ABSTRACT
Filamentous bundles are ubiquitous in Nature, achieving highly adaptive functions and structural integrity from assembly of diverse mesoscale supramolecular elements. Engineering routes to synthetic, topologically integrated analogs demands precisely coordinated control of multiple filaments' shapes and positions, a major challenge when performed without complex machinery or labor-intensive processing. Here, we demonstrate a photocreasing design that encodes local curvature and twist into mesoscale polymer filaments, enabling their programmed transformation into target 3-dimensional geometries. Importantly, patterned photocreasing of filament arrays drives autonomous spinning to form linked filament bundles that are highly entangled and structurally robust. In individual filaments, photocreases unlock paths to arbitrary, 3-dimensional curves in space. Collectively, photocrease-mediated bundling establishes a transformative paradigm enabling smart, self-assembled mesostructures that mimic performance-differentiating structures in Nature (e.g., tendon and muscle fiber) and the macro-engineered world (e.g., rope).
ABSTRACT
We report fabrication of highly flexible micron-sized helices from nanometer-thick ribbons. Building upon the helical coiling of such ultrathin ribbons mediated by surface tension, we demonstrate that the enhanced creep properties of highly confined materials can be leveraged to shape helices into the desired geometry with full control of the final shape. The helical radius, total length, and pitch angle are all freely and independently tunable within a wide range: radius within â¼1-100 µm, length within â¼100-3000 µm, and pitch angle within â¼0-70°. This fabrication method is validated for three different materials: poly(methyl methacrylate), poly(dimethylaminoethyl methacrylate), and transition metal chalcogenide quantum dots, each corresponding to a different solid-phase structure: respectively a polymer glass, a cross-linked hydrogel, and a nanoparticle array. This demonstrates excellent versatility with respect to material selection, enabling further control of the helix mechanical properties.
ABSTRACT
Recent advances in memristive nanocrystal assemblies leverage controllable colloidal chemistry to induce a broad range of defect-mediated electrochemical reactions, switching phenomena, and modulate active parameters. The sample geometry of virtually all resistive switching studies involves thin film layers comprising monomodal diameter nanocrystals. Here we explore the evolution of bipolar and threshold resistive switching across highly ordered, solution-processed nanoribbon assemblies and mixtures comprising BaZrO3 (BZO) and SrZrO3 (SZO) nanocrystals. The effects of nanocrystal size, packing density, and A-site substitution on operating voltage (VSET and VTH) and switching mechanism were studied through a systematic comparison of nanoribbon heterogeneity (i.e., BZO-BZO vs BZO-SZO) and monomodal vs bimodal size distributions (i.e., small-small and small-large). Analysis of the current-voltage response confirms that tip-induced, trap-mediated space-charge-limited current and trap-assisted tunneling processes drive the low- and high-resistance states, respectively. Our results demonstrate that both smaller nanocrystals and heavier alkaline earth substitution decrease the onset voltage and improve stability and state retention of monomodal assemblies and bimodal nanocrystal mixtures, thus providing a base correlation that informs fabrication of solution-processed, memristive nanocrystal assemblies.
ABSTRACT
Local, micromechanical environment is known to influence cellular function in heterogeneous hydrogels, and knowledge gained in micromechanics will facilitate the improved design of biomaterials for tissue regeneration. In this study, a system comprising microstructured resilin-like polypeptide (RLP)-poly(ethylene glycol) (PEG) hydrogels is utilized. The micromechanical properties of RLP-PEG hydrogels are evaluated with oscillatory shear rheometry, compression dynamic mechanic analysis, small-strain microindentation, and large-strain indentation and puncture over a range of different deformation length scales. The measured elastic moduli are consistent with volume averaging models, indicating that volume fraction, not domain size, plays a dominant role in determining the low strain mechanical response. Large-strain indentation under a confocal microscope enables the visualization of the microstructured hydrogel micromechanical deformation, emphasizing the translation, rotation, and deformation of RLP-rich domains. The fracture initiation energy results demonstrate that failure of the composite hydrogels is controlled by the RLP-rich phase, and their independence with domain size suggested that failure initiation is controlled by multiple domains within the strained volume. This approach and findings provide new quantitative insight into the micromechanical response of soft hydrogel composites and highlight the opportunities in employing these methods to understand the physical origins of mechanical properties of soft synthetic and biological materials.
Subject(s)
Elastomers/chemistry , Hydrogels/chemistry , Mechanical Phenomena , Insect Proteins/chemistry , Peptides/chemistry , Polyethylene Glycols/chemistryABSTRACT
Materials composed of well-defined mesoscale building blocks are ubiquitous in nature, with noted ability to assemble into hierarchical structures possessing exceptional physical and mechanical properties. Fabrication of similar synthetic mesoscale structures will offer opportunities for precise conformational tuning toward advantageous bulk properties, such as increased toughness or elastic modulus. This requires new materials designs to be discovered to impart such structural control. Here, the preparation of mesoscale polymers is achieved by solution fabrication of functional polymers containing photoinduced chemical triggers. Subsequent photopatterning affords mesoscale block copolymers composed of distinct segments of alternating chemical composition. When dispersed in appropriate solvents, selected segments form helices to generate architectures resembling block copolymers, but on an optically observable size scale. This approach provides a platform for producing mesoscale geometries with structural control and potential for driving materials assembly comparable to examples found in nature.