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Fast Photoactuation Driven by Supramolecular Polymers Integrated into Covalent Networks
Abstract The design of robotic soft matter capable of emulating the complex movements of living organisms such as mechanical actuation, shape transformation, and autonomous translation remains a grand challenge in soft materials science. Functionalized hydrogels are excellent candidates for such materials since they can operate in water and are highly responsive to their environment, but their response times can be slow. This work investigates fast photoactuation of hybrid bonding hydrogels composed of peptide amphiphile (PA) supramolecular nanofibers bonded covalently to merocyanine‐based (MCH + ) photoresponsive networks. By incorporating ionizable acrylic acid (AA) co‐monomers in these networks, photoactuation at nearly neutral pH is observed, which in turn enables a new mechanism to accelerate the response by triggering the bundling of supramolecular nanofibers by rapid proton exchange reactions. Furthermore, this rapid response and its consequent large shape transformations lead to hydrogels capable of spontaneously tracking external light sources inspired by pedicellariae, defensive organs present in echinoderms like the starfish and the sea urchin. This work suggests that hybrid bonding polymers (HBPs), which leverage the interplay between supramolecular assemblies and covalent networks, offer novel strategies to design rapidly actuating soft robotic materials.
Reactor physics characterization of triply periodic minimal surface-based nuclear fuel lattices
Triply periodic minimal surface (TPMS) lattices are receiving substantial attention in numerous engineering fields due to their impressive topology-driven physical characteristics. TPMS lattices are periodic structures of two distinct intertwined volume domains separated by an area-minimizing surface or wall. TPMS lattices have been observed in nature, such as biological membranes, skeletons, block copolymers, sea urchins, butterfly wings, and equipotential surfaces in crystals. Intriguingly, the topology of TPMS lattices can be easily parametrized via level-set equations and thus are heavily numerically and experimentally studied. Here, a significant research effort is currently applying TPMS lattices for heat exchangers and sinks. This paper extends TPMS lattice applications to nuclear reactor fuel designs, with a focus on identifying relevant TPMS geometric parameters controlling neutronics characteristics, such as reactivity, neutron spectrum, and heat removal properties. We found that fuel surface-area-to-volume ratios for TPMS lattices can be two orders of magnitude larger than current cylindrical fuel rods. Further, the selected TPMS lattice and its implicit equation, the unit cell pitch, wall thickness, and structure porosity are design parameters enabling neutronics optimization for both thermal and fast spectrum configurations, paving the way for exceptionally compact and dense nuclear core concepts.
Role of the Mineral in the Self-Healing of Cracks in Human Enamel
Human enamel is an incredibly resilient biological material, withstanding repeated daily stresses for decades. The mechanisms behind this resilience remain an open question, with recent studies demonstrating a crack-deflection mechanism contributing to enamel toughness and other studies detailing the roles of the organic matrix and remineralization. Here, we focus on the mineral and hypothesize that self-healing of cracks in enamel nanocrystals may be an additional mechanism acting to prevent catastrophic failure. To test this hypothesis, we used a molecular dynamics (MD) approach to compare the fracture behavior of hydroxyapatite (HAP) and calcite, the main minerals in human enamel and sea urchin teeth, respectively. In this work, we find that cracks heal under pressures typical of mastication by fusion of crystals in HAP but not in calcite, which is consistent with the resilience of HAP enamel that calcite teeth lack. Scanning transmission electron microscopy (STEM) images of structurally intact ("sound") human enamel show dashed-line nanocracks that resemble and therefore might be the cracks healed by fusion of crystals produced in silico . The fast, self-healing mechanism shown here is common in soft materials and ceramics but has not been observed in single crystalline materials at room temperature. The crack self-healing in sound enamel nanocrystals, therefore, is unique in the human body and unique in materials science, with potential applications in designing bioinspired materials.
Myriad Mapping of nanoscale minerals reveals calcium carbonate hemihydrate in forming nacre and coral biominerals
Abstract Calcium carbonate (CaCO 3 ) is abundant on Earth, is a major component of marine biominerals and thus of sedimentary and metamorphic rocks and it plays a major role in the global carbon cycle by storing atmospheric CO 2 into solid biominerals. Six crystalline polymorphs of CaCO 3 are known—3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO 3 ·6H 2 O), monohydrocalcite (CaCO 3 ·1H 2 O, MHC), and calcium carbonate hemihydrate (CaCO 3 ·½H 2 O, CCHH). CCHH was recently discovered and characterized, but exclusively as a synthetic material, not as a naturally occurring mineral. Here, analyzing 200 million spectra with Myriad Mapping (MM) of nanoscale mineral phases, we find CCHH and MHC, along with amorphous precursors, on freshly deposited coral skeleton and nacre surfaces, but not on sea urchin spines. Thus, biomineralization pathways are more complex and diverse than previously understood, opening new questions on isotopes and climate. Crystalline precursors are more accessible than amorphous ones to other spectroscopies and diffraction, in natural and bio-inspired materials.
Unusual dynamic susceptibility arising from soft ferromagnetic domains in MnBi 8 Te 13 and Sb-doped MnBi 2n Te 3n+1 (n = 2, 3)
MnBi$_{2n}$Te$_{3n+1}$ (MBT) is the first intrinsic magnetic topological insulator and is promising to host emergent phenomena such as quantum anomalous Hall effect. They can be made ferromagnetic by having n ≥ 4 or with Sb doping. In this work, we studied the magnetic dynamics in a few selected ferromagnetic (FM) MBT compounds, including MnBi 8 Te 13 and Sb doped MnBi$_{2n}$Te$_{3n+1}$ ($n = 2, 3)$ using AC susceptibility and magneto-optical imaging. Slow relaxation behavior is observed in all three compounds, suggesting its universality among FM MBT. We attribute the origin of the relaxation behavior to the irreversible domain movements since they only appear below the saturation fields when ferromagnetic domains form. The very soft ferromagnetic domain nature is revealed by the low-field fine-structured domains and high-field sea-urchin-shaped remanent-state domains imaged via our magneto-optical measurements. Finally, we ascribe the rare 'double-peak' behavior observed in the AC susceptibility under small DC bias fields to the very soft ferromagnetic domain formations.
Biomineral mesostructure
Abstract Biominerals formed by animals are most frequently calcium carbonate or phosphate polycrystalline materials with complex hierarchical structures. This article will focus on the 10-nm–10-µm scale, termed “mesoscale,” at which the “mesostructure” differs greatly across biominerals, is relevant to their mechanical properties, and reveals formation mechanisms in sea urchin teeth, mollusk shell prisms and nacre, human enamel, and coral skeletons. This article will conclude by focusing on important unanswered questions to inspire future research. Graphical abstract