Effect of Materials Parameters on the Shape of Face-On Lamellae in Semi-Conducting Polymers: Insights From Qualitative Theory.

Polymer semiconductors frequently form crystals or mesophases with lamellae, that comprise alternating layers of stacked backbones and side chains. Controlling lamellar orientation in films is essential for obtaining efficient charge carrier transport. Herein, lamellar orientation is investigated in an application-relevant setup: lamellae assembled on a substrate that strongly favors face-on orientation, but exposed to a film surface that promotes orientation along an "easy" direction, other than face on. It is assumed that the face-on order propagates from the substrate, but the lamellae bend to reduce their surface energy. A qualitative free-energy model is developed. The deformation is investigated as a function of film thickness, effective Young modulus, anchoring coefficient, and easy direction at the free surface. The calculations highlight the importance of elastic constants - lamellae can substantially deform already when Young moduli are only an order of magnitude smaller than the values that are reported for crystals. Softer Young moduli are expected when lamellar assembly occurs in a non-solidified mesophase that can be an equilibrium or (more speculatively) a transient state prior to crystallization. The alternative scenario of a two-layered film is also evaluated, where edge-on and face-on grains form, respectively, at the free surface and substrate.

Spontaneous Synchronization of Two Bistable Pyridine-Furan Nanosprings Connected by an Oligomeric Bridge.

The intensive development of nanodevices acting as two-state systems has motivated the search for nanoscale molecular structures whose long-term conformational dynamics are similar to the dynamics of bistable mechanical systems such as Euler arches and Duffing oscillators. Collective synchrony in bistable dynamics of molecular-sized systems has attracted immense attention as a potential pathway to amplify the output signals of molecular nanodevices. Recently, pyridine-furan oligomers of helical shape that are a few nanometers in size and exhibit bistable dynamics similar to a Duffing oscillator have been identified through molecular dynamics simulations. In this article, we present the case of dynamical synchronization of these bistable systems. We show that two pyridine-furan springs connected by a rigid oligomeric bridge spontaneously synchronize vibrations and stochastic resonance enhances the synchronization effect.

Spontaneous Vibrations and Stochastic Resonance of Short Oligomeric Springs.

There is growing interest in molecular structures that exhibit dynamics similar to bistable mechanical systems. These structures have the potential to be used as two-state operating units for various functional purposes. Particularly intriguing are the bistable systems that display spontaneous vibrations and stochastic resonance. Previously, via molecular dynamics simulations, it was discovered that short pyridine-furan springs in water, when subjected to stretching with power loads, exhibit the bistable dynamics of a Duffing oscillator. In this study, we extend these simulations to include short pyridine-pyrrole and pyridine-furan springs in a hydrophobic solvent. Our findings demonstrate that these systems also display the bistable dynamics, accompanied by spontaneous vibrations and stochastic resonance activated by thermal noise.

Short Pyridine-Furan Springs Exhibit Bistable Dynamics of Duffing Oscillators.

The intensive development of nanodevices acting as two-state systems has motivated the search for nanoscale molecular structures whose dynamics are similar to those of bistable mechanical systems, such as Euler arches and Duffing oscillators. Of particular interest are the molecular structures capable of spontaneous vibrations and stochastic resonance. Recently, oligomeric molecules that were a few nanometers in size and exhibited the bistable dynamics of an Euler arch were identified through molecular dynamics simulations of short fragments of thermo-responsive polymers subject to force loading. In this article, we present molecular dynamics simulations of short pyridine-furan springs a few nanometers in size and demonstrate the bistable dynamics of a Duffing oscillator with thermally-activated spontaneous vibrations and stochastic resonance.

Oligomeric "Catastrophe Machines" with Thermally Activated Bistability and Stochastic Resonance.

The desire to create nanometer-scale switching devices has motivated an active search for bistate macromolecular systems allowing for sharp conformational transitions in response to stimuli. Using full-atomic simulations, we found particular oligomers of thermosensitive polymers, themselves only a few nanometers in size, that possessed conformational bistability and reacted to power loads as nonlinear mechanical systems, termed "catastrophe machines". We established the bifurcation and hysteresis effects, spontaneous vibrations, and stochastic resonance for these oligomers. It is important to note that the spontaneous vibrations and stochastic resonance were activated by thermal fluctuations. Because of such mechanic-like characteristics, short oligomers are a promising platform for the design of nanodevices and molecular machines.

Self-Assembly of Lecithin and Bile Salt in the Presence of Inorganic Salt in Water: Mesoscale Computer Simulation.

The influence of inorganic salt on the structure of lecithin/bile salt mixtures in aqueous solution is studied by means of dissipative particle dynamics simulations. We propose a coarse-grained model of phosphatidylcholine and two types of bile salts (sodium cholate and sodium deoxycholate) and also take into account the presence of low molecular weight salt. This model allows us to study the system on rather large time and length scales (up to about ∼20 µs and 50 nm) and to reveal mechanisms of experimentally observed increasing viscosity upon increasing the low molecular weight salt concentration in this system. We show that increasing the low molecular weight salt concentration induces the growth of cylinder-like micelles formed in lecithin/bile salt mixtures in water. These wormlike micelles can entangle into transient networks displaying perceptible viscoelastic properties. Computer simulation results are in good qualitative agreement with experimental observations.