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64 result(s) for "Ashby, Paul D."
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Reconfigurable ferromagnetic liquid droplets
Solid ferromagnetic materials are rigid in shape and cannot be reconfigured. Ferrofluids, although reconfigurable, are paramagnetic at room temperature and lose their magnetization when the applied magnetic field is removed. Here, we show a reversible paramagnetic-to-ferromagnetic transformation of ferrofluid droplets by the jamming of a monolayer of magnetic nanoparticles assembled at the water-oil interface. These ferromagnetic liquid droplets exhibit a finite coercivity and remanent magnetization. They can be easily reconfigured into different shapes while preserving themagnetic properties of solid ferromagnets with classic north-south dipole interactions. Their translational and rotational motions can be actuated remotely and precisely by an external magnetic field, inspiring studies on active matter, energy-dissipative assemblies, and programmable liquid constructs.
Harnessing liquid-in-liquid printing and micropatterned substrates to fabricate 3-dimensional all-liquid fluidic devices
Systems comprised of immiscible liquids held in non-equilibrium shapes by the interfacial assembly and jamming of nanoparticle−polymer surfactants have significant potential to advance catalysis, chemical separations, energy storage and conversion. Spatially directing functionality within them and coupling processes in both phases remains a challenge. Here, we exploit nanoclay−polymer surfactant assemblies at an oil−water interface to produce a semi-permeable membrane between the liquids, and from them all-liquid fluidic devices with bespoke properties. Flow channels are fabricated using micropatterned 2D substrates and liquid-in-liquid 3D printing. The anionic walls of the device can be functionalized with cationic small molecules, enzymes, and colloidal nanocrystal catalysts. Multi-step chemical transformations can be conducted within the channels under flow, as can selective mass transport across the liquid−liquid interface for in-line separations. These all-liquid systems become automated using pumps, detectors, and control systems, revealing a latent ability for chemical logic and learning. Non-equilibrium systems of immiscible liquids have significant potential to advance different technologies, but control over morphology or functionality remains unexplored. Here, the authors demonstrate an all-liquid fluidic device by exploiting surfactant assemblies to produce a semi-permeable membrane between the liquids.
The living interface between synthetic biology and biomaterial design
Recent far-reaching advances in synthetic biology have yielded exciting tools for the creation of new materials. Conversely, advances in the fundamental understanding of soft-condensed matter, polymers and biomaterials offer new avenues to extend the reach of synthetic biology. The broad and exciting range of possible applications have substantial implications to address grand challenges in health, biotechnology and sustainability. Despite the potentially transformative impact that lies at the interface of synthetic biology and biomaterials, the two fields have, so far, progressed mostly separately. This Perspective provides a review of recent key advances in these two fields, and a roadmap for collaboration at the interface between the two communities. We highlight the near-term applications of this interface to the development of hierarchically structured biomaterials, from bioinspired building blocks to ‘living’ materials that sense and respond based on the reciprocal interactions between materials and embedded cells. This Perspective reviews the complementary developments in synthetic biology and biomaterials and discusses how convergence of these two fields creates a promising design strategy for the fabrication of tailored living materials for medicine and biotechnology.
Angle between DNA linker and nucleosome core particle regulates array compaction revealed by individual-particle cryo-electron tomography
The conformational dynamics of nucleosome arrays generate a diverse spectrum of microscopic states, posing challenges to their structural determination. Leveraging cryogenic electron tomography (cryo-ET), we determine the three-dimensional (3D) structures of individual mononucleosomes and arrays comprising di-, tri-, and tetranucleosomes. By slowing the rate of condensation through a reduction in ionic strength, we probe the intra-array structural transitions that precede inter-array interactions and liquid droplet formation. Under these conditions, the arrays exhibite irregular zig-zag conformations with loose packing. Increasing the ionic strength promoted intra-array compaction, yet we do not observe the previously reported regular 30-nanometer fibers. Interestingly, the presence of H1 do not induce array compaction; instead, one-third of the arrays display nucleosomes invaded by foreign DNA, suggesting an alternative role for H1 in chromatin network construction. We also find that the crucial parameter determining the structure adopted by chromatin arrays is the angle between the entry and exit of the DNA and the corresponding tangents to the nucleosomal disc. Our results provide insights into the initial stages of intra-array compaction, a critical precursor to condensation in the regulation of chromatin organization. Here, using cryo-ET, the 3D structures of individual nucleosome particles were characterized to observe changes under varying ionic strengths and in the presence of protein H1, revealing key regulatory roles in chromatin organization dynamics.
A de novo matrix for macroscopic living materials from bacteria
Engineered living materials (ELMs) embed living cells in a biopolymer matrix to create materials with tailored functions. While bottom-up assembly of macroscopic ELMs with a de novo matrix would offer the greatest control over material properties, we lack the ability to genetically encode a protein matrix that leads to collective self-organization. Here we report growth of ELMs from Caulobacter crescentus cells that display and secrete a self-interacting protein. This protein formed a de novo matrix and assembled cells into centimeter-scale ELMs. Discovery of design and assembly principles allowed us to tune the composition, mechanical properties, and catalytic function of these ELMs. This work provides genetic tools, design and assembly rules, and a platform for growing ELMs with control over both matrix and cellular structure and function. Engineered living materials (ELMs) embed living cells in a biopolymer matrix to create novel materials with tailored functions. In this work, the authors engineered bacteria to grow novel macroscopic materials that can be reshaped, functionalized, and used to filter contaminated water while also showing that the stiffness of these materials can be tuned through genetic changes.
Visualizing nanoscale excitonic relaxation properties of disordered edges and grain boundaries in monolayer molybdenum disulfide
Two-dimensional monolayer transition metal dichalcogenide semiconductors are ideal building blocks for atomically thin, flexible optoelectronic and catalytic devices. Although challenging for two-dimensional systems, sub-diffraction optical microscopy provides a nanoscale material understanding that is vital for optimizing their optoelectronic properties. Here we use the ‘Campanile’ nano-optical probe to spectroscopically image exciton recombination within monolayer MoS 2 with sub-wavelength resolution (60 nm), at the length scale relevant to many critical optoelectronic processes. Synthetic monolayer MoS 2 is found to be composed of two distinct optoelectronic regions: an interior, locally ordered but mesoscopically heterogeneous two-dimensional quantum well and an unexpected ∼300-nm wide, energetically disordered edge region. Further, grain boundaries are imaged with sufficient resolution to quantify local exciton-quenching phenomena, and complimentary nano-Auger microscopy reveals that the optically defective grain boundary and edge regions are sulfur deficient. The nanoscale structure–property relationships established here are critical for the interpretation of edge- and boundary-related phenomena and the development of next-generation two-dimensional optoelectronic devices. Understanding the dynamics of light-induced carriers is vital for employing two-dimensional materials in optoelectronic applications. Here, the authors use a sub diffraction-limit optical technique to reveal the excitonic properties of monolayer molybdenum disulfide at the nanoscale.
Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite
Photovoltaic devices based on hybrid perovskite materials have exceeded 22% efficiency due to high charge-carrier mobilities and lifetimes. Properties such as photocurrent generation and open-circuit voltage are influenced by the microscopic structure and orientation of the perovskite crystals, but are difficult to quantify on the intra-grain length scale and are often treated as homogeneous within the active layer. Here, we map the local short-circuit photocurrent, open-circuit photovoltage, and dark drift current in state-of-the-art methylammonium lead iodide solar cells using photoconductive atomic force microscopy. We find, within individual grains, spatially correlated heterogeneity in short-circuit current and open-circuit voltage up to 0.6 V. These variations are related to different crystal facets and have a direct impact on the macroscopic power conversion efficiency. We attribute this heterogeneity to a facet-dependent density of trap states. These results imply that controlling crystal grain and facet orientation will enable a systematic optimization of polycrystalline and single-crystal devices for photovoltaic and lighting applications. The photovoltaic properties of hybrid organic–inorganic perovskites are sensitive to the local microstructure, but difficult to quantify at the nanoscale. Leblebici et al.  use conductive atomic force microscopy to map the local short-circuit current and open-circuit voltage, finding heterogeneity within individual grains.
Hanging droplets from liquid surfaces
Natural and man-made robotic systems use the interfacial tension between two fluids to support dense objects on liquid surfaces. Here, we show that coacervate-encased droplets of an aqueous polymer solution can be hung from the surface of a less dense aqueous polymer solution using surface tension. The forces acting on and the shapes of the hanging droplets can be controlled. Sacs with homogeneous and heterogeneous surfaces are hung from the surface and, by capillary forces, form well-ordered arrays. Locomotion and rotation can be achieved by embedding magnetic microparticles within the assemblies. Direct contact of the droplet with air enables in situ manipulation and compartmentalized cascading chemical reactions with selective transport. Applications including functional microreactors, motors, and biomimetic robots are evident.
Visualization of the flat electronic band in twisted bilayer graphene near the magic angle twist
Bilayer graphene has been predicted to host a moiré miniband with flat dispersion if the layers are stacked at specific twist angles known as the ’magic angles’1,2. Recently, twisted bilayer graphene (tBLG) with a magic angle twist was reported to exhibit a correlated insulating state and superconductivity3,4, where the presence of the flat miniband in the system is thought to be essential for the emergence of these ordered phases in the transport measurements. Although tunnelling spectroscopy5–9 and electronic compressibility measurements10 in tBLG have found a van Hove singularity that is consistent with the presence of the flat miniband, a direct observation of the flat dispersion in the momentum space of such a moiré miniband in tBLG is still lacking. Here, we report the visualization of this flat moiré miniband by using angle-resolved photoemission spectroscopy with nanoscale resolution. The high spatial resolution of this technique enabled the measurement of the local electronic structure of the tBLG. The measurements demonstrate the existence of the flat moiré band near the charge neutrality for tBLG close to the magic angle at room temperature.The flat electronic bands that are associated with ordered phases in twisted bilayer graphene at a magic twist angle have been imaged using angle-resolved photoemission spectroscopy.