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  1. Abstract

    A growing number of two-dimensional superconductors are being discovered in the family of exfoliated van der Waals materials. Due to small sample volume, the superfluid response of these materials has not been characterized. Here, we use a local magnetic probe to directly measure this key property of the tunable, gate-induced superconducting state in MoS2. We find that the backgate changes the transition temperature non-monotonically whereas the superfluid stiffness at low temperature and the normal state conductivity monotonically increase. In some devices, we find direct signatures in agreement with a Berezinskii-Kosterlitz-Thouless transition, whereas in others we find a broadened onset of the superfluid response. We show that the observed behavior is consistent with disorder playing an important role in determining the properties of superconducting MoS2. Our work demonstrates that magnetic property measurements are within reach for superconducting devices based on exfoliated sheets and reveals that the superfluid response significantly deviates from simple BCS-like behavior.

     
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  2. Abstract

    Metal‐organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes with myriad potential applications in chemical separations, catalysis, and drug delivery. A major barrier to the application of MOFs is their poor scalability, as most frameworks are prepared under highly dilute solvothermal conditions using toxic organic solvents. Herein, we demonstrate that combining a range of linkers with low‐melting metal halide (hydrate) salts leads directly to high‐quality MOFs without added solvent. Frameworks prepared under these ionothermal conditions possess porosities comparable to those prepared under traditional solvothermal conditions. In addition, we report the ionothermal syntheses of two frameworks that cannot be prepared directly under solvothermal conditions. Overall, the user‐friendly method reported herein should be broadly applicable to the discovery and synthesis of stable metal‐organic materials.

     
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  3. Abstract

    Polar skyrmions are predicted to emerge from the interplay of elastic, electrostatic and gradient energies, in contrast to the key role of the anti-symmetric Dzyalozhinskii-Moriya interaction in magnetic skyrmions. Here, we explore the reversible transition from a skyrmion state (topological charge of −1) to a two-dimensional, tetratic lattice of merons (with topological charge of −1/2) upon varying the temperature and elastic boundary conditions in [(PbTiO3)16/(SrTiO3)16]8membranes. This topological phase transition is accompanied by a change in chirality, from zero-net chirality (in meronic phase) to net-handedness (in skyrmionic phase). We show how scanning electron diffraction provides a robust measure of the local polarization simultaneously with the strain state at sub-nm resolution, while also directly mapping the chirality of each skyrmion. Using this, we demonstrate strain as a crucial order parameter to drive isotropic-to-anisotropic structural transitions of chiral polar skyrmions to non-chiral merons, validated with X-ray reciprocal space mapping and phase-field simulations.

     
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  4. Abstract

    Load‐bearing soft tissues are soft but strong, strong yet tough. These properties can only be replicated in synthetic hydrogels, which do not have the biocomplexity required by many biomedical applications. By contrast, natural hydrogels, although retaining the native complexity, are weak and fragile. Here a thermomechanical casting method is presented to achieve the mechanical capabilities of synthetic materials in biopolymer hydrogels. The thermomechanical cast and chemically crosslinked biopolymer chains form a short‐range disordered but long‐range ordered structure in water. Upon stretch, the disordered structure transforms to a hierarchically ordered structure. This disorder‐order transformation resembles the synergy of the disordered elastin and ordered collagen in load‐bearing soft tissues. As entropy drives a reverse order‐disorder transformation, the hydrogels can resist repeated cycles of loads without deterioration in mechanical properties. Gelatin hydrogels produced by this method combine tissue‐like tunable mechanical properties that outperform the gelatin prepared by synthetic approaches, and in vivo biocomplexity beyond current natural systems. Unlike polymer engineering approaches, which rely on specific crosslinks provided by special polymers, this strategy utilizes the entropy of swollen chains and is generalizable to many other biopolymers. It could thus significantly accelerate translational success of biomaterials.

     
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  5. Abstract

    Early phases of green material development can be accelerated by identifying driving factors that control material properties to understand potential tradeoffs. Full investigation of fabrication variables is often prohibitively expensive. We propose a pared‐down design of experiments (DOE) approach to identify driving variables in limited data scenarios using tunable polydimethylsiloxane (PDMS) foams made via sacrificial templating as an example system. This new approach systematically determines the dependencies of porosity, transparency, and fluid flow by varying the template particle size and packing while using a more sustainable solvent. Factor screening identified template particle size and packing density as the driving factors for foam performance by controlling pore size and interconnectivity. The framework developed provides a robust, foundational understanding of how to green and tune a novel material's properties using an efficient and effective exploration of the design space. Recommendations for applying this method to a broad suite of experiments are provided.

     
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  6. Abstract

    The relationship between root, stem, and leaf hydraulic status and stomatal conductance during drought (field capacities: 100–25%) and drought recovery was studied in Helianthus annuus and five tree species (Populus×canadensis, Acer saccharum, A. saccharinum, Picea glauca, and Tsuga canadensis). Measurements of stomatal conductance (gs), organ water potential, and vessel embolism were performed and the following was observed: (i) cavitation only occurred in the petioles and not the roots or stems of tree species regardless of drought stress; (ii) in contrast, all H. annuus organs exhibited cavitation to an increasing degree from root to petiole; and (iii) all species initiated stomatal closure before cavitation events occurred or the expected turgor loss point was reached. After rewatering: (i) cavitated vessels in petioles of Acer species recovered whereas those of P. ×canadensis did not and leaves were shed; (ii) in H. annuus, cavitated xylem vessels were refilled in roots and petioles, but not in stems; and (iii) despite refilled embolisms in petioles of some species during drought recovery, gs never returned to pre-drought conditions. Conclusions are drawn with respect to the hydraulic segmentation hypothesis for above- and below-ground organs, and the timeline of embolism occurrence and repair is discussed.

     
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  7. Abstract

    Magnetic nanoparticle chains offer the anisotropic magnetic properties that are often desirable for micro‐ and nanoscale systems; however, to date, large‐scale fabrication of these nanochains is limited by the need for an external magnetic field during the synthesis. In this work, the unique self‐assembly of nanoparticles into chains as a result of their intrinsic dipolar interactions only is examined. In particular, it is shown that in a high concentration reaction regime, the dipole–dipole coupling between two neighboring magnetic iron cobalt (FeCo) nanocubes, was significantly strengthened due to small separation between particles and their high magnetic moments. This dipole–dipole interaction enables the independent alignment and synthesis of magnetic FeCo nanochains without the assistance of any templates, surfactants, or even external magnetic field. Furthermore, the precursor concentration ([M] = 0.016, 0.021, 0.032, 0.048, 0.064, and 0.096m) that dictates the degree of dipole interaction is examined—a property dependent on particle size and inter‐particle distance. By varying the spinner speed, it is demonstrated that the balance between magnetic dipole coupling and fluid dynamics can be used to understand the self‐assembly process and control the final structural topology from that of dimers to linear chains (with aspect ratio >10:1) and even to branched networks. Simulations unveil the magnetic and fluid force landscapes that determine the individual nanoparticle interactions and provide a general insight into predicting the resulting nanochain morphology. This work uncovers the enormous potential of an intrinsic magnetic dipole‐induced assembly, which is expected to open new doors for efficient fabrication of 1D magnetic materials, and the potential for more complex assemblies with further studies.

     
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  8. Abstract

    Smart materials are versatile material systems which exhibit a measurable response to external stimuli. Recently, smart material systems have been developed which incorporate graphene in order to share on its various advantageous properties, such as mechanical strength, electrical conductivity, and thermal conductivity as well as to achieve unique stimuli‐dependent responses. Here, a graphene fiber‐based smart material that exhibits reversible electrical conductivity switching at a relatively low temperature (60 °C), is reported. Using molecular dynamics (MD) simulation and density functional theory‐based non‐equilibrium Green's function (DFT‐NEGF) approach, it is revealed that this thermo‐response behavior is due to the change in configuration of amphiphilic triblock dispersant molecules occurring in the graphene fiber during heating or cooling. These conformational changes alter the total number of graphene‐graphene contacts within the composite material system, and thus the electrical conductivity as well. Additionally, this graphene fiber fabrication approach uses a scalable, facile, water‐based method, that makes it easy to modify material composition ratios. In all, this work represents an important step forward to enable complete functional tuning of graphene‐based smart materials at the nanoscale while increasing commercialization viability.

     
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  9. Abstract

    Poly(styrene‐coN‐maleimide) copolymers bearingtert‐butoxycarbonyl (t‐BOC)‐protected amine groups attached to side chains of varying lengths are synthesized via activators regenerated by electron transfer atom transfer radical polymerization (ARGET‐ATRP) and investigated from the perspective of photoresist applications. The length of the alkyl substituents enables control of thermal properties as well as hydrophobicity, which are critically important for resist processing. Removal of the acid labilet‐BOC group during deep‐UV (DUV)exposure shifts solubility in the exposed areas and well‐defined line space patterns of 1 µm are obtained for the selected copolymers. The correlation between glass transition temperature (Tg) and solubility contrast determines the lithographic performance where the copolymers with shorter alkyl chains exhibit promising results.

     
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  10. Abstract

    Emissive covalent organic frameworks (COFs) have recently emerged as next‐generation porous materials with attractive properties such as tunable topology, porosity, and inherent photoluminescence. Among the different types of COFs, substoichiometric frameworks (so‐called Type III COFs) are especially attractive due to the possibility of not only generating unusual topology and complex pore architectures but also facilitating the introduction of well‐defined functional groups at precise locations for desired functions. Herein, the first example of a highly emissive (PLQY 6.8%) substoichiometric 2D‐COF (COF‐SMU‐1) featuring free uncondensed aldehyde groups is reported. In particular,COF‐SMU‐1features a dual‐pore architecture with an overallbexnet topology, tunable emission in various organic solvents, and distinct colorimetric changes in the presence of water. To gain further insights into its photoluminescence properties, the charge transfer, excimer emission, and excited state exciton dynamics ofCOF‐SMU‐1are investigated using femtosecond transient absorption spectroscopy in different organic solvents. Additionally, highly enhanced atmospheric water‐harvesting properties ofCOF‐SMU‐1are revealed using FT‐IR and water sorption studies.The findings will not only lead to in‐depth understanding of structure–property relationships in emissive COFs but also open new opportunities for designing COFs for potential applications in solid‐state lighting and water harvesting.

     
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