Dynamic covalent polymer networks exhibit unusual adaptability while maintaining the robustness of conventional covalent networks. Typically, their network topology is statistically nonchangeable, and their material properties are therefore nonprogrammable. By introducing topological heterogeneity, we demonstrate a concept of topology isomerizable network (TIN) that can be programmed into many topological states. Using a photo-latent catalyst that controls the isomerization reaction, spatiotemporal manipulation of the topology is realized. The overall result is that the network polymer can be programmed into numerous polymers with distinctive and spatially definable (thermo-) mechanical properties. Among many opportunities for practical applications, the unique attributes of TIN can be explored for use as shape-shifting structures, adaptive robotic arms, and fracture-resistant stretchable devices, showing a high degree of design versatility. The TIN concept enriches the design of polymers, with potential expansion into other materials with variations in dynamic covalent chemistries, isomerizable topologies, and programmable macroscopic properties.

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Valvular heart diseases are complex disorders, varying in pathophysiological mechanism and affected valve components. Understanding the effects of these diseases on valve functionality requires a thorough characterization of the mechanics and structure of the healthy heart valves. In this study, we performed biaxial mechanical experiments with extensive testing protocols to examine the mechanical behaviors of the mitral valve and tricuspid valve leaflets. We also investigated the effect of loading rate, testing temperatures, species (porcine versus ovine hearts), and age (juvenile vs adult ovine hearts) on the mechanical responses of the leaflet tissues. In addition, we evaluated the structure of chordae tendineae within each valve and performed histological analysis on each atrioventricular leaflet. We found all tissues displayed a characteristic nonlinear anisotropic mechanical response, with radial stretches on average 30.7% higher than circumferential stretches under equibiaxial physiological loading. Tissue mechanical responses showed consistent mechanical stiffening in response to increased loading rate and minor temperature dependence in all five atrioventricular heart valve leaflets. Moreover, our anatomical study revealed similar chordae quantities in the porcine mitral (30.5 ± 1.43 chords) and tricuspid valves (35.3 ± 2.45 chords) but significantly more chordae in the porcine than the ovine valves (p < 0.010). Our histological analyses quantified the relative thicknesses of the four distinct morphological layers in each leaflet. This study provides a comprehensive database of the mechanics and structure of the atrioventricular valves, which will be beneficial to development of subject-specific atrioventricular valve constitutive models and toward multi-scale biomechanical investigations of heart valve function to improve valvular disease treatments.

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Spatially heterogeneous distribution of active components is key to the diverse shape-morphing behaviors of biological species and their associated functions. Artificial morphing materials employing similar strategies have widened the design space for advanced functional devices. Typically, the spatial heterogeneity is introduced during the material synthesis/fabrication step and cannot be altered afterward. An approach that allows spatio-selective programming of crystallinity in a shape-memory polymer (SMP) by a digital photothermal effect is reported. The light-patternable crystallinity affects greatly the shape morphing behavior. Consequently, a pre-stretched 2D film with spatial heterogeneity in crystallinity can morph with time into designable 3D permanent shapes, achieving the 4D transformation. This approach utilizes a reprocessible thermoplastic SMP (polylactide) and the programming relies on a physical phase transformation (crystallization) instead of chemical heterogeneity. This allows repeated erasing and reprogramming using the same material, suggesting a versatile and sustainable means for manufacturing advanced morphing devices.

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Intracranial aneurysms (ICAs) are focal dilations in the brain's arteries. When left untreated, ICAs can grow to the point of rupture, accounting for 50-80% of subarachnoid hemorrhage cases. Current treatments include surgical clipping and endovascular coil embolization to block circulation into the aneurysmal space for preventing aneurysm rupture. As for endovascular embolization, patients could experience aneurysm recurrence due to an incomplete coil filling or compaction over time. The use of shape memory polymers (SMPs) in place of conventional platinum coils could provide more control and predictability for mitigating these complications. This study was focused on characterization of an aliphatic urethane-based SMP to evaluate its potential as a novel biomaterial for endovascular embolization. Twelve compositions of the SMP were synthesized and their thermomechanical properties together with the shape recovery behavior were comprehensively investigated. Our results showed that the SMPs experienced a significant decrease in storage and loss moduli as heated above their glass transition temperatures (32.3-83.2 °C), and that all SMPs were thermally stable up to 265 °C. Moreover, the SMPs exhibited both composition-dependent stress relaxation and a decrease in elastic modulus during cyclic loading. The shape recovery time was less than 11 s for all SMP compositions, which is sufficiently short for shape changing during embolization procedures. Several candidate compositions were identified, which possess a glass transition temperature above body temperature (37 °C) and below the threshold of causing tissue damage (45 °C). They also exhibit high material strength and low stress relaxation behavior, suggesting their potential applicability to endovascular embolization of ICAs.

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