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The controllable response of materials to small-molecule absorbates helps control the information duration on rewritable paper., Controlling the duration that information lasts on paper so that it disappears as desired is crucial for information security. However, this area is rarely studied. Here, we report [TEMA]2SbCl5 (1, TEMA+ = methyltriethylammonium), [TEA]2SbCl5 (2, TEA+ = tetraethylammonium), [TEBA]2SbCl5 (3, TEBA+ = benzyltriethylammonium), and [Ph4P]2SbCl5 (4, Ph4P+ = tetraphenylphosphonium) with structure-dependent reversible photoluminescent switching induced by the absorption and thermal release of small guest molecules including H2O, methanol, and ethylene glycol. Comparing the structural disorder levels, bond lengths, and luminescent Stokes shifts of the compounds aided in understanding their selective absorption behavior. Our results indicated that the information duration on the rewritable paper coated with the title compounds is easily tuned by changing the cation of the compounds, the type of guest molecules, and laser heating power. Our study opens previously unidentified avenues for information security and extends the potential applications of rewritable paper.

Lunaria annua plants grow fruits in the form of mechanically strong, low-density (70% air), reflective cellulose sheets., Bright, iridescent colors observed in nature are often caused by light interference within nanoscale periodic lattices, inspiring numerous strategies for coloration devoid of inorganic pigments. Here, we describe and characterize the septum of the Lunaria annua plant that generates large (multicentimeter), freestanding iridescent sheets, with distinctive silvery-white reflective appearance. This originates from the thin-film assembly of cellulose fibers in the cells of the septum that induce thin-film interference–like colors at the microscale, thus accounting for the structure’s overall silvery-white reflectance at the macroscale. These cells further assemble into two thin layers, resulting in a mechanically robust, iridescent septum, which is also significantly light due to its high air porosity (>70%) arising from the cells’ hollow-core structure. This combination of hierarchical structure comprising mechanical and optical function can inspire technological classes of devices and interfaces based on robust, light, and spectrally responsive natural substrates.

Stacked paper skiving paves the way for industrial manufacturing of paper-based analytical devices for barcode assays., This paper shows that stacked sheets of paper preincubated with different biological reagents and skiving them into uniform test paper sheets allow mass manufacturing of multiplexed immunoassay devices and simultaneous detection of multiplex targets that can be read out by a barcode scanner. The thickness of one sheet of paper can form the width of a module for the barcode; when stacked, these sheets of paper can form a series of barcodes representing the targets, depending on the color contrast provided by a colored precipitate of an immunoassay. The uniform thickness of sheets of paper allows high-quality signal readout. The manufacturing method allows highly efficient fabrication of the materials and substrates for a straightforward assay of targets that range from drugs of abuse to biomarkers of blood-transmitted infections. In addition, as a novel alternative to the conventional point-of-care testing method, the paper-based barcode assay system can provide highly efficient, accurate, and objective diagnoses.

The sulfate-reducing bacteria and related corrosion can be inhibited by charge-reversal surfactant antibiotic material., The corrosions caused by sulfate-reducing bacteria (SRB) are serious problems in petroleum exploitation and transportation, which can lead to safety problems, environmental pollutions, and economic losses. Here, a charge-reversal surfactant antibiotic material N-dodecyl-1-carboxylic acid-1-cyclohexenyl-2-carboxamide (C12N-DCA) is designed and synthesized. C12N-DCA is a negatively charged surfactant, which cannot be adsorbed by soil and rock in a large amount. Therefore, it can reach the “lesion location”, with enough concentration. After being hydrolyzed and charge reversed under the acceleration of H2S produced by SRB, C12N-DCA becomes a positively charged surfactant dodecane ammonium salt to kill SRB. Through a simulating experiment, it is found that C12N-DCA can reach the SRB inhibition ratio of almost 100%, and it can reduce iron corrosion by 88%. Such an antibiotic material or its homologs may be added to the chemical flooding fluids, killing SRB during petroleum exploitation and reducing the SRB-induced corrosion in the petroleum exploitation and transportation.

Stable isotope labeling of agricultural polyesters enables demonstration of their microbial utilization in soils., Plastic materials are widely used in agricultural applications to achieve food security for the growing world population. The use of biodegradable instead of nonbiodegradable polymers in single-use agricultural applications, including plastic mulching, promises to reduce plastic accumulation in the environment. We present a novel approach that allows tracking of carbon from biodegradable polymers into CO2 and microbial biomass. The approach is based on 13C-labeled polymers and on isotope-specific analytical methods, including nanoscale secondary ion mass spectrometry (NanoSIMS). Our results unequivocally demonstrate the biodegradability of poly(butylene adipate-co-terephthalate) (PBAT), an important polyester used in agriculture, in soil. Carbon from each monomer unit of PBAT was used by soil microorganisms, including filamentous fungi, to gain energy and to form biomass. This work advances both our conceptual understanding of polymer biodegradation and the methodological capabilities to assess this process in natural and engineered environments.

A new graphene structure allowing unprecedented stretchability in graphene electrodes was designed., Two-dimensional materials, such as graphene, are attractive for both conventional semiconductor applications and nascent applications in flexible electronics. However, the high tensile strength of graphene results in fracturing at low strain, making it challenging to take advantage of its extraordinary electronic properties in stretchable electronics. To enable excellent strain-dependent performance of transparent graphene conductors, we created graphene nanoscrolls in between stacked graphene layers, referred to as multilayer graphene/graphene scrolls (MGGs). Under strain, some scrolls bridged the fragmented domains of graphene to maintain a percolating network that enabled excellent conductivity at high strains. Trilayer MGGs supported on elastomers retained 65% of their original conductance at 100% strain, which is perpendicular to the direction of current flow, whereas trilayer films of graphene without nanoscrolls retained only 25% of their starting conductance. A stretchable all-carbon transistor fabricated using MGGs as electrodes exhibited a transmittance of >90% and retained 60% of its original current output at 120% strain (parallel to the direction of charge transport). These highly stretchable and transparent all-carbon transistors could enable sophisticated stretchable optoelectronics.

A type of glassy graphene thin film was studied and applied for laser direct writing circuits., Large-area graphene thin films are prized in flexible and transparent devices. We report on a type of glassy graphene that is in an intermediate state between glassy carbon and graphene and that has high crystallinity but curly lattice planes. A polymer-assisted approach is introduced to grow an ultra-smooth (roughness

Differential cross-sectional cusps, occurring at the vicinity of newly open channels, are used for enhanced avionic sensing., Typical sensors detect small perturbations by measuring their effects on a physical observable, using a linear response principle (LRP). It turns out that once LRP is abandoned, new opportunities emerge. A prominent example is resonant systems operating near Nth-order exceptional point degeneracies (EPDs) where a small perturbation ε ≪ 1 activates an inherent sublinear response ∼εN≫ε in resonant splitting. Here, we propose an alternative sublinear optomechanical sensing scheme that is rooted in Wigner’s cusp anomalies (WCAs), first discussed in the framework of nuclear reactions: a frequency-dependent square-root singularity of the differential scattering cross section around the energy threshold of a newly opened channel, which we use to amplify small perturbations. WCA hypersensitivity can be applied in a variety of sensing applications, besides optomechanical accelerometry discussed in this paper. Our WCA platforms are compact, do not require a judicious arrangement of active elements (unlike EPD platforms), and, if chosen, can be cavity free.

A self-calibrated flexible epidermal biomicrofluidic device is proposed for wearable accurate blood glucose monitoring., This paper reports a flexible electronics-based epidermal biomicrofluidics technique for clinical continuous blood glucose monitoring, overcoming the drawback of the present wearables, unreliable measurements. A thermal activation method is proposed to improve the efficiency of transdermal interstitial fluid (ISF) extraction, enabling extraction with a low current density to notably reduce skin irritation. An Na+ sensor and a correction model are proposed to eliminate the effect of individual differences, which leads to fluctuations in the amount of ISF extraction. An electrochemical sensor with a 3D nanostructured working electrode surface is designed to enable precise in situ glucose measurement. A differential structure is proposed to eliminate the effect of passive perspiration, which leads to inaccurate blood glucose prediction. Fabrications of the epidermal biomicrofluidic device including formation of flexible electrodes, nanomaterial modification, and enzyme immobilization are fully realized by inkjet printing to enable facile manufacturing with low cost, which benefits practical production.

A highly sensitive odorant sensor was developed by using insect olfactory receptors reconstituted into a lipid bilayer membrane., This paper reports a volatile organic compound (VOC) sensor based on olfactory receptors that were reconstituted into a lipid bilayer and used in a specifically designed gas flow system for rapid parts per billion (ppb)–level detection. This VOC sensor achieves both rapid detection and high detection probability because of its gas flow system and array design. Specifically, the gas flow system includes microchannels and hydrophobic microslits, which facilitate both the introduction of gas into the droplet and droplet mixing. We installed this system into a parallel lipid bilayer device and subsequently demonstrated parts per billion–level (0.5 ppb) detection of 1-octen-3-ol in human breath. Therefore, this system extends the various applications of biological odorant sensing, including breath diagnosis systems and environmental monitoring.

A tissue-engineered model of the trabecular bone microenvironment elucidates spatiotemporal aspects of bone remodeling processes., Trabecular bone maintains physiological homeostasis and consistent structure and mass through repeated cycles of bone remodeling by means of tightly localized regulation. The molecular and cellular processes that regulate localized bone remodeling are poorly understood because of a lack of relevant experimental models. A tissue-engineered model is described here that reproduces bone tissue complexity and bone remodeling processes with high fidelity and control. An osteoid-inspired biomaterial—demineralized bone paper—directs osteoblasts to deposit structural mineralized bone tissue and subsequently acquire the resting-state bone lining cell phenotype. These cells activate and shift their secretory profile to induce osteoclastogenesis in response to chemical stimulation. Quantitative spatial mapping of cellular activities in resting and activated bone surface coculture showed that the resting-state bone lining cell network actively directs localized bone remodeling by means of paracrine signaling and cell-to-cell contact. This model may facilitate further investigation of trabecular bone niche biology.

An in situ surface observation reveals the surface structural changes during heating of a Li–10 wt % Mg alloy sheet., Li–10 wt % Mg alloy (Li–10 Mg) is used as an anode material for a solid-state battery with excellent electrochemical performance and no evidence of dendrite formation during cycling. Thermal treatment of Li metal during manufacturing improves the interfacial contact between a Li metal electrode and solid electrolyte to achieve an all solid-state battery with increased performance. To understand the properties of the alloy passivation layer, this paper presents the first direct observation of its evolution at elevated temperatures (up to 325°C) by in situ scanning electron microscopy. We found that the morphology of the surface passivation layer was unchanged above the alloy melting point, while the bulk of the material below the surface was melted at the expected melting point, as confirmed by in situ electron backscatter diffraction. In situ heat treatment of Li-based materials could be a key method to improve battery performance.

Soft robotic sensor arrays for left-atrial mapping demonstrate highly conformal contact to complex patient anatomies., Devices that perform cardiac mapping and ablation to treat atrial fibrillation provide an effective means of treatment. Current devices, however, have limitations that either require tedious point-by-point mapping of a cardiac chamber or have limited ability to conform to the complex anatomy of a patient’s cardiac chamber. In this work, a detailed, scalable, and manufacturable technique is reported for fabrication of a multielectrode, soft robotic sensor array. These devices exhibit high conformability (~85 to 90%) and are equipped with an array of stretchable electronic sensors for voltage mapping. The form factor of the device is intended to match that of the entire left atrium and has a hydraulically actuated soft robotic structure whose profile facilitates deployment from a 13.5-Fr catheter. We anticipate that the methods described in this paper will serve a new generation of conformable medical devices that leverage the unique characteristics of stretchable electronics and soft robotics.

This paper reports that a fine-tuning of orbital hybridization opens a door to atomic-level engineering of spin-orbit physics., Current-induced spin-orbit torques provide an effective way to manipulate magnetization in spintronic devices, promising for fast switching applications in nonvolatile memory and logic units. Recent studies have revealed that the spin-orbit torque is strongly altered by the oxidation of heterostructures with broken inversion symmetry. Although this finding opens a new field of metal-oxide spin-orbitronics, the role of the oxidation in the spin-orbit physics is still unclear. Here, we demonstrate a marked enhancement of the spin-orbit torque induced by a fine-tuning of oxygen-induced modification of orbital hybridization. This is evidenced by a concomitant enhancement of the interface spin-orbit torque, interface spin loss, and interface perpendicular magnetic anisotropy within a narrow range of the oxidation level of metallic heterostructures. This result reveals the crucial role of the atomic-scale effects in the generation of the spin-orbit torques, opening the door to atomic-level engineering of the spin-orbit physics.

N-type ZrCoBi-based half-Heusler thermoelectric performance is predicted by weighted mobility ratio and experimentally verified., Thermoelectric modules, consisting of multiple pairs of n- and p-type legs, enable converting heat into electricity and vice versa. However, the thermoelectric performance is often asymmetrical, in that one type outperforms the other. In this paper, we identified the relationship between the asymmetrical thermoelectric performance and the weighted mobility ratio, a correlation that can help predict the thermoelectric performance of unreported materials. Here, a reasonably high ZT for the n-type ZrCoBi-based half-Heuslers is first predicted and then experimentally verified. A high peak ZT of ~1 at 973 K can be realized by ZrCo0.9Ni0.1Bi0.85Sb0.15. The measured heat-to-electricity conversion efficiency for the unicouple of ZrCoBi-based materials can be as high as ~10% at the cold-side temperature of ~303 K and at the hot-side temperature of ~983 K. Our work demonstrates that the ZrCoBi-based half-Heuslers are highly promising for the application of mid- and high-temperature thermoelectric power generation.

We demonstrate a counterintuitive mechanism of converting compressive impact to tensile waves in origami-based metamaterials., The principles underlying the art of origami paper folding can be applied to design sophisticated metamaterials with unique mechanical properties. By exploiting the flat crease patterns that determine the dynamic folding and unfolding motion of origami, we are able to design an origami-based metamaterial that can form rarefaction solitary waves. Our analytical, numerical, and experimental results demonstrate that this rarefaction solitary wave overtakes initial compressive strain waves, thereby causing the latter part of the origami structure to feel tension first instead of compression under impact. This counterintuitive dynamic mechanism can be used to create a highly efficient—yet reusable—impact mitigating system without relying on material damping, plasticity, or fracture.

Failed attempts to reproduce measurements suffer from lower resolution not ghosts., Gehring et al. argue that a splitting observed by us in the transverse acoustic (TA) phonon in the relaxor ferroelectric Pb[(Mg1/3Nb2/3)1−xTix]O3 with x = 0.30 (PMN-30PT) is caused by a combination of inelastic-elastic multiple scattering processes called ghostons. Their argument is motivated by differences observed between their measurements made on a triple-axis spectrometer and our measurements on a time-of-flight spectrometer. We show that the differences can be explained by differences in the instrument resolution functions. We demonstrate that the multiple scattering conditions proposed by Gehring et al. do not work for our scattering geometry. We also show that, when a ghoston is present, it is too weak to detect and therefore cannot explain the splitting. Last, this phonon splitting is just one part of the argument, and the overall conclusion of the original paper is supported by other results.

Subsurface Fe, Co, and Ni can promote the Pt-catalyzed propane dehydrogenation while exposed adversely on the surface., Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This paper describes a facile construction of well-defined Pt-skin catalysts modified by different 3d transition metal (3dTM) atoms in subsurface regions. However, on the catalyst containing both surface and subsurface 3dTMs, the selectivity of propane dehydrogenation decreases in the sequences of Pt ~ PtFe > PtCo > PtNi due to the easier C–C cracking on exposed Co and Ni sites. After the exposed 3dTMs were removed completely, the C3H6 selectivity was found to increase markedly in the row Pt < PtNi@Pt < PtCo@Pt < PtFe@Pt, which is in line with the calculated trend of d-band center shifting. The established relationship between reactivity and d-band center shifting illustrates the role of subsurface catalysis in dehydrogenation reaction.

Waterproof epidermal microfluidics enable collection and analysis of sweat during aquatic exercise., Noninvasive, in situ biochemical monitoring of physiological status, via the use of sweat, could enable new forms of health care diagnostics and personalized hydration strategies. Recent advances in sweat collection and sensing technologies offer powerful capabilities, but they are not effective for use in extreme situations such as aquatic or arid environments, because of unique challenges in eliminating interference/contamination from surrounding water, maintaining robust adhesion in the presence of viscous drag forces and/or vigorous motion, and preventing evaporation of collected sweat. This paper introduces materials and designs for waterproof, epidermal, microfluidic and electronic systems that adhere to the skin to enable capture, storage, and analysis of sweat, even while fully underwater. Field trials demonstrate the ability of these devices to collect quantitative in situ measurements of local sweat chloride concentration, local sweat loss (and sweat rate), and skin temperature during vigorous physical activity in controlled, indoor conditions and in open-ocean swimming.

Stretchable fibers dissipate energy via the sequential fracturing of a metallic core held together by an elastomeric shell., Tough, biological materials (e.g., collagen or titin) protect tissues from irreversible damage caused by external loads. Mimicking these protective properties is important in packaging and in emerging applications such as durable electronic skins and soft robotics. This paper reports the formation of tough, metamaterial-like core-shell fibers that maintain stress at the fracture strength of a metal throughout the strain of an elastomer. The shell experiences localized strain enhancements that cause the higher modulus core to fracture repeatedly, increasing the energy dissipated during extension. Normally, fractures are catastrophic. However, in this architecture, the fractures are localized to the core. In addition to dissipating energy, the metallic core provides electrical conductivity and enables repair of the fractured core for repeated use. The fibers are 2.5 times tougher than titin and hold more than 15,000 times their own weight for a period 100 times longer than a hollow elastomeric fiber.

This paper reports the first demonstration of current-induced magnetization switching using an ordinary insulator., Current-induced magnetization switching through spin-orbit torques is the fundamental building block of spin-orbitronics, which promises high-performance, low-power memory and logic devices. The spin-orbit torques generally arise from spin-orbit coupling of heavy metals. However, even in a heterostructure where a metallic magnet is sandwiched by two different insulators, a nonzero spin-orbit torque is expected because of the broken inversion symmetry; an electrical insulator can be a source of the spin-orbit torques. We demonstrate current-induced magnetization switching using an insulator. We show that oxygen incorporation into the most widely used spintronic material, Pt, turns the heavy metal into an electrically insulating generator of the spin-orbit torques, which enables the electrical switching of perpendicular magnetization in a ferrimagnet sandwiched by insulating oxides. We also show that the spin-orbit torques generated from the Pt oxide can be controlled electrically through voltage-driven oxygen migration. These findings open a route toward energy-efficient, voltage-programmable spin-orbit devices based on insulating metal oxides.

Electrochemical twin channels make glucose in vessels measurable by noninvasive ultrathin skin-like highly sensitive biosensors., Currently, noninvasive glucose monitoring is not widely appreciated because of its uncertain measurement accuracy, weak blood glucose correlation, and inability to detect hyperglycemia/hypoglycemia during sleep. We present a strategy to design and fabricate a skin-like biosensor system for noninvasive, in situ, and highly accurate intravascular blood glucose monitoring. The system integrates an ultrathin skin-like biosensor with paper battery–powered electrochemical twin channels (ETCs). The designed subcutaneous ETCs drive intravascular blood glucose out of the vessel and transport it to the skin surface. The ultrathin (~3 μm) nanostructured biosensor, with high sensitivity (130.4 μA/mM), fully absorbs and measures the glucose, owing to its extreme conformability. We conducted in vivo human clinical trials. The noninvasive measurement results for intravascular blood glucose showed a high correlation (>0.9) with clinically measured blood glucose levels. The system opens up new prospects for clinical-grade noninvasive continuous glucose monitoring.

Water is an essential comonomer in a supramolecular polymer that is used as a recyclable, water-activated glue., Although the concept of structural water that is bound inside hydrophobic pockets and helps to stabilize protein structures is well established, water has rarely found a similar role in supramolecular polymers. Water is often used as a solvent for supramolecular polymerization, however without taking the role of a comonomer for the supramolecular polymer structure. We report a low–molecular weight monomer whose supramolecular polymerization is triggered by the incorporation of water. The presence of water molecules as comonomers is essential to the polymerization process. The supramolecular polymeric material exhibits strong adhesion to surfaces, such as glass and paper. It can be used as a water-activated glue, which can be released at higher temperatures and reused many times without losing its performance.

Capillary rise of water in porous cellulose sponges is investigated considering hygroscopic shape evolutions of micropores., We mundanely observe cellulose (kitchen) sponges swell while absorbing water. Fluid flows in deformable porous media, such as soils and hydrogels, are classically described on the basis of the theories of Darcy and poroelasticity, where the expansion of media arises due to increased pore pressure. However, the situation is qualitatively different in cellulosic porous materials like sponges because the pore expansion is driven by wetting of the surrounding cellulose walls rather than by increase of the internal pore pressure. We address a seemingly so simple but hitherto unanswered question of how fast water wicks into the swelling sponge. Our experiments uncover a power law of the wicking height versus time distinct from that for nonswelling materials. The observation using environmental scanning electron microscopy reveals the coalescence of microscale wall pores with wetting, which allows us to build a mathematical model for pore size evolution and the consequent wicking dynamics. Our study sheds light on the physics of water absorption in hygroscopically responsive multiscale porous materials, which have far more implications than everyday activities (for example, cleaning, writing, and painting) carried out with cellulosic materials (paper and sponge), including absorbent hygiene products, biomedical cell cultures, building safety, and cooking.

We demonstrate an innovative strategy for sequentially self-folding 2D polymer sheets into 3D objects using light., Shape plays an important role in defining the function of materials, particularly those found in nature. Several strategies exist to program materials to change from one shape to another; however, few can temporally and spatially control the shape. Programming the sequence of shape transformation with temporal control has been driven by the desire to generate complex shapes with high yield and to create multiple shapes from the same starting material. This paper demonstrates a markedly simple strategy for programmed self-folding of two-dimensional (2D) polymer sheets into 3D objects in a sequential manner using external light. Printed ink on the surface of the polymer sheets discriminately absorbs light on the basis of the wavelength of the light and the color of the ink that defines the hinge about which the sheet folds. The absorbed light gradually heats the underlying polymer across the thickness of the sheet, which causes relief of strain to induce folding. These color patterns can be designed to absorb only specific wavelengths of light (or to absorb differently at the same wavelength using color hues), thereby providing control of sheet folding with respect to time and space. This type of shape programming may have numerous applications, including reconfigurable electronics, actuators, sensors, implantable devices, smart packaging, and deployable structures.

Crystalline characterization of large-area graphene and study of adsorbates on it can be realized with low-energy electron beam., Two-dimensional (2D) materials have attracted interest because of their excellent properties and potential applications. A key step in realizing industrial applications is to synthesize wafer-scale single-crystal samples. Until now, single-crystal samples, such as graphene domains up to the centimeter scale, have been synthesized. However, a new challenge is to efficiently characterize large-area samples. Currently, the crystalline characterization of these samples still relies on selected-area electron diffraction (SAED) or low-energy electron diffraction (LEED), which is more suitable for characterizing very small local regions. This paper presents a highly efficient characterization technique that adopts a low-energy electrostatically focused electron gun and a super-aligned carbon nanotube (SACNT) film sample support. It allows rapid crystalline characterization of large-area graphene through a single photograph of a transmission-diffracted image at a large beam size. Additionally, the low-energy electron beam enables the observation of a unique diffraction pattern of adsorbates on the suspended graphene at room temperature. This work presents a simple and convenient method for characterizing the macroscopic structures of 2D materials, and the instrument we constructed allows the study of the weak interaction with 2D materials.