Shape-Programmed Folding of Stimuli-Responsive Polymer Bilayers

Self-folding polymer films were only recently proposed as an alternative method for the design of three-dimensional constructs. Due to the relative novelty of the approach, insufficient amount of data on the behavior of such systems is available in the literature. This study is bound to fill the gaps and give a deeper insight into the understanding of how and why different types of folding occur. In this study, four different types of folding of polymer bilayers are presented. Rectangles are one of the simplest geometrical forms and were therefore adopted as a convenient initial system for the investigation of the folding behavior of polymer bilayers. We chose PNIPAM for the active polymer, as it is a well-studied polymer with sharp Lower Critical Transition Temperature at around 33 C. For the passive layer, poly(methyl methacrylate) and poly(caprolactone) were chosen. The influence of different parameters of the system, such as polymer thickness and temperature was thoroughly investigated in order to be accounted for in later experiments. It was demonstrated that bilayers placed on a substrate start to roll from the corners due to quicker diffusion of water. Rolling from the long-side starts later but dominates at high aspect ratio. We showed that the main reasons causing a variety of rolling scenarios are (i) non-homogenous swelling due to slow diffusion of water in hydrogels and (ii) adhesion of polymer to a substrate until a certain threshold. Moreover, non-homogenous swelling determines folding in the first moments, while adhesion plays a decisive role at later stages of folding. After having understood the abovementioned basics, we decided to explore how those applied to more complex shapes. For the purpose, four- and six-arm stars were chosen, the main idea behind this being the creation of self-folding polymer capsules capable of encapsulation of microparticles and cells. Adjusting the polymer thickness and thus the radius of folding allowed creating structures, capable of reversible self-folding and unfolding. The possibility to reversibly encapsulate and release objects in the micro-range was demonstrated on the example of yeast cells. Noteworthy, the capsules were produced by means of the same process we used for the design of tubes – when compared to the folding of rectangles, it was the shape of the initial pattern and the folding radius that were changed; the mechanism was the same – simple one-step folding towards the center of the bilayer. Clearly the number of structures that can be generated by this method is fairly limited. The search for means to overcome this constraint led to the idea of hierarchical multi-step folding. Due to the edge-activation of the bilayers, the observed deformed shapes differ from the classical ones obtained by homogeneous activation. It was found that films could demonstrate several kinds of actuation behavior such as wrinkling, bending and folding that result in a variety of shapes. It was demonstrated that one can introduce hinges into the folded structure by proper design of the bilayer's external shape through diffusion without having to use site selective deposition of active polymers. Experimental observations led us to derive four empirical rules: 1) “Bilayer polymer films placed on a substrate start to fold from their periphery and the number of formed wrinkles/tubes decreases until the angle between adjacent wrinkles/tubes approaches 130°”; 2) “After the wrinkles along the perimeter of the film form tubes, further folding proceeds along the lines connecting the vertexes of the folded film”; 3) “The folding goes along the lines which are closer to the periphery of the films”; 4) „Folding of the rays may result in blocking of the neighboring rays if the angle between the base of the folded ray and the shoulders of the neighboring rays is close to 180°”. These rules were then applied to direct the folding of edge-activated polymer bilayers through a concrete example - the design of a 3D pyramid. One consequence of the second and third rules is that generally triangles are formed during the multi-step folding process. In order to create a cube, or any other 3D structure with non-triangular sides, an effective way to stop the folding along the lines, connecting neighboring vertexes had to be thought of. A possible solution would be the insertion of a rigid element inside the bilayer, perpendicular to the direction of folding. The solution of this problem was to design structures with pores. A pore would normally decrease the rigidity of a structure but in our case, a pore basically comprised an edge inside the structure and could thus form tubes which, as was already shown, exhibit much higher rigidity than a film. On the other hand, a pore, or many pores, would expose different parts of the active layer to the solvent and would strongly influence its swelling and, as a consequence, folding behavior. Hence, the influence of a pore on the swelling and the folding behavior of polymer bilayers had to be investigated. It was shown that pores of the right form and dimensions did indeed hinder the folding as intended. Instead, the polymer films took other ways to fold. As a result, despite the correctness of our reasoning, we failed to produce a cube by hierarchical folding of polymer bilayers. However, other sophisticated 3D objects were obtained, further increasing the arsenal of available structures, as well as giving an in-depth insight on the folding process

Stress analysis of a link for slat chain conveyor

This paper analyzes stresses in a link of a slat chain conveyor loaded with rock mass. Tensometric data and results from numerical simulation with Finite Element Method (FEM) are used. The tensometric measurements are performed in real life conditions. For numerical simulation an adequate model with FEM has been created. The adequacy of the model is confirmed by the comparison of the experimental and numerical results. The factor of safety used in the design of the conveyor links is determined

Programmed assembly of oppositely charged homogeneously decorated and Janus particles

The exploitation of colloidal building blocks with morphological and functional anisotropy facilitates the generation of complex structures with unique properties, which are not exhibited by isotropic particle assemblies. Herein, we demonstrate an easy and scalable bottom-up approach for the programmed assembly of hairy oppositely charged homogeneously decorated and Janus particles based on electrostatic interactions mediated by polyelectrolytes grafted onto their surface. Two different assembly routes are proposed depending on the target structures: raspberry-like/half-raspberry-like or dumbbell-like micro-clusters. Ultimately, stable symmetric and asymmetric microstructures could be obtained in a well-controlled manner for the homogeneous–homogeneous and homogeneous–Janus particle assemblies, respectively. The spatially separated functionalities of the asymmetric Janus particle-based micro-clusters allow their further assembly into complex hierarchical constructs, which may potentially lead to the design of materials with tailored plasmonics and optical properties

Stimuli‐responsive microjets with reconfigurable shape

Flexible thermoresponsive polymeric microjets are formed by the self‐folding of polymeric layers containing a thin Pt film used as catalyst for self‐propulsion in solutions containing hydrogen peroxide. The flexible microjets can reversibly fold and unfold in an accurate manner by applying changes in temperature to the solution in which they are immersed. This effect allows microjets to rapidly start and stop multiple times by controlling the radius of curvature of the microjet. This work opens many possibilities in the field of artificial nanodevices, for fundamental studies on self‐propulsion at the microscale, and also for biorelated applications

High Level Electronic Structure Calculation of Molecular Solid-State NMR Shielding Constants

International audienceIn this work, we present a quantum mechanics/molecular mechanics (QM/MM) approach for the computation of solid-state nuclear magnetic resonance (SS-NMR) shielding constants (SCs) for molecular crystals. Besides applying standard-DFT functionals like GGAs (PBE), meta-GGAs (TPSS), and hybrids (B3LYP), we apply a double-hybrid (DSD-PBEP86) functional as well as MP2, using the domain-based local pair natural orbital (DLPNO) formalism, to calculate the NMR SCs of six amino acid crystals. All the electronic structure methods used exhibit good correlation of the NMR shieldings with respect to experimental chemical shifts for both (1)H and (13)C. We also find that local electronic structure is much more important than the long-range electrostatic effects for these systems, implying that cluster approaches using all-electron/Gaussian basis set methods might offer great potential for predictive computations of solid-state NMR parameters for organic solids

Surfaces with Self-repairable Ultrahydrophobicity Based on Self-organizing Freely Floating Colloidal Particles

We report an approach for the design of materials with self-repairable ultrahydrophobic properties. The materials are based on highly fluorinated crystalline fusible wax with incorporated colloidal particles. Due to the highly pronounced tendency of the wax to crystallize, the formation of blends with rough fractal surfaces was observed. In order to prove their self-repairing ability, we mechanically damaged them by scratching, which removed most of the particles from the surface. Melting of the damaged blend resulted in reorganization of the particles at the wax-air interface, restoring the initial structure and thus the ultrahydrophobic behavior

Surfaces with Self-repairable Ultrahydrophobicity Based on Self-organizing Freely Floating Colloidal Particles

We report an approach for the design of materials with self-repairable ultrahydrophobic properties. The materials are based on highly fluorinated crystalline fusible wax with incorporated colloidal particles. Due to the highly pronounced tendency of the wax to crystallize, the formation of blends with rough fractal surfaces was observed. In order to prove their self-repairing ability, we mechanically damaged them by scratching, which removed most of the particles from the surface. Melting of the damaged blend resulted in reorganization of the particles at the wax-air interface, restoring the initial structure and thus the ultrahydrophobic behavior