to function as a rewriteable haptic interface.

Self-regulated non-reciprocal motions in single-material microstructures.

Living cilia stir, sweep and steer via swirling strokes of complex bending and twisting, paired with distinct reverse arcs1,2. Efforts to mimic such dynamics synthetically rely on multimaterial designs but face limits to programming arbitrary motions or diverse behaviours in one structure3-8. Here we show how diverse, complex, non-reciprocal, stroke-like trajectories emerge in a single-material system through self-regulation. When a micropost composed of photoresponsive liquid crystal elastomer with mesogens aligned oblique to the structure axis is exposed to a static light source, dynamic dances evolve as light initiates a travelling order-to-disorder transition front, transiently turning the structure into a complex evolving bimorph that twists and bends via multilevel opto-chemo-mechanical feedback. As captured by our theoretical model, the travelling front continuously reorients the molecular, geometric and illumination axes relative to each other, yielding pathways composed from series of twisting, bending, photophobic and phototropic motions. Guided by the model, here we choreograph a wide range of trajectories by tailoring parameters, including illumination angle, light intensity, molecular anisotropy, microstructure geometry, temperature and irradiation intervals and duration. We further show how this opto-chemo-mechanical self-regulation serves as a foundation for creating self-organizing deformation patterns in closely spaced microstructure arrays via light-mediated interpost communication, as well as complex motions of jointed microstructures, with broad implications for autonomous multimodal actuators in areas such as soft robotics7,9,10, biomedical devices11,12 and energy transduction materials13, and for fundamental understanding of self-regulated systems14,15.

Twist again: Dynamically and reversibly controllable chirality in liquid crystalline elastomer microposts.

Photoresponsive liquid crystalline elastomers (LCEs) constitute ideal actuators for soft robots because their light-induced macroscopic shape changes can be harnessed to perform specific articulated motions. Conventional LCEs, however, do not typically exhibit complex modes of bending and twisting necessary to perform sophisticated maneuvers. Here, we model LCE microposts encompassing side-chain mesogens oriented along a magnetically programmed nematic director, and azobenzene cross-linkers, which determine the deformations of illuminated posts. On altering the nematic director orientation from vertical to horizontal, the post's bending respectively changes from light-seeking to light-avoiding. Moreover, both modeling and subsequent experiments show that with the director tilted at 45°, the initially achiral post reversibly twists into a right- or left-handed chiral structure, controlled by the angle of incident light. We exploit this photoinduced chirality to design "chimera" posts (encompassing two regions with distinct director orientations) that exhibit simultaneous bending and twisting, mimicking motions exhibited by the human musculoskeletal system.

Multiresponsive polymeric microstructures with encoded predetermined and self-regulated deformability.

Dynamic functions of biological organisms often rely on arrays of actively deformable microstructures undergoing a nearly unlimited repertoire of predetermined and self-regulated reconfigurations and motions, most of which are difficult or not yet possible to achieve in synthetic systems. Here, we introduce stimuli-responsive microstructures based on liquid-crystalline elastomers (LCEs) that display a broad range of hierarchical, even mechanically unfavored deformation behaviors. By polymerizing molded prepolymer in patterned magnetic fields, we encode any desired uniform mesogen orientation into the resulting LCE microstructures, which is then read out upon heating above the nematic-isotropic transition temperature (TN-I) as a specific prescribed deformation, such as twisting, in- and out-of-plane tilting, stretching, or contraction. By further introducing light-responsive moieties, we demonstrate unique multifunctionality of the LCEs capable of three actuation modes: self-regulated bending toward the light source at T < TN-I, magnetic-field-encoded predetermined deformation at T > TN-I, and direction-dependent self-regulated motion toward the light at T > TN-I We develop approaches to create patterned arrays of microstructures with encoded multiple area-specific deformation modes and show their functions in responsive release of cargo, image concealment, and light-controlled reflectivity. We foresee that this platform can be widely applied in switchable adhesion, information encryption, autonomous antennae, energy harvesting, soft robotics, and smart buildings.

Optimizing Micromixer Surfaces To Deter Biofouling.

Using computational modeling, we show that the dynamic interplay between a flowing fluid and the appropriately designed surface relief pattern can inhibit the fouling of the substrate. We specifically focus on surfaces that are decorated with three-dimensional (3D) chevron or sawtooth "micromixer" patterns and model the fouling agents (e.g., cells) as spherical microcapsules. The interaction between the imposed shear flow and the chevrons on the surface generates 3D vortices in the system. We pinpoint a range of shear rates where the forces from these vortices can rupture the bonds between the two mobile microcapsules near the surface. Notably, the patterned surface offers fewer points of attachment than a flat substrate, and the shear flows readily transport the separated capsules away from the layer. We contrast the performance of surfaces that encompass rectangular posts, chevrons, and asymmetric sawtooth patterns and thereby identify the geometric factors that cause the sawtooth structure to be most effective at disrupting the bonding between the capsules. By breaking up nascent clusters of contaminant cells, these 3D relief patterns can play a vital role in disrupting the biofouling of surfaces immersed in flowing fluids.

Transitions of Double-Stranded DNA Between the A- and B-Forms.

The structure of double-stranded DNA (dsDNA) is sensitive to solvent conditions. In solution, B-DNA is the favored conformation under physiological conditions, while A-DNA is the form found under low water activity. The A-form is induced locally in some protein-DNA complexes, and repeated transitions between the B- and A-forms have been proposed to generate the forces used to drive dsDNA into viral capsids during genome packaging. Here, we report analyses on previous molecular dynamics (MD) simulations on B-DNA, along with new MD simulations on the transition from A-DNA to B-DNA in solution. We introduce the A-B Index (ABI), a new metric along the A-B continuum, to quantify our results. When A-DNA is placed in an equilibrated solution at physiological ionic strength, there is no energy barrier to the transition to the B-form, which begins within about 1 ns. The transition is essentially complete within 5 ns, although occasionally a stretch of a few base pairs will remain A-like for up to ∼10 ns. A comparison of four sequences with a range of predicted A-phobicities shows that more A-phobic sequences make the transition more rapidly than less A-phobic sequences. Simulations on dsDNA with a region of roughly one turn locked in the A-form allow us to characterize the A/B junction, which has an average bend angle of 20-30°. Fluctuations in this angle occur with characteristic times of about 10 ns.

DNA Scrunching in the Packaging of Viral Genomes.

The motors that drive double-stranded DNA (dsDNA) genomes into viral capsids are among the strongest of all biological motors for which forces have been measured, but it is not known how they generate force. We previously proposed that the DNA is not a passive substrate but that it plays an active role in force generation. This "scrunchworm hypothesis" holds that the motor proteins repeatedly dehydrate and rehydrate the DNA, which then undergoes cyclic shortening and lengthening motions. These are captured by a coupled protein-DNA grip-and-release cycle to rectify the motion and translocate the DNA into the capsid. In this study, we examined the interactions of dsDNA with the dodecameric connector protein of bacteriophage ϕ29, using molecular dynamics simulations on four different DNA sequences, starting from two different conformations (A-DNA and B-DNA). In all four simulations starting with the protein equilibrated with A-DNA in the channel, we observed transitions to a common, metastable, highly scrunched conformation, designated A*. This conformation is very similar to one recently reported by Kumar and Grubmüller in much longer MD simulations on B-DNA docked into the ϕ29 connector. These results are significant for four reasons. First, the scrunched conformations occur spontaneously, without requiring lever-like protein motions often believed to be necessary for DNA translocation. Second, the transition takes place within the connector, providing the location of the putative "dehydrator". Third, the protein has more contacts with one strand of the DNA than with the other; the former was identified in single-molecule laser tweezer experiments as the "load-bearing strand". Finally, the spontaneity of the DNA-protein interaction suggests that it may play a role in the initial docking of DNA in motors like that of T4 that can load and package any sequence.

Force distribution in a semiflexible loop.

Loops undergoing thermal fluctuations are prevalent in nature. Ringlike or cross-linked polymers, cyclic macromolecules, and protein-mediated DNA loops all belong to this category. Stability of these molecules are generally described in terms of free energy, an average quantity, but it may also be impacted by local fluctuating forces acting within these systems. The full distribution of these forces can thus give us insights into mechanochemistry beyond the predictive capability of thermodynamics. In this paper, we study the force exerted by an inextensible semiflexible polymer constrained in a looped state. By using a simulation method termed "phase-space sampling," we generate the equilibrium distribution of chain conformations in both position and momentum space. We compute the constraint forces between the two ends of the loop in this chain ensemble using Lagrangian mechanics, and show that the mean of these forces is equal to the thermodynamic force. By analyzing kinetic and potential contributions to the forces, we find that the mean force acts in the direction of increasing extension not because of bending stress, but in spite of it. Furthermore, we obtain a distribution of constraint forces as a function of chain length, extension, and stiffness. Notably, increasing contour length decreases the average force, but the additional freedom allows fluctuations in the constraint force to increase. The force distribution is asymmetric and falls off less sharply than a Gaussian distribution. Our work exemplifies a system where large-amplitude fluctuations occur in a way unforeseen by a purely thermodynamic framework, and offers computational tools useful for efficient, unbiased simulation of a constrained system.

Calculation of a fluctuating entropic force by phase space sampling.

A polymer chain pinned in space exerts a fluctuating force on the pin point in thermal equilibrium. The average of such fluctuating force is well understood from statistical mechanics as an entropic force, but little is known about the underlying force distribution. Here, we introduce two phase space sampling methods that can produce the equilibrium distribution of instantaneous forces exerted by a terminally pinned polymer. In these methods, both the positions and momenta of mass points representing a freely jointed chain are perturbed in accordance with the spatial constraints and the Boltzmann distribution of total energy. The constraint force for each conformation and momentum is calculated using Lagrangian dynamics. Using terminally pinned chains in space and on a surface, we show that the force distribution is highly asymmetric with both tensile and compressive forces. Most importantly, the mean of the distribution, which is equal to the entropic force, is not the most probable force even for long chains. Our work provides insights into the mechanistic origin of entropic forces, and an efficient computational tool for unbiased sampling of the phase space of a constrained system.