Controlled Exfoliation of Layered Silicate Heterostructures into Bilayers and Their Conversion into Giant Janus Platelets.

Ordered heterostructures of layered materials where interlayers with different reactivities strictly alternate in stacks offer predetermined slippage planes that provide a precise route for the preparation of bilayer materials. We use this route for the synthesis of a novel type of reinforced layered silicate bilayer that is 15 % stiffer than the corresponding monolayer. Furthermore, we will demonstrate that triggering cleavage of bilayers by osmotic swelling gives access to a generic toolbox for an asymmetrical modification of the two vis-à-vis standing basal planes of monolayers. Only two simple steps applying arbitrary commercial polycations are needed to obtain such Janus-type monolayers. The generic synthesis route will be applicable to many other layered compounds capable of osmotic swelling, rendering this approach interesting for a variety of materials and applications.

Influence of the molecular structure and morphology of self-assembled 1,3,5-benzenetrisamide nanofibers on their mechanical properties.

The influence of molecular structure on the mechanical properties of self-assembled 1,3,5-benzenetrisamide nanofibers is investigated. Three compounds with different amide connectivity and different alkyl substituents are compared. All the trisamides form well-defined fibers and exhibit significant differences in diameters of up to one order of magnitude. Using nanomechanical bending experiments, the rigidity of the nanofibers shows a difference of up to three orders of magnitude. Calculation of Young's modulus reveals that these differences are a size effect and that the moduli of all systems are similar and in the lower GPa range. This demonstrates that variation of the molecular structure allows changing of the fibers' morphology, whereas it has a minor influence on their modulus. Consequently, the stiffness of the self-assembled nanofibers can be tuned over a wide range--a crucial property for applications as versatile nano- and micromechanical components.

Mechanoresponsive Hydrogel Particles as a Platform for Three-Dimensional Force Sensing.

We introduce a novel concept for mechanosensitive hydrogel microparticles, which translate deformation into changes in fluorescence and can thus function as mechanical probes. The hydrogel particles with controlled polymer network are produced via droplet microfluidics from poly(ethylene glycol) (PEG) precursors. Förster resonance energy transfer donors and acceptors are coupled to the PEG hydrogel network for reporting local deformations as fluorescence shifts. We show that global network deformations, which occur upon drying/rehydration, can be detected via a characteristic fluorescence shift. Combined characterization with confocal laser scanning microscopy and atomic force microscopy (AFM) shows that also local deformation of the particles can be detected. Using AFM, the mechanical properties of the particles can be quantified, which allows linking strain with stress and thus force sensing in a three-dimensional environment. Microfluidic material design allows for precisely varying the size of our hydrogel microparticles as well as their mechanical properties and polymer network structure with regard to the choice of the macromolecular precursors and their functionalization with fluorophores. Thus, concomitant changes in mechanical properties and mechanosensitivity qualify these hydrogel microparticles as an adjustable material platform for force sensing in structural mechanics or cell culturing.

Monitoring the Contact Stress Distribution of Gecko-Inspired Adhesives Using Mechano-Sensitive Surface Coatings.

The contact geometry of microstructured adhesive surfaces is of high relevance for adhesion enhancement. Theoretical considerations indicate that the stress distribution in the contact zone is crucial for the detachment mechanism, but direct experimental evidence is missing so far. In this work, we propose a method that allows, for the first time, the detection of local stresses at the contact area of biomimetic adhesive microstructures during contact formation, compression and detachment. We use a mechano-sensitive polymeric layer, which turns mechanical stresses into changes of fluorescence intensity. The biomimetic surface is brought into contact with this layer in a well-defined fashion using a microcontact printer, while the contact area is monitored with fluorescence microscopy in situ. Thus, changes in stress distribution across the contact area during compression and pull-off can be visualized with a lateral resolution of 1 µm. We apply this method to study the enhanced adhesive performance of T-shaped micropillars, compared to flat punch microstructures. We find significant differences in the stress distribution of the both differing contact geometries during pull-off. In particular, we find direct evidence for the suppression of crack nucleation at the edge of T-shaped pillars, which confirms theoretical models for the superior adhesive properties of these structures.