Shaping Organs: Shared Structural Principles Across Kingdoms.

Development encapsulates the morphogenesis of an organism from a single fertilized cell to a functional adult. A critical part of development is the specification of organ forms. Beyond the molecular control of morphogenesis, shape in essence entails structural constraints and thus mechanics. Revisiting recent results in biophysics and development, and comparing animal and plant model systems, we derive key overarching principles behind the formation of organs across kingdoms. In particular, we highlight how growing organs are active rather than passive systems and how such behavior plays a role in shaping the organ. We discuss the importance of considering different scales in understanding how organs form. Such an integrative view of organ development generates new questions while calling for more cross-fertilization between scientific fields and model system communities.

Reductionist Approach in Peptide-Based Nanotechnology.

The formation of ordered nanostructures by molecular self-assembly of proteins and peptides represents one of the principal directions in nanotechnology. Indeed, polyamides provide superior features as materials with diverse physical properties. A reductionist approach allowed the identification of extremely short peptide sequences, as short as dipeptides, which could form well-ordered amyloid-like ß-sheet-rich assemblies comparable to supramolecular structures made of much larger proteins. Some of the peptide assemblies show remarkable mechanical, optical, and electrical characteristics. Another direction of reductionism utilized a natural noncoded amino acid, α-aminoisobutryic acid, to form short superhelical assemblies. The use of this exceptional helix inducer motif allowed the fabrication of single heptad repeats used in various biointerfaces, including their use as surfactants and DNA-binding agents. Two additional directions of the reductionist approach include the use of peptide nucleic acids (PNAs) and coassembly techniques. The diversified accomplishments of the reductionist approach, as well as the exciting future advances it bears, are discussed.

Tailoring chemical bonds to design unconventional glasses.

Glasses are commonly described as disordered counterparts of the corresponding crystals; both usually share the same short-range order, but glasses lack long-range order. Here, a quantification of chemical bonding in a series of glasses and their corresponding crystals is performed, employing two quantum-chemical bonding descriptors, the number of electrons transferred and shared between adjacent atoms. For popular glasses like SiO2, GeSe2, and GeSe, the quantum-chemical bonding descriptors of the glass and the corresponding crystal hardly differ. This explains why these glasses possess a similar short-range order as their crystals. Unconventional glasses, which differ significantly in their short-range order and optical properties from the corresponding crystals are only found in a distinct region of the map spanned by the two bonding descriptors. This region contains crystals of GeTe, Sb2Te3, and GeSb2Te4, which employ metavalent bonding. Hence, unconventional glasses are only obtained for solids, whose crystals employ theses peculiar bonds.

Light management by algal aggregates in living photosynthetic hydrogels.

Rapid progress in algal biotechnology has triggered a growing interest in hydrogel-encapsulated microalgal cultivation, especially for the engineering of functional photosynthetic materials and biomass production. An overlooked characteristic of gel-encapsulated cultures is the emergence of cell aggregates, which are the result of the mechanical confinement of the cells. Such aggregates have a dramatic effect on the light management of gel-encapsulated photobioreactors and hence strongly affect the photosynthetic outcome. To evaluate such an effect, we experimentally studied the optical response of hydrogels containing algal aggregates and developed optical simulations to study the resultant light intensity profiles. The simulations are validated experimentally via transmittance measurements using an integrating sphere and aggregate volume analysis with confocal microscopy. Specifically, the heterogeneous distribution of cell aggregates in a hydrogel matrix can increase light penetration while alleviating photoinhibition more effectively than in a flat biofilm. Finally, we demonstrate that light harvesting efficiency can be further enhanced with the introduction of scattering particles within the hydrogel matrix, leading to a fourfold increase in biomass growth. Our study, therefore, highlights a strategy for the design of spatially efficient photosynthetic living materials that have important implications for the engineering of future algal cultivation systems.

Neuromorphic one-shot learning utilizing a phase-transition material.

Design of hardware based on biological principles of neuronal computation and plasticity in the brain is a leading approach to realizing energy- and sample-efficient AI and learning machines. An important factor in selection of the hardware building blocks is the identification of candidate materials with physical properties suitable to emulate the large dynamic ranges and varied timescales of neuronal signaling. Previous work has shown that the all-or-none spiking behavior of neurons can be mimicked by threshold switches utilizing material phase transitions. Here, we demonstrate that devices based on a prototypical metal-insulator-transition material, vanadium dioxide (VO2), can be dynamically controlled to access a continuum of intermediate resistance states. Furthermore, the timescale of their intrinsic relaxation can be configured to match a range of biologically relevant timescales from milliseconds to seconds. We exploit these device properties to emulate three aspects of neuronal analog computation: fast (~1 ms) spiking in a neuronal soma compartment, slow (~100 ms) spiking in a dendritic compartment, and ultraslow (~1 s) biochemical signaling involved in temporal credit assignment for a recently discovered biological mechanism of one-shot learning. Simulations show that an artificial neural network using properties of VO2 devices to control an agent navigating a spatial environment can learn an efficient path to a reward in up to fourfold fewer trials than standard methods. The phase relaxations described in our study may be engineered in a variety of materials and can be controlled by thermal, electrical, or optical stimuli, suggesting further opportunities to emulate biological learning in neuromorphic hardware.

Directed evolution of material-producing microorganisms.

Nature is home to a variety of microorganisms that create materials under environmentally friendly conditions. While this offers an attractive approach for sustainable manufacturing, the production of materials by native microorganisms is usually slow and synthetic biology tools to engineer faster microorganisms are only available when prior knowledge of genotype-phenotype links is available. Here, we utilize a high-throughput directed evolution platform to enhance the fitness of whole microorganisms under selection pressure and identify genetic pathways to enhance the material production capabilities of native species. Using Komagataeibacter sucrofermentans as a model cellulose-producing microorganism, we show that our droplet-based microfluidic platform enables the directed evolution of these bacteria toward a small number of cellulose overproducers from an initial pool of 40,000 random mutants. Sequencing of the evolved strains reveals an unexpected link between the cellulose-forming ability of the bacteria and a gene encoding a protease complex responsible for protein turnover in the cell. The ability to enhance the fitness of microorganisms toward a specific phenotype and to unravel genotype-phenotype links makes this high-throughput directed evolution platform a promising tool for the development of new strains for the sustainable manufacturing of materials.

Synergistic material-microbe interface toward deeper anaerobic defluorination.

Per- and polyfluoroalkyl substances (PFAS), particularly the perfluorinated ones, are recalcitrant to biodegradation. By integrating an enrichment culture of reductive defluorination with biocompatible electrodes for the electrochemical process, a deeper defluorination of a C6-perfluorinated unsaturated PFAS was achieved compared to the biological or electrochemical system alone. Two synergies in the bioelectrochemical system were identified: i) The in-series microbial-electrochemical defluorination and ii) the electrochemically enabled microbial defluorination of intermediates. These synergies at the material-microbe interfaces surpassed the limitation of microbial defluorination and further turned the biotransformation end products into less fluorinated products, which could be less toxic and more biodegradable in the environment. This material-microbe hybrid system brings opportunities in the bioremediation of PFAS driven by renewable electricity and warrants future research on mechanistic understanding of defluorinating and electroactive microorganisms at the material-microbe interface for system optimizations.

Decoupling particle-impact dissipation mechanisms in 3D architected materials.

Ultralight architected materials enabled by advanced manufacturing processes have achieved density-normalized strength and stiffness properties that are inaccessible to bulk materials. However, the majority of this work has focused on static loading and elastic-wave propagation. Fundamental understanding of the mechanical behavior of architected materials under large-deformation dynamic conditions remains limited, due to the complexity of mechanical responses and shortcomings of characterization methods. Here, we present a microscale suspended-plate impact testing framework for three-dimensional micro-architected materials, where supersonic microparticles to velocities of up to 850 m/s are accelerated against a substrate-decoupled architected material to quantify its energy dissipation characteristics. Using ultra-high-speed imaging, we perform in situ quantification of the impact energetics on two types of architected materials as well as their constituent nonarchitected monolithic polymer, indicating a 47% or greater increase in mass-normalized energy dissipation under a given impact condition through use of architecture. Post-mortem characterization, supported by a series of quasi-static experiments and high-fidelity simulations, shed light on two coupled mechanisms of energy dissipation: material compaction and particle-induced fracture. Together, experiments and simulations indicate that architecture-specific resistance to compaction and fracture can explain a difference in dynamic impact response across architectures. We complement our experimental and numerical efforts with dimensional analysis which provides a predictive framework for kinetic-energy absorption as a function of material parameters and impact conditions. We envision that enhanced understanding of energy dissipation mechanisms in architected materials will serve to define design considerations toward the creation of lightweight impact-mitigating materials for protective applications.

Network physics of attractive colloidal gels: Resilience, rigidity, and phase diagram.

Colloidal gels exhibit solid-like behavior at vanishingly small fractions of solids, owing to ramified space-spanning networks that form due to particle-particle interactions. These networks give the gel its rigidity, and with stronger attractions the elasticity grows as well. The emergence of rigidity can be described through a mean field approach; nonetheless, fundamental understanding of how rigidity varies in gels of different attractions is lacking. Moreover, recovering an accurate gelation phase diagram based on the system's variables has been an extremely challenging task. Understanding the nature of colloidal clusters, and how rigidity emerges from their connections is key to controlling and designing gels with desirable properties. Here, we employ network analysis tools to interrogate and characterize the colloidal structures. We construct a particle-level network, having all the spatial coordinates of colloids with different attraction levels, and also identify polydisperse rigid fractal clusters using a Gaussian mixture model, to form a coarse-grained cluster network that distinctly shows main physical features of the colloidal gels. A simple mass-spring model then is used to recover quantitatively the elasticity of colloidal gels from these cluster networks. Interrogating the resilience of these gel networks shows that the elasticity of a gel (a dynamic property) is directly correlated to its cluster network's resilience (a static measure). Finally, we use the resilience investigations to devise [and experimentally validate] a fully resolved phase diagram for colloidal gelation, with a clear solid-liquid phase boundary using a single volume fraction of particles well beyond this phase boundary.

Magnetism and metallicity in moiré transition metal dichalcogenides.

The ability to control the properties of twisted bilayer transition metal dichalcogenides in situ makes them an ideal platform for investigating the interplay of strong correlations and geometric frustration. Of particular interest are the low energy scales, which make it possible to experimentally access both temperature and magnetic fields that are of the order of the bandwidth or the correlation scale. In this manuscript, we analyze the moiré Hubbard model, believed to describe the low energy physics of an important subclass of the twisted bilayer compounds. We establish its magnetic and the metal-insulator phase diagram for the full range of magnetic fields up to the fully spin-polarized state. We find a rich phase diagram including fully and partially polarized insulating and metallic phases of which we determine the interplay of magnetic order, Zeeman-field, and metallicity, and make connection to recent experiments.

Intelligent electroactive material systems with self-adaptive mechanical memory and sequential logic.

By synthesizing the requisite functionalities of intelligence in an integrated material system, it may become possible to animate otherwise inanimate matter. A significant challenge in this vision is to continually sense, process, and memorize information in a decentralized way. Here, we introduce an approach that enables all such functionalities in a soft mechanical material system. By integrating nonvolatile memory with continuous processing, we develop a sequential logic-based material design framework. Soft, conductive networks interconnect with embedded electroactive actuators to enable self-adaptive behavior that facilitates autonomous toggling and counting. The design principles are scaled in processing complexity and memory capacity to develop a model 8-bit mechanical material that can solve linear algebraic equations based on analog mechanical inputs. The resulting material system operates continually to monitor the current mechanical configuration and to autonomously search for solutions within a desired error. The methods created in this work are a foundation for future synthetic general intelligence that can empower materials to autonomously react to diverse stimuli in their environment.

Supramolecular coordination platinum metallacycle-based multilevel wound dressing for bacteria sensing and wound healing.

The exploitation of novel wound healing methods with real-time infection sensing and high spatiotemporal precision is highly important for human health. Pt-based metal-organic cycles/cages (MOCs) have been employed as multifunctional antibacterial agents due to their superior Pt-related therapeutic efficiency, various functional subunits and specific geometries. However, how to rationally apply these nanoscale MOCs on the macroscale with controllable therapeutic output is still challenging. Here, a centimeter-scale Pt MOC film was constructed via multistage assembly and subsequently coated on a N,N'-dimethylated dipyridinium thiazolo[5,4-d]thiazole (MPT)-stained silk fabric to form a smart wound dressing for bacterial sensing and wound healing. The MPT on silk fabric could be used to monitor wound infection in real-time through the bacteria-mediated reduction of MPT to its radical form via a color change. The MPT radical also exhibited an excellent photothermal effect under 660 nm light irradiation, which could not only be applied for photothermal therapy but also induce the disassembly of the Pt MOC film suprastructure. The highly ordered Pt MOC film suprastructure exhibited high biosafety, while it also showed improved antibacterial efficiency after thermally induced disassembly. In vitro and in vivo studies revealed that the combination of the Pt MOC film and MPT-stained silk can provide real-time information on wound infection for timely treatment through noninvasive techniques. This study paves the way for bacterial sensing and wound healing with centimeter-scale metal-organic materials.

Elasticity and rheology of auxetic granular metamaterials.

The flowing, jamming, and avalanche behavior of granular materials is satisfyingly universal and vexingly hard to tune: A granular flow is typically intermittent and will irremediably jam if too confined. Here, we show that granular metamaterials made from particles with a negative Poisson's ratio yield more easily and flow more smoothly than ordinary granular materials. We first create a collection of auxetic grains based on a re-entrant mechanism and show that each grain exhibits a negative Poisson's ratio regardless of the direction of compression. Interestingly, we find that the elastic and yielding properties are governed by the high compressibility of granular metamaterials: At a given confinement, they exhibit lower shear modulus, lower yield stress, and more frequent, smaller avalanches than materials made from ordinary grains. We further demonstrate that granular metamaterials promote flow in more complex confined geometries, such as intruder and hopper geometries, even when the packing contains only a fraction of auxetic grains. Moreover, auxetic granular metamaterials exhibit enhanced impact absorption. Our findings blur the boundary between complex fluids and metamaterials and could help in scenarios that involve process, transport, and reconfiguration of granular materials.

Sustainable, low-cost, high-contrast electrochromic displays via host-guest interactions.

Electrochromic (EC) displays with electronically regulating the transmittance of solar radiation offer the opportunity to increase the energy efficiency of the building and electronic products and improve the comfort and lifestyle of people. Despite the unique merit and vast application potential of EC technologies, long-awaited EC windows and related visual content displays have not been fully commercialized due to unsatisfactory production cost, durability, color, and complex fabrication processes. Here we develop a unique EC strategy and system based on the natural host and guest interactions to address the above issues. A completely reusable and sustainable EC device has been fabricated with potential advantages of extremely low cost, ideal user-/environment friendly property, and excellent optical modulation, which is benefited from the extracted biomass EC materials and reusable transparent electrodes involved in the system. The as-prepared EC window and nonemissive transparent display also show comprehensively excellent properties: high transmittance change (>85%), broad spectra modulation covering Ultraviolet (UV), Visible (Vis) to Infrared (IR) ranges, high durability (no attenuation under UV radiation for more than 1.5 mo), low open voltage (0.9 V), excellent reusability (>1,200 cycles) of the device's key components and reversibility (>4,000 cycles) with a large transmittance change, and pleasant multicolor. It is anticipated that unconventional exploration and design principles of dynamic host-guest interactions can provide unique insight into different energy-saving and sustainable optoelectronic applications.

Optimizing non-Newtonian fluids for impact protection of laminates.

Non-Newtonian fluids can be used for the protection of flexible laminates. Understanding the coupling between the flow of the protecting fluid and the deformation of the protected solids is necessary in order to optimize this functionality. We present a scaling analysis of the problem based on a single coupling variable, the effective width of a squeeze flow between flat rigid plates, and predict that impact protection for laminates is optimized by using shear-thinning, and not shear-thickening, fluids. The prediction is verified experimentally by measuring the velocity and pressure in impact experiments. Our scaling analysis should be generically applicable for non-Newtonian fluid-solid interactions in diverse applications.

In situ formed depot of elastin-like polypeptide-hirudin fusion protein for long-acting antithrombotic therapy.

Thrombosis, induced by abnormal coagulation or fibrinolytic systems, is the most common pathology associated with many life-threatening cardio-cerebrovascular diseases. However, first-line anticoagulant drugs suffer from rapid drug elimination and risk of hemorrhagic complications. Here, we developed an in situ formed depot of elastin-like polypeptide (ELP)-hirudin fusion protein with a prodrug-like feature for long-term antithrombotic therapy. Highly secretory expression of the fusion protein was achieved with the assistance of the Ffu312 tag. Integration of hirudin, ELP, and responsive moiety can customize fusion proteins with properties of adjustable in vivo retention and controllable recovery of drug bioactivity. After subcutaneous injection, the fusion protein can form a reservoir through temperature-induced coacervation of ELP and slowly diffuse into the blood circulation. The biological activity of hirudin is shielded due to the N-terminal modification, while the activated key proteases upon thrombus occurrence trigger the cleavage of fusion protein together with the release of hirudin, which has antithrombotic activity to counteract thrombosis. We substantiated that the optimized fusion protein produced long-term antithrombotic effects without the risk of bleeding in multiple animal thrombosis models.

Spin-orbit exciton-induced phonon chirality in a quantum magnet.

The interplay of charge, spin, lattice, and orbital degrees of freedom in correlated materials often leads to rich and exotic properties. Recent studies have brought new perspectives to bosonic collective excitations in correlated materials. For example, inelastic neutron scattering experiments revealed non-trivial band topology for magnons and spin-orbit excitons (SOEs) in a quantum magnet CoTiO3 (CTO). Here, we report phonon properties resulting from a combination of strong spin-orbit coupling, large crystal field splitting, and trigonal distortion in CTO. Specifically, the interaction between SOEs and phonons endows chirality to two [Formula: see text] phonon modes and leads to large phonon magnetic moments observed in magneto-Raman spectra. The remarkably strong magneto-phononic effect originates from the hybridization of SOEs and phonons due to their close energy proximity. While chiral phonons have been associated with electronic topology in some materials, our work suggests opportunities may arise by exploring chiral phonons coupled to topological bosons.

Disconnection flow-mediated grain rotation.

Grain rotation is commonly observed during the evolution of microstructures in polycrystalline materials of different kinds, including metals, ceramics, and colloidal crystals. It is widely accepted that interface migration in these systems is mediated by the motion of line defects with step and dislocation character, i.e., disconnections. We propose a crystallography-respecting continuum model for arbitrarily curved grain boundaries or heterophase interfaces, accounting for the disconnections' role in grain rotation. Numerical simulations demonstrate that changes in grain orientations, as well as interface morphology and internal stress field, are associated with disconnection flow. Our predictions agree with molecular dynamics simulation results for pure capillarity-driven evolution of grain boundaries and are interpreted through an extended Cahn-Taylor model.

Atomic observation and structural evolution of covalent organic framework rotamers.

Dynamic 3D covalent organic frameworks (COFs) have shown concerted structural transformation and adaptive gas adsorption due to the conformational diversity of organic linkers. However, the isolation and observation of COF rotamers constitute undergoing challenges due to their comparable free energy and subtle rotational energy barrier. Here, we report the atomic-level observation and structural evolution of COF rotamers by cryo-3D electron diffraction and synchrotron powder X-ray diffraction. Specifically, we optimize the crystallinity and morphology of COF-320 to manifest its coherent dynamic responses upon adaptive inclusion of guest molecules. We observe a significant crystal expansion of 29 vol% upon hydration and a giant swelling with volume change up to 78 vol% upon solvation. We record the structural evolution from a non-porous contracted phase to two narrow-pore intermediate phases and the fully opened expanded phase using n-butane as a stabilizing probe at ambient conditions. We uncover the rotational freedom of biphenylene giving rise to significant conformational changes on the diimine motifs from synclinal to syn-periplanar and anticlinal rotamers. We illustrate the 10-fold increment of pore volumes and 100% enhancement of methane uptake capacity of COF-320 at 100 bar and 298 K. The present findings shed light on the design of smarter organic porous materials to maximize host-guest interaction and boost gas uptake capacity through progressive structural transformation.

The elementary reactions for incorporation into crystals.

The growth rates of crystals are largely dictated by the chemical reaction between solute and kinks, in which a solute molecule severs its bonds with the solvent and establishes new bonds with the kink. Details on this sequence of bond breaking and rebuilding remain poorly understood. To elucidate the reaction at the kinks we employ four solvents with distinct functionalities as reporters on the microscopic structures and their dynamics along the pathway into a kink. We combine time-resolved in situ atomic force microscopy and x-ray and optical methods with molecular dynamics simulations. We demonstrate that in all four solvents the solute, etioporphyrin I, molecules reach the steps directly from the solution; this finding identifies the measured rate constant for step growth as the rate constant of the reaction between a solute molecule and a kink. We show that the binding of a solute molecule to a kink divides into two elementary reactions. First, the incoming solute molecule sheds a fraction of its solvent shell and attaches to molecules from the kink by bonds distinct from those in its fully incorporated state. In the second step, the solute breaks these initial bonds and relocates to the kink. The strength of the preliminary bonds with the kink determines the free energy barrier for incorporation into a kink. The presence of an intermediate state, whose stability is controlled by solvents and additives, may illuminate how minor solution components guide the construction of elaborate crystal architectures in nature and the search for solution compositions that suppress undesirable or accelerate favored crystallization in industry.