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Microorganisms hosted in abiotic structures have led to engineered living materials that can grow, sense, and adapt in ways that mimic biological systems. Although porous structures should favor colonization by microorganisms, they have not yet been exploited as abiotic scaffolds for the development of living materials. Here, porous ceramics are reported that are colonized by bacteria to form an engineered living material with self-regulated and genetically programmable carbon capture and gas-sensing functionalities. The carbon capture capability is achieved using wild-type photosynthetic cyanobacteria, whereas the gas-sensing function is generated utilizing genetically engineered E. coli. Hierarchical porous clay is used as a ceramic scaffold and evaluated in terms of bacterial growth, water uptake, and mechanical properties. Using state-of-the-art chemical analysis techniques, the ability of the living porous ceramics are demonstrated to capture CO 2 directly from the air and to metabolically turn minute amounts of toxic gas into a benign scent detectable by humans., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Silicones find use in a myriad of applications from sealants and adhesives to cooking utensils and medical implants. However, state-of-the-art silicone parts fall short in terms of shape complexity and reprocessability. Advances in three-dimensional printing and the discovery of vitrimers have recently opened opportunities for shaping and recycling of silicone objects. Here, we report the 3D printing via direct ink writing of silicone vitrimers into complex-shaped parts with high strength and room-temperature reprocessability. The reprocessing properties of the printed objects result from the adaptive nature of the silicone vitrimer, which can deform under stress without losing its network connectivity. Rheological and mechanical experiments reveal that printable inks can be tuned to generate strong parts with high creep resistance and room-temperature reprocessability, two properties that are usually challenging to reconcile in vitrimers. By combining printability, high strength, and room-temperature reprocessability, the reported silicone vitrimers represent an attractive sustainable alternative to currently available elastomers in a broad range of established and prospective applications.

Airway stents are life-saving medical devices used to treat malignant or benign central airway stenoses. Unfortunately, these devices, typically manufactured from silicone alone and/or nitinol, can result in serious complications, such as stent migration, bacterial colonization, and tissue granulation, eventually forcing stent removal. Customized airway stents exhibit reduced migration and they can be tailored to address other complications by releasing drugs, such as the antibiotic levofloxacin and the antifibrotic drug nintedanib. Herein, the incorporation of these molecules in customized, bioresorbable 3D printed airway stents was investigated. Nintedanib (1.5 wt%) and levofloxacin (2.0 wt%) were incorporated in the polymer-based resin, which was used to 3D print tracheal stents with adequate mechanical and drug release properties. The drug-loaded stents were then deployed into rabbit tracheas and found to deliver the drugs locally with minimal systemic exposure. Drug activities were demonstrated by inhibition of bacterial colonization and reduced interleukin 8 (IL8) local expression. Although the application of these tracheal stents requires further exploration in larger animal models, this work paves the way for the rapid manufacturing of personalized medical devices with therapeutic functions., Competing Interests: Declaration of competing interest None., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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., Competing Interests: Competing interests statement:Two patent applications were submitted based on the results reported in this research.

Silica-based glasses can be shaped into complex geometries using a variety of additive manufacturing technologies. While the three-dimensional printing of glasses opens unprecedented design opportunities, the development of up-scaled, reliable manufacturing processes is crucial for the broader dissemination of this technology. Here, we design and study phase-separating resins that enable light-based 3D printing of oxide glasses with high-aspect-ratio features and enhanced manufacturing yields. The effect of the resin composition on the microstructure, mechanical properties and delamination resistance of parts printed by digital light processing is investigated with the help of printing experiments, compression tests and electron microscopy analysis. The chemical composition and microstructure of the cured resins were found to strongly affect the stiffness, delamination resistance, and calcination behavior of printed parts. These findings provide useful guidelines to enhance the reliability and yield of the DLP printing process of multicomponent silica-based glasses., (© 2024. The Author(s).)

Self-healing silicones that are able to restore functionalities and extend the lifetime of soft devices hold great potential in many applications. However, currently available silicones need to be triggered to self-heal or suffer from creep-induced irreversible deformation during use. Here, a platform is proposed to design and print silicone objects that are programmed at the molecular and architecture levels to achieve self-healing at room temperature while simultaneously resisting creep. At the molecular scale, dioxaborolanes moieties are incorporated into silicones to synthesize self-healing vitrimers, whereas conventional covalent bonds are exploited to make creep-resistant elastomers. When combined into architectured printed parts at a coarser length scale, the layered materials exhibit fast healing at room temperature without compromising the elastic recovery obtained from covalent polymer networks. A patient-specific vascular phantom and fluidic chambers are printed to demonstrate the potential of architectured silicones in creating damage-resilient functional devices using molecularly designed elastomer materials., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

The hemodynamics in the aorta as well as the durability of aortic valve prostheses vary greatly between different types of devices. Although placement and sizing of surgical aortic valve prostheses are excellent, the valve geometry of common devices cannot be customized to fit the patient's anatomy perfectly. Similarly, transcatheter aortic valve implantation (TAVI) devices are not customizable and may be orientated unfavorably during implantation. Imperfect fit of an aortic valve prosthesis may result in suboptimal performance and in some cases the need for additional surgery. Leveraging the advent of precision, multi-material 3D-printing, a bioinspired silicone aortic valve was developed. The manufacturing technique makes it fully customizable and significantly cheaper to develop and produce than common prostheses. In this study, we assess the hemodynamic performance of such a 3D-printed aortic valve and compare it to two TAVI devices as well as to a severely stenosed valve. We investigate the blood flow distal to the valve in an anatomically accurate, compliant aorta model via three-dimensional particle tracking velocimetry measurements. Our results demonstrate that the 3D-printed aortic valve induces flow patterns and topology compatible with the TAVI valves and showing similarity to healthy aortic blood flow. Compared to the stenosis, the 3D-printed aortic valve reduces turbulent kinetic energy levels and irreversible energy losses by over 75%, reaching values compatible with healthy subjects and conventional TAVIs. Our study substantiates that the 3D-printed heart valve displays a hemodynamic performance similar to established devices and underscores its potential for driving innovation towards patient specific valve prostheses., (© 2024. The Author(s).)

Diatoms have long been used as living biological indicators for the assessment of water quality in lakes and rivers worldwide. While this approach benefits from the great diversity of these unicellular algae, established protocols are time-consuming and require specialized equipment. Here, this work 3D prints diatom-laden hydrogels that can be used as a simple multiplex bio-indicator for water assessment. The hydrogel-based living materials are created with the help of a desktop extrusion-based printer using a suspension of diatoms, cellulose nanocrystals (CNC) and alginate as bio-ink constituents. Rheology and mechanical tests are employed to establish optimum bio-ink formulations, whereas cell culture experiments are utilized to evaluate the proliferation of the entrapped diatoms in the presence of selected water contaminants. Bioprinting of diatom-laden hydrogels is shown to be an enticing approach to generate living materials that can serve as low-cost bio-indicators for water quality assessment., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Advances in additive manufacturing have led to diverse patient-specific implant designs utilizing computed tomography, but this requires intensive work and financial implications. Here, Digital Light Processing is used to fabricate a hive-structured assemblable bespoke scaffold (HIVE). HIVE can be manually assembled in any shape/size with ease, so a surgeon can create a scaffold that will best fit a defect before implantation. Simultaneously, it can have site-specific treatments by working as a carrier filled with microcryogels (MC) incorporating different biological factors in different pockets of HIVE. After characterization, possible site-specific applications are investigated by utilizing HIVE as a versatile carrier with incorporated treatments such as growth factors (GF), bioceramic, or cells. HIVE as a GF-carrier shows a controlled release of bone morphogenetic protein/vascular endothelial growth factor (BMP/VEGF) and induced osteogenesis/angiogenesis from human mesenchymal stem cells (hMSC)/human umbilical vein endothelial cells (HUVECs). Furthermore, as a bioceramic-carrier, HIVE demonstrates enhanced mineralization and osteogenesis, and as a HUVEC carrier, it upregulates both osteogenic and angiogenic gene expression of hMSCs. HIVE with different combinations of MCs yields a distinct local effect and successful cell migration is confirmed within assembled HIVEs. Finally, an in vivo rat subcutaneous implantation demonstrates site-specific osteogenesis and angiogenesis., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Colloidal glasses display angle-independent structural color that is tunable by the size and local arrangement of sub-micrometer particles. While films, droplets, and microcapsules with isotropic structural color have been demonstrated, the shaping of colloidal glasses in three dimensions remains an open manufacturing challenge. Here, a light-based printing platform for the shaping of colloidal glasses into 3D objects featuring complex geometries and vivid structural color after thermal treatment is reported. Rheology, photopolymerization, and calcination experiments are performed to design the photoreactive resins leading to printable colloidal glasses. With the help of microscopy, scattering, and optical characterization, it is shown that the photonic properties of the printed objects reflect the locally ordered microstructure of the glass. The capability of the platform in creating 3D objects with isotropic structural color is illustrated by printing lattices and miniaturized sculpture replicas with unique shapes and multimaterial designs., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Limbless crawling on land requires breaking symmetry of the friction with the ground and exploiting an actuation mechanism to generate propulsive forces. Here, kirigami cuts are introduced into a soft magnetic sheet that allow to achieve effective crawling of untethered soft robots upon application of a rotating magnetic field. Bidirectional locomotion is achieved under clockwise and counterclockwise rotating magnetic fields with distinct locomotion patterns and crawling speed in forward and backward propulsions. The crawling and deformation profiles of the robot are experimentally characterized and combined with detailed multiphysics numerical simulations to extract locomotion mechanisms in both directions. It is shown that by changing the shape of the cuts and orientation of the magnet the robot can be steered, and if combined with translational motion of the magnet, complex crawling paths are programed. The proposed magnetic kirigami robot offers a simple approach to developing untethered soft robots with programmable motion., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

4D printing has a great potential for the manufacturing of soft robotics and medical devices. The alliance of digital light processing (DLP) 3D printing and novel shape-memory photopolymers allows for the fabrication of smart 4D-printed medical devices in high resolution and with tailorable functionalities. However, most of the reported 4D-printed materials are nondegradable, which limits their clinical applications. On the other hand, 4D printing of biodegradable shape-memory elastomers is highly challenging, especially when transition points close to physiological temperature and shape fixation under ambient conditions are required. Here, we report the 4D printing of biodegradable shape-memory elastomers with tailorable transition points covering physiological temperature, by using poly(D,L-lactide-co-trimethylene carbonate) methacrylates at various monomer feed ratios. After the programming step, the high-resolution DLP printed stents preserved their folded shape at room temperature, and showed efficient shape recovery at 37 °C. The materials were cytocompatible and readily degradable under physiological conditions. Furthermore, drug-loaded devices with tuneable release kinetics were realized by DLP-printing with resins containing polymers and levofloxacin or nintedanib. This study offers a new perspective for the development of next-generation 4D-printed medical devices., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Porous structures offer an attractive approach to reduce the amount of natural resources used while maintaining relatively high mechanical efficiency. However, for some applications the drop in mechanical properties resulting from the introduction of porosity is too high, which has limited the broader utilization of porous materials in industry. Here, it is shown that steel monoliths can be designed to display high mechanical efficiency and reversible self-reinforcing properties when made with porous architectures with up to three hierarchical levels. Ultralight steel structures that can float on water and autonomously adapt their stiffness are manufactured by the thermal reduction and sintering of 3D printed foam templates. Using distinct mechanical testing techniques, image analysis, and finite element simulations, the mechanisms leading to the high mechanical efficiency and self-stiffening ability of the hierarchical porous monoliths are studied. The design and fabrication of mechanically stable porous monoliths using iron as a widely available natural resource is expected to contribute to the future development of functional materials with a more sustainable footprint., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The strong clinical demand for more accurate and personalized health monitoring technologies has called for the development of additively manufactured wearable devices. While the materials palette for additive manufacturing continues to expand, the integration of materials, designs and digital fabrication methods in a unified workflow remains challenging. In this work, a 3D printing platform is proposed for the integrated fabrication of silicone-based soft wearables with embedded piezoresistive sensors. Silicone-based inks containing cellulose nanocrystals and/or carbon black fillers were thoroughly designed and used for the direct ink writing of a shoe insole demonstrator with encapsulated sensors capable of measuring both normal and shear forces. By fine-tuning the material properties to the expected plantar pressures, the patient-customized shoe insole was fully 3D printed at room temperature to measure in-situ gait forces during physical activity. Moreover, the digitized approach allows for rapid adaptation of the sensor layout to meet specific user needs and thereby fabricate improved insoles in multiple quick iterations. The developed materials and workflow enable a new generation of fully 3D printed soft electronic devices for health monitoring., (© 2023. The Author(s).)

Living materials with embedded microorganisms can genetically encode attractive sensing, self-repairing, and responsive functionalities for applications in medicine, robotics, and infrastructure. While the synthetic toolbox for genetically engineering bacteria continues to expand, technologies to shape bacteria-laden living materials into complex 3D geometries are still rather limited. Here, it is shown that bacteria-laden hydrogels can be shaped into living materials with unusual architectures and functionalities using readily available light-based printing techniques. Bioluminescent and melanin-producing bacteria are used to create complex materials with autonomous chemical-sensing capabilities by harnessing the metabolic activity of wild-type and engineered microorganisms. The shaping freedom offered by printing technologies and the rich biochemical diversity available in bacteria provides ample design space for the creation and exploration of complex living materials with programmable functionalities for a broad range of applications., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Biological living materials, such as animal bones and plant stems, are able to self-heal, regenerate, adapt and make decisions under environmental pressures. Despite recent successful efforts to imbue synthetic materials with some of these remarkable functionalities, many emerging properties of complex adaptive systems found in biology remain unexplored in engineered living materials. Here, we describe a three-dimensional printing approach that harnesses the emerging properties of fungal mycelia to create living complex materials that self-repair, regenerate and adapt to the environment while fulfilling an engineering function. Hydrogels loaded with the fungus Ganoderma lucidum are three-dimensionally printed into lattice architectures to enable mycelial growth in a balanced exploration and exploitation pattern that simultaneously promotes colonization of the gel and bridging of air gaps. To illustrate the potential of such mycelium-based living complex materials, we three-dimensionally print a robotic skin that is mechanically robust, self-cleaning and able to autonomously regenerate after damage., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Bacterial cellulose is an attractive resource for the manufacturing of sustainable materials, but it is usually challenging to shape it into elaborate three-dimensional structures. Here, we report a manufacturing platform for the creation of complex-shaped cellulose objects by printing inks loaded with bacteria into a silicone-based granular gel. The gel provides the viscoelastic behavior necessary to shape the bacteria-laden ink in three dimensions and the gas permeability required to sustain cellular growth and cellulose formation after the printing process. Using Gluconacetobacter xylinus as model cellulose-producing bacteria, we study the growth and the mechanical properties of cellulose fiber networks obtained upon incubation of the printed inks. Diffusion processes within the ink were found to control the growth of the cellulose structures, which display mechanical properties within the range expected for conventional hydrogels. By keeping the bacteria alive in the printed object, we produce living materials in complex geometries that are able to self-regenerate their cellulose fiber network after damage. Such living hydrogels represent an enticing development towards functional materials with autonomous self-healing and self-regenerating capabilities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Digital light processing (DLP) 3D printing is a promising technique for the rapid manufacturing of customized medical devices with high precision. To be successfully translated to a clinical setting, challenges in the development of suitable photopolymerizable materials have yet to be overcome. Besides biocompatibility, it is often desirable for the printed devices to be biodegradable, elastic, and with a therapeutic function. Here, a multifunctional DLP printed material system based on the composite of gold nanorods and polyester copolymer is reported. The material demonstrates robust near-infrared (NIR) responsiveness, allowing rapid and stable photothermal effect leading to the time-dependent cell death. NIR light-triggerable shape transformation is demonstrated, resulting in a facilitated insertion and expansion of DLP printed stent ex vivo. The proposed strategy opens a promising avenue for the design of multifunctional therapeutic devices based on nanoparticle-polymer composites., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Biological materials such as nacre have evolved microstructural design principles that result in outstanding mechanical properties. While nacre's design concepts have led to bio-inspired materials with enhanced fracture toughness, the microstructural features underlying the remarkable damping properties of this biological material have not yet been fully explored in synthetic composites. Here, we study the damping behavior of nacre-like composites containing mineral bridges and platelet asperities as nanoscale structural features within its brick-and-mortar architecture. Dynamic mechanical analysis was performed to experimentally elucidate the role of these features on the damping response of the nacre-like composites. By enhancing stress transfer between platelets and at the brick/mortar interface, mineral bridges and nano-asperities were found to improve the damping performance of the composite to levels that surpass many biological and man-made materials. Surprisingly, the improved properties are achieved without reaching the perfect organization of the biological counterparts. Our nacre-like composites display a loss modulus 2.4-fold higher than natural nacre and 1.4-fold more than highly dissipative natural fiber composites. These findings shed light on the role of nanoscale structural features on the dynamic mechanical properties of nacre and offer design concepts for the manufacturing of bio-inspired composites for high-performance damping applications.

3D printing is a powerful manufacturing technology for shaping materials into complex structures. While the palette of printable materials continues to expand, the rheological and chemical requisites for printing are not always easy to fulfill. Here, a universal manufacturing platform is reported for shaping materials into intricate geometries without the need for their printability, but instead using light-based printed salt structures as leachable molds. The salt structures are printed using photocurable resins loaded with NaCl particles. The printing, debinding, and sintering steps involved in the process are systematically investigated to identify ink formulations enabling the preparation of crack-free salt templates. The experiments reveal that the formation of a load-bearing network of salt particles is essential to prevent cracking of the mold during the process. By infiltrating the sintered salt molds and leaching the template in water, complex-shaped architectures are created from diverse compositions such as biomedical silicone, chocolate, light metals, degradable elastomers, and fiber composites, thus demonstrating the universal, cost-effective, and sustainable nature of this new manufacturing platform., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Structural color is frequently exploited by living organisms for biological functions and has also been translated into synthetic materials as a more durable and less hazardous alternative to conventional pigments. Additive manufacturing approaches were recently exploited for the fabrication of exquisite photonic objects, but the angle-dependence observed limits a broader application of structural color in synthetic systems. Here, we propose a manufacturing platform for the 3D printing of complex-shaped objects that display isotropic structural color generated from photonic colloidal glasses. Structurally colored objects are printed from aqueous colloidal inks containing monodisperse silica particles, carbon black, and a gel-forming copolymer. Rheology and Small-Angle-X-Ray-Scattering measurements are performed to identify the processing conditions leading to printed objects with tunable structural colors. Multimaterial printing is eventually used to create complex-shaped objects with multiple structural colors using silica and carbon as abundant and sustainable building blocks., (© 2022. The Author(s).)

Colors enable interaction and communication between living species in a myriad of biological and artificial environments. While living organisms feature low-power mechanisms to dynamically control color in soft tissues, man-made color-changing devices remain predominantly rigid and energy intensive. Here, architectured composites that display striking color changes when stretched in selective directions under ambient light with minimum power input are reported. The orientation-dependent color change results from the rotation of reflective coated platelets that are embedded in a soft polymer matrix and pre-aligned in a well-defined architecture. The light reflected by the platelets generates structural color defined by the oxide coating on the platelet surface. By magnetically programming the initial orientation and spatial distribution of selected platelets within the soft matrix, composites with strain-modulated color-changing effects that cannot be achieved using state-of-the-art technologies are created. The proposed concept of strain-induced architectured color can be harnessed to develop low-power smart stretchable displays, tactile synthetic skins, and autonomous soft robotic devices that undergo fast and reversible color changes through the mechano-optic coupling programmed within their soft composite architecture., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Nanowires are often key ingredients of high-tech composite materials. The properties and performance of devices created using these, depend heavily on the structure and density of the embedded nanowires. Despite significant efforts, a process that can be adapted to different materials, compatible with current nanowire deposition methods, and that is able to control both variables simultaneously has not been achieved yet. In this work, we show that we can use low magnetic fields (80 mT) to manipulate nanowires by electrostatically coating them with superparamagnetic iron oxide nanoparticles in an aqueous solution. Monolayers, multilayers, and hierarchical structures of oriented nanowires were achieved in a highly ordered manner using vacuum filtration for two types of nanowires: silver and gold-coated titanium dioxide nanowires. The produced films were embedded in an elastomer, and the strain-dependent electrical properties of the resulting composites were investigated. The orientation of the assembly with respect to the tensile strain heavily impacts the performance of the composites. Composites containing nanowires perpendicular to the strain direction exhibit an extremely low gauge factor. On the other hand, when nanowires are arranged parallel to the strain direction, the composites have a high gauge factor. The possibility to orient nanowires during the processing steps is not only interesting for the shown strain sensing application but also expected to be useful in many other areas of material science.

Monolithic aerogels composed of crystalline nanoparticles enable photocatalysis in three dimensions, but they suffer from low mechanical stability and it is difficult to produce them with complex geometries. Here, an approach to control the geometry of the photocatalysts to optimize their photocatalytic performance by introducing carefully designed 3D printed polymeric scaffolds into the aerogel monoliths is reported. This allows to systematically study and improve fundamental parameters in gas phase photocatalysis, such as the gas flow through and the ultraviolet light penetration into the aerogel and to customize its geometric shape to a continuous gas flow reactor. Using photocatalytic methanol reforming as a model reaction, it is shown that the optimization of these parameters leads to an increase of the hydrogen production rate by a factor of three from 400 to 1200 µmol g -1 h -1 . The rigid scaffolds also enhance the mechanical stability of the aerogels, lowering the number of rejects during synthesis and facilitating handling during operation. The combination of nanoparticle-based aerogels with 3D printed polymeric scaffolds opens up new opportunities to tailor the geometry of the photocatalysts for the photocatalytic reaction and for the reactor to maximize overall performance without necessarily changing the material composition., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

Porous materials are relevant for a broad range of technologies from catalysis and filtration, to tissue engineering and lightweight structures. Controlling the porosity of these materials over multiple length scales often leads to enticing new functionalities and higher efficiency but has been limited by manufacturing challenges and the poor understanding of the properties of hierarchical structures. Here, we report an experimental platform for the design and manufacturing of hierarchical porous materials via the stereolithographic printing of stable photo-curable Pickering emulsions. In the printing process, the micron-sized droplets of the emulsified resins work as soft templates for the incorporation of microscale porosity within sequentially photo-polymerized layers. The light patterns used to polymerize each layer on the building stage further generate controlled pores with bespoke three-dimensional geometries at the millimetre scale. Using this combined fabrication approach, we create architectured lattices with mechanical properties tuneable over several orders of magnitude and large complex-shaped inorganic objects with unprecedented porous designs., (© 2021. The Author(s).)

Cu 0 -mediated surface-initiated ATRP (Cu 0 SI-ATRP) emerges as a versatile, oxygen-tolerant process to functionalize three-dimensional (3D), microporous supports forming single and multiple polymer-brush gradients with a fully tunable composition. When polymerization mixtures are dispensed on a Cu 0 -coated plate, this acts as oxygen scavenger and source of active catalyst. In the presence of an ATRP initiator-bearing microporous elastomer placed in contact with the metallic plate, the reaction solution infiltrates by capillarity through the support, simultaneously triggering the controlled growth of polymer brushes. The polymer grafting process proceeds with kinetics that are determined by the progressive infiltration of the reaction solution within the microporous support and by the continuous diffusion of catalyst regenerated at the Cu 0 surface. The combination of these effects enables the accessible generation of 3D polymer-brush gradients extending across the microporous scaffolds used as supports, finally providing materials with a continuous variation of interfacial composition and properties.

Cells sense and respond to scaffold pore geometry and mechanical stimuli. Many fabrication methods used in bone tissue engineering render structures with poorly controlled pore geometries. Given that cell-scaffold interactions are complex, drawing a conclusion on how cells sense and respond to uncontrolled scaffold features under mechanical loading is difficult. In this study, monodisperse templated scaffolds (MTSC) were fabricated and used as well-defined porous scaffolds to study the effect of dynamic culture conditions on bone-like tissue formation. Human bone marrow-derived stromal cells were cultured on MTSC or conventional salt-leached scaffolds (SLSC) for up to 7 weeks, either under static or dynamic conditions (wall shear stress [WSS] using spinner flask bioreactors). The influence of controlled spherical pore geometry of MTSC subjected to static or dynamic conditions on osteoblast cell differentiation, bone-like tissue formation, structure, and distribution was investigated. WSS generated within the two idealized geometrical scaffold features was assessed. Distinct response to fluid flow in osteoblast cell differentiation were shown to be dependent on scaffold pore geometry. As revealed by collagen staining and microcomputed tomography images, dynamic conditions promoted a more regular extracellular matrix (ECM) formation and mineral distribution in both scaffold types compared with static conditions. The results showed that regulation of bone-related genes and the amount and the structure of mineralized ECM were dependent on scaffold pore geometry and the mechanical cues provided by the two different culture conditions. Under dynamic conditions, SLSC favored osteoblast cell differentiation and ECM formation, whereas MTSC enhanced ECM mineralization. The spherical pore shape in MTSC supported a more trabecular bone-like structure under dynamic conditions compared with MTSC statically cultured or to SLSC under either static or dynamic conditions. These results suggest that cell activity and bone-like tissue formation is driven not only by the pore geometry but also by the mechanical environment. This should be taken into account in the future design of complex scaffolds, which should favor cell differentiation while guiding the formation, structure, and distribution of the engineered bone tissue. This could help to mimic the anatomical complexity of the bone tissue structure and to adapt to each bone defect needs. Impact statement Aging of the human population leads to an increasing need for medical implants with high success rate. We provide evidence that cell activity and the amount and structure of bone-like tissue formation is dependent on the scaffold pore geometry and on the mechanical environment. Fabrication of complex scaffolds comprising concave and planar pore geometries might represent a promising direction toward the tunability and mimicry the structural complexity of the bone tissue. Moreover, the use of fabrication methods that allow a systematic fabrication of reproducible and geometrically controlled structures would simplify scaffold design optimization.

Microcapsules made of synthetic polymers are used for the release of cargo in agriculture, food, and cosmetics but are often difficult to be degraded in the environment. To diminish the environmental impact of microcapsules, we use the biofilm-forming ability of bacteria to grow cellulose-based biodegradable microcapsules. The present work focuses on the design and optimization of self-grown bacterial cellulose capsules. In contrast to their conventionally attributed pathogenic role, bacteria and their self-secreted biofilms represent a multifunctional class of biomaterials. The bacterial strain used in this work, Gluconacetobacter xylinus , is able to survive and proliferate in various environmental conditions by forming biofilms as part of its lifecycle. Cellulose is one of the main components present in these self-secreted protective layers and is known for its outstanding mechanical properties. Provided enough nutrients and oxygen, these bacteria and the produced cellulose are able to self-assemble at the interface of any given three-dimensional template and could be used as a novel stabilization concept for water-in-oil emulsions. Using a microfluidic setup for controlled emulsification, we demonstrate that bacterial cellulose capsules can be produced with tunable size and monodispersity. Furthermore, we show that successful droplet stabilization and bacterial cellulose formation are functions of the bacteria concentration, droplet size, and surfactant type. The obtained results represent the first milestone in the production of self-assembled biodegradable cellulose capsules to be used in a vast range of applications such as flavor, fragrance, agrochemicals, nutrients, and drug encapsulation.

The increasing use of lightweight composite materials in structural applications requires the development of new damage monitoring technologies to ensure their safe use and prevent accidents. Although several molecular strategies have been proposed to report damage in polymers through mechanochromic responses, these approaches have not yet been translated into lightweight bioinspired composites for load-bearing applications. Here, we report on the development of bioinspired laminates of alternating polymer and nacre-like layers that combine optical translucency, high fracture toughness, and damage-reporting capabilities. The composites signal damage via a fluorescence color change that arises from the force activation of mechanophore molecules embedded in the material's polymer phase. A quantitative correlation between the applied strain and the fluorescence intensity was successfully established. We demonstrate that optical imaging of mechanically loaded composites allows for the localized detection of damage prior to fracture. This fluorescence-based self-reporting mechanism offers a promising approach for the early detection of damage in lightweight structural composites and can serve as a useful tool for the analysis of fracture processes in bulk transparent materials.

Central airway obstruction is a life-threatening disorder causing a high physical and psychological burden to patients. Standard-of-care airway stents are silicone tubes, which provide immediate relief but are prone to migration. Thus, they require additional surgeries to be removed, which may cause tissue damage. Customized bioresorbable airway stents produced by 3D printing would be highly needed in the management of this disorder. However, biocompatible and biodegradable materials for 3D printing of elastic medical implants are still lacking. Here, we report dual-polymer photoinks for digital light 3D printing of customized and bioresorbable airway stents. These stents exhibit tunable elastomeric properties with suitable biodegradability. In vivo study in healthy rabbits confirmed biocompatibility and showed that the stents stayed in place for 7 weeks after which they became radiographically invisible. This work opens promising perspectives for the rapid manufacturing of the customized medical devices for which high precision, elasticity, and degradability are sought., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY).)

Precise control over the motion of magnetically responsive particles in fluidic chambers is important for probing and manipulating tasks in prospective microrobotic and bio-analytical platforms. We have previously exploited such colloids as shuttles for the microscale manipulation of objects. Here, we study the rolling motion of magnetically driven Janus colloids on solid substrates under the influence of an orthogonal external electric field. Electrically induced attractive interactions were used to tune the load on the Janus colloid and thereby the friction with the underlying substrate, leading to control over the forward velocity of the particle. Our experimental data suggest that the frictional coupling required to achieve translation, transitions from a hydrodynamic regime to one of mixed contact coupling with increasing load force. Based on this insight, we show that our colloidal microrobots can probe the local friction coefficient of various solid surfaces, which makes them potentially useful as tribological microsensors. Lastly, we precisely manipulate porous cargos using our colloidal rollers, a feat that holds promise for bio-analytical applications.

The brick-and-mortar architecture of biological nacre has inspired the development of synthetic composites with enhanced fracture toughness and multiple functionalities. While the use of metals as the "mortar" phase is an attractive option to maximize fracture toughness of bulk composites, non-mechanical functionalities potentially enabled by the presence of a metal in the structure remain relatively limited and unexplored. Using iron as the mortar phase, we develop and investigate nacre-like composites with high fracture toughness and stiffness combined with unique magnetic, electrical and thermal functionalities. Such metal-ceramic composites are prepared through the sol-gel deposition of iron-based coatings on alumina platelets and the magnetically-driven assembly of the pre-coated platelets into nacre-like architectures, followed by pressure-assisted densification at 1450 °C. With the help of state-of-the-art characterization techniques, we show that this processing route leads to lightweight inorganic structures that display outstanding fracture resistance, show noticeable magnetization and are amenable to fast induction heating. Materials with this set of properties might find use in transport, aerospace and robotic applications that require weight minimization combined with magnetic, electrical or thermal functionalities.

The properties of conventional materials result from the arrangement of and the interaction between atoms at the nanoscale. Metamaterials have shifted this paradigm by offering property control through structural design at the mesoscale, thus broadening the design space beyond the limits of traditional materials. A family of mechanical metamaterials consisting of soft sheets featuring a patterned array of reconfigurable bistable domes is reported here. The domes in this metamaterial architecture can be reversibly inverted at the local scale to generate programmable multistable shapes and tunable mechanical responses at the global scale. By 3D printing a robotic gripper with energy-storing skin and a structure that can memorize and compute spatially-distributed mechanical signals, it is shown that these metamaterials are an attractive platform for novel mechanologic concepts and open new design opportunities for structures used in robotics, architecture, and biomedical applications., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by Wiley‐VCH GmbH.)

Designing electrodes with tailored architecture is an efficient mean to enhance the performance of metal-ion batteries by minimizing electronic and ionic transport limitations and increasing the fraction of active material in the electrode. However, the fabrication of architectured electrodes often involves multiple laborious steps that are not directly scalable to current manufacturing platforms. Here, we propose a processing route in which Cu-coated ZnO powders are directly shaped into architectured electrodes using a simple uniaxial pressing step. Uniaxial pressing leads to a percolating Cu phase with enhanced electrical conductivity between the active ZnO particles and improved mechanical stability, thus dispensing the use of carbon-based additives and polymeric binders in the electrode composition. The additive-free percolating copper network obtained upon pressing leads to highly loaded integrated anodes displaying volumetric charge capacity 6-10 fold higher than Cu-free ZnO films and that matches the electrochemical performance reported for advanced cathode structures. Achieving this high charge capacity using a readily available pressing tool makes this approach a promising route for the facile manufacturing of high-performance electrodes at large industrial scales.

We report a versatile method to form bacterial cellulose coatings through simple dip-coating of 3D objects in suspensions of cellulose-producing bacteria. The adhesion of cellulose-secreting bacteria on objects was promoted through surface roughness and chemistry. Immobilized bacteria secreted highly porous hydrogels with high water content directly from the surface of a variety of materials. The out-of-plane orientation of cellulose fibers present in this coating leads to high mechanical stability and energy dissipation with minimal cellulose concentration. The conformal, biocompatible, and lubricious nature of the in situ grown cellulose surfaces makes the coated 3D objects attractive for biomedical applications.

The digital fabrication of oxide glasses by three-dimensional (3D) printing represents a major paradigm shift in the way glasses are designed and manufactured, opening opportunities to explore functionalities inaccessible by current technologies. The few enticing examples of 3D printed glasses are limited in their chemical compositions and suffer from the low resolution achievable with particle-based or molten glass technologies. Here, we report a digital light-processing 3D printing platform that exploits the photopolymerization-induced phase separation of hybrid resins to create glass parts with complex shapes, high spatial resolutions and multi-oxide chemical compositions. Analogously to conventional porous glass fabrication methods, we exploit phase separation phenomena to fabricate complex glass parts displaying light-controlled multiscale porosity and dense multicomponent transparent glasses with arbitrary geometry using a desktop printer. Because most functional properties of glasses emerge from their transparency and multicomponent nature, this 3D printing platform may be useful for distinct technologies, sciences and arts.

Responsive materials with birefringent optical properties have been exploited for the manipulation of light in several modern electronic devices. While electrical fields are often utilized to achieve optical modulation, magnetic stimuli may offer an enticing complementary approach for controlling and manipulating light remotely. Here, the synthesis and characterization of magnetically responsive birefringent microparticles with unusual magneto-optical properties are reported. These functional microparticles are prepared via a microfluidic emulsification process, in which water-based droplets are generated in a flow-focusing device and stretched into anisotropic shapes before conversion into particles via photopolymerization. Birefringence properties are achieved by aligning cellulose nanocrystals within the microparticles during droplet stretching, whereas magnetic responsiveness results from the addition of superparamagnetic nanoparticles to the initial droplet template. When suspended in a fluid, the microparticles can be controllably manipulated via an external magnetic field to result in unique magneto-optical coupling effects. Using a remotely actuated magnetic field coupled to a polarized optical microscope, these microparticles can be employed to convert magnetic into optical signals or to estimate the viscosity of the suspending fluid through magnetically driven microrheology., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Porosity is an essential feature in a wide range of applications that combine light weight with high surface area and tunable density. Porous materials can be easily prepared with a vast variety of chemistries using the salt-leaching technique. However, this templating approach has so far been limited to the fabrication of structures with random porosity and relatively simple macroscopic shapes. Here, a technique is reported that combines the ease of salt leaching with the complex shaping possibilities given by additive manufacturing (AM). By tuning the composition of surfactant and solvent, the salt-based paste is rheologically engineered and printed via direct ink writing into grid-like structures displaying structured pores that span from the sub-millimeter to the macroscopic scale. As a proof of concept, dried and sintered NaCl templates are infiltrated with magnesium (Mg), which is typically highly challenging to process by conventional AM techniques due to its highly oxidative nature and high vapor pressure. Mg scaffolds with well-controlled, ordered porosity are obtained after salt removal. The tunable mechanical properties and the potential to be predictably bioresorbed by the human body make these Mg scaffolds attractive for biomedical implants and demonstrate the great potential of this additive technique., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Adsorption heat pumps offer a clean, zero-emission technology for universally applicable cooling or heating utilizing water as a refrigerant and waste or renewable heat as driving energy instead of electricity. Despite their attractive environmentally friendly prospects, the broader application of such classes of heat pumps has not yet been possible, mainly because of the low power density of adsorption heat exchangers and the corresponding large size and high cost of the adsorption heat pumps. We report an inexpensive route for the fabrication of zeolite coatings with high adsorption power density based on the bottom-up assembly of colloids directed by magnetic and capillary forces. Such an assembly process relies on the chaining of oil droplets under an external magnetic field during deposition of the coating, followed by the formation of a percolating network of bridged adsorbent particles upon drying. This results in vertically open channels and thermal bridges that facilitate directed mass and heat transport across the structured zeolite coating during sorption cycles. By reaching up to 3.3-fold higher performance than their unstructured counterparts using readily available zeolite as an adsorbent material, the architectured coatings produced through this facile, upscalable approach hold great potential for next-generation adsorption heat pumps.

Materials combining optical transparency and mechanical strength are highly demanded for electronic displays, structural windows and in the arts, but the oxide-based glasses currently used in most of these applications suffer from brittle fracture and low crack tolerance. We report a simple approach to fabricate bulk transparent materials with a nacre-like architecture that can effectively arrest the propagation of cracks during fracture. Mechanical characterization shows that our glass-based composites exceed up to a factor of 3 the fracture toughness of common glasses, while keeping flexural strengths comparable to transparent polymers, silica- and soda-lime glasses. Due to the presence of stiff reinforcing platelets, the hardness of the obtained composites is an order of magnitude higher than that of transparent polymers. By implementing biological design principles into glass-based materials at the microscale, our approach opens a promising new avenue for the manufacturing of structural materials combining antagonistic functional properties.

Multi-layered composites in nature often show functional properties that are determined by the specific orientation of inorganic building blocks within each layer. The shell of bivalve molluscs and the exoskeleton of crustaceans constitute prominent examples. An effective approach to artificially produce textured microstructures inspired by such complex composites is magnetically assisted slip casting (MASC). MASC is a colloidal process in which anisotropic particles are magnetically oriented at arbitrarily defined angles and collected at the surface of a porous mould to grow the material in an additive manner. Whereas a number of proof-of-concept studies have established the potential of the technique, the full design space available for MASC-fabricated structures, and the limits of the approach, have so far not been explored systematically. To fill this gap, we have studied both theoretically and experimentally the various torques that act on the particles at the different stages of the assembly process. We define the boundary conditions of the MASC process for magnetically responsive alumina platelets suspended in a low-viscosity aqueous suspension, considering the composition of the colloidal suspension and the dynamics of the particle alignment process under a rotating magnetic field. These findings lead to design guidelines for the fabrication of bio-inspired composites with customized multi-scale structures for a broad range of applications.

Mechanosensing is ubiquitous in natural systems. From the skin ridges of our finger tips to the microscopic ion channels in cells, mechanosensors allow organisms to probe their environment and gather information needed for processing, decision making, and actuation. Despite technological advances in synthetic mechanosensing, it remains challenging to achieve this functionality at the scale of large stiff structures where both the amount of data to sense locally and the diversity of input stresses that the sensors have to withstand require highly tunable systems. Filtered sensing using mechanical displacement is an effective strategy developed by organisms to cope with large sets of stimuli. Inspired by this biological strategy, we fabricate bistable elements that can passively filter mechanical inputs, translate them into electrical signals, and be reset to their original sensing state using an external magnetic field. These multiple functionalities are achieved using hierarchically structured composites that can be arranged in large-area arrays. The filtering capability and fast passive response of our mechanosensors are experimentally demonstrated using simple electrical circuits and magnets. Thanks to their scalability and applicability to a wide range of material systems, these low-power sensors are avenues for the fabrication of load-bearing structures that are able to sense, compute, communicate, and autonomously adapt in response to external magneto-mechanical stimuli.

The complex behavior of highly deformable mechanical metamaterials can substantially enhance the performance of soft robots., (Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Hierarchical porous materials are widespread in nature and find an increasing number of applications as catalytic supports, biological scaffolds and lightweight structures. Recent advances in additive manufacturing and 3D printing technologies have enabled the digital fabrication of porous materials in the form of lattices, cellular structures and foams across multiple length scales. However, current approaches do not allow for the fast manufacturing of bulk porous materials featuring pore sizes that span broadly from macroscopic dimensions down to the nanoscale. Here, ink formulations are designed and investigated to enable 3D printing of hierarchical materials displaying porosity at the nano-, micro- and macroscales. Pores are generated upon removal of nanodroplets and microscale templates present in the initial ink. Using particles to stabilize the droplet templates is key to obtain Pickering nanoemulsions that can be 3D printed through direct ink writing. The combination of such self-assembled templates with the spatial control offered by the printing process allows for the digital manufacturing of hierarchical materials exhibiting thus far inaccessible multiscale porosity and complex geometries.

The nacreous layer of mollusk shells holds design concepts that can effectively enhance the fracture resistance of lightweight brittle materials. Mineral bridges are known to increase the fracture resistance of nacre-inspired materials, but their role is difficult to quantify due to the lack of experimental systems where only this parameter is controllably varied. In this study, we fabricate tunable nacre-like composites that are used as a model to experimentally quantify the influence of the density of mineral bridges alone on the fracture properties of nacre-like architectures. The composites exhibit a brick-and-mortar architecture comprising highly aligned alumina platelets that are interconnected by titania mineral bridges and infiltrated by an epoxy organic phase. By combining experimental mechanical data with image analysis of such composite microstructures, an analytical model is put forward based on a simple balance of forces acting on an individual bridged platelet. Based on this model, we predict the flexural strength of the nacre-like composite to scale linearly with the density of mineral bridges, as long as the mineral interconnectivity is low enough to keep fracture in a platelet pullout mode. Increasing the mineral interconnectivity beyond this limit leads to platelet fracture and catastrophic failure of the composite. This structure-property correlation provides powerful quantitative guidelines for the design of lightweight brittle materials with enhanced fracture resistance. We illustrate this potential by fabricating nacre-like bulk composites with unparalleled flexural strength combined with noncatastrophic failure., Competing Interests: The authors declare no conflict of interest.