Geometry, mechanics and actuation of intrinsically curved folds.

We combine theory and experiments to explore the kinematics and actuation of intrinsically curved folds (ICFs) in otherwise developable shells. Unlike origami folds, ICFs are not bending isometries of flat sheets, but arise via non-isometric processes (growth/moulding) or by joining sheets along curved boundaries. Experimentally, we implement both, first making joined ICFs from paper, then fabricating flat liquid crystal elastomer (LCE) sheets that morph into ICFs upon heating/swelling via programmed metric changes. Theoretically, an ICF's intrinsic geometry is defined by the geodesic curvatures on either side, κgi. Given these, and a target 3D fold-line, one can construct the entire surface isometrically, and compute the bending energy. This construction shows ICFs are bending mechanisms, with a continuous family of isometries trading fold angle against fold-line curvature. In ICFs with symmetric κgi, straightening the fold-line culminates in a fully-folded flat state that is deployable but weak, while asymmetric ICFs ultimately lock with a mechanically strong finite-angle. When unloaded, freely-hinged ICFs simply adopt the (thickness t independent) isometry that minimizes the bend energy. In contrast, in LCE ICFs a competition between flank and ridge selects a ridge curvature that, unusually, scales as t-1/7. Finally, we demonstrate how multiple ICFs can be combined in one LCE sheet, to create a versatile intrinsically curved gripper that lifts a heavy weight.

Experimental Open Air Burning of Vegetation Enhances Organic Matter Chemical Heterogeneity Compared to Laboratory Burns.

Wildfires produce solid residuals that have unique chemical and physical properties compared to unburned materials, which influence their cycling and fate in the natural environment. Visual burn severity assessment is used to evaluate post-fire alterations to the landscape in field-based studies, yet muffle furnace methods are commonly used in laboratory studies to assess molecular scale alterations along a temperature continuum. Here, we examined solid and leachable organic matter characteristics from chars visually characterized as low burn severity that were created either on an open air burn table or from low-temperature muffle furnace burns. We assessed how the different combustion conditions influence solid and dissolved organic matter chemistries and explored the potential influence of these results on the environmental fate and reactivity. Notably, muffle furnace chars produced less leachable carbon and nitrogen than open air chars across land cover types. Organic matter produced from muffle furnace burns was more homogeneous than open air chars. This work highlights chemical heterogeneities that exist within a single burn severity category, potentially influencing our conceptual understanding of pyrogenic organic matter cycling in the natural environment, including transport and processing in watersheds. Therefore, we suggest that open air burn studies are needed to further advance our understanding of pyrogenic organic matter's environmental reactivity and fate.

Evaluating Accuracy in Five Commercial Sleep-Tracking Devices Compared to Research-Grade Actigraphy and Polysomnography.

The development of consumer sleep-tracking technologies has outpaced the scientific evaluation of their accuracy. In this study, five consumer sleep-tracking devices, research-grade actigraphy, and polysomnography were used simultaneously to monitor the overnight sleep of fifty-three young adults in the lab for one night. Biases and limits of agreement were assessed to determine how sleep stage estimates for each device and research-grade actigraphy differed from polysomnography-derived measures. Every device, except the Garmin Vivosmart, was able to estimate total sleep time comparably to research-grade actigraphy. All devices overestimated nights with shorter wake times and underestimated nights with longer wake times. For light sleep, absolute bias was low for the Fitbit Inspire and Fitbit Versa. The Withings Mat and Garmin Vivosmart overestimated shorter light sleep and underestimated longer light sleep. The Oura Ring underestimated light sleep of any duration. For deep sleep, bias was low for the Withings Mat and Garmin Vivosmart while other devices overestimated shorter and underestimated longer times. For REM sleep, bias was low for all devices. Taken together, these results suggest that proportional bias patterns in consumer sleep-tracking technologies are prevalent and could have important implications for their overall accuracy.

Surface Instability in a Nematic Elastomer.

Liquid crystal elastomers (LCEs) are soft phase-changing solids that exhibit large reversible contractions upon heating, Goldstone-like soft modes, and resultant microstructural instabilities. We heat a planar LCE slab to isotropic, clamp the lower surface, then cool back to nematic. Clamping prevents macroscopic elongation, producing compression and microstructure. We see that the free surface destabilizes, adopting topography with amplitude and wavelength similar to thickness. To understand the instability, we numerically compute the microstructural relaxation of a "nonideal" LCE energy. Linear stability reveals a Biot-like scale-free instability, but with oblique wave vector. However, simulation and experiment show that, unlike classic elastic creasing, instability culminates in a crosshatch without cusps or hysteresis, and is constructed entirely from low-stress soft modes.

Synthesis and Additive Manufacturing of Hydrazone-Linked Covalent Organic Framework Aerogels.

Covalent Organic Frameworks (COFs) are crystalline, porous organic materials. Recent studies have demonstrated novel processing strategies for COFs to form adaptable architectures, but these have focused primarily on imine-linked COFs. This work presents a new synthesis and processing route to produce crystalline hydrazone-linked COF gels and aerogels with hierarchical porosity. The method was implemented to produce a series of hydrazone-linked COFs with different alkyl side-chain substituents, achieving control of the hydrophilicity of the final aerogel. Variation in the length of the alkyl substituents yielded materials with controllable form factors that can preferentially adsorb water or nonpolar organic solvents. Additionally, a method for additive manufacturing of hydrazone-linked COFs using hydroxymethylcellulose as a sacrificial additive is presented. This work demonstrates an effective and simple approach to the fabrication of hydrazone COF aerogels and additive manufacturing to produce hydrazone COFs of desired shape.

Understanding the effect of liquid crystal content on the phase behavior and mechanical properties of liquid crystal elastomers.

Liquid crystal elastomers are stimuli-responsive, shape-shifting materials. They typically require high temperatures for actuation which prohibits their use in many applications, such as biomedical devices. In this work, we demonstrate a simple and general approach to tune the order-to-disorder transition temperature (TODT) or nematic-to-isotropic transition temperature (TNI) of LCEs through variation of the overall liquid crystal mass content. We demonstrate reduction of the TNI in nematic LCEs through the incorporation of non-mesogenic linkers or the addition of lithium salts, and show that the TNI varies linearly with liquid crystal mass content over a broad range, approximately 50 °C. We also analyze data from prior reports that include three different mesogens, different network linking chemistries, and different alignment strategies, and show that the linear trend in TODT with liquid crystal mass content also holds for these systems. Finally, we demonstrate a simple approach to quantifying the maximum actuation strain through measurement of the soft elastic plateau and demonstrate applications of nematic LCEs with low TODTs, including the first body-responsive LCE that curls around a human finger due to body heat, and a fluidic channel that directionally pumps liquid when heated.

Phosphorus Speciation in Atmospherically Deposited Particulate Matter and Implications for Terrestrial Ecosystem Productivity.

Chemical forms of phosphorus (P) in airborne particulate matter (PM) are poorly known and do not correlate with solubility or extraction measurements commonly used to infer speciation. We used P X-ray absorption near-edge structure (XANES) and 31P nuclear magnetic resonance (NMR) spectroscopies to determine P species in PM collected at four mountain sites (Colorado and California). Organic P species dominated samples from high elevations, with organic P estimated at 65-100% of total P in bulk samples by XANES and 79-88% in extracted fractions (62-84% of total P) by NMR regardless of particle size (≥10 or 1-10 µm). Phosphorus monoester and diester organic species were dominant and present in about equal proportions, with low fractions of inorganic P species. By comparison, PM from low elevation contained mixtures of organic and inorganic P, with organic P estimated at 30-60% of total P. Intercontinental PM transport determined from radiogenic lead (Pb) isotopes varied from 0 to 59% (mean 37%) Asian-sourced Pb at high elevation, whereas stronger regional PM inputs were found at low elevation. Airborne flux of bioavailable P to high-elevation ecosystems may be twice as high as estimated by global models, which will disproportionately affect net primary productivity.

Direct shape programming of liquid crystal elastomers.

Liquid crystal elastomers (LCEs) are shape morphing materials promising for many applications including soft robotics, actuators, and biomedical devices, but current LCE synthesis techniques lack a simple method to program new and arbitrary shape changes. Here, we demonstrate a straightforward method to directly program complex, reversible, non-planar shape changes in nematic LCEs. We utilize a double network synthesis process that results in a competitive double network LCE. By optimizing the crosslink densities of the first and second network we can mechanically program non-planar shapes with strains between 4-100%. This enables us to directly program LCEs using mechanical deformations that impart low or high strains in the LCE including stamping, curling, stretching and embossing methods. The resulting LCEs reversibly shape-shift between the initial and programmed shape. This work widens the potential application of LCEs in biomedical devices, soft-robotics and micro-fluidics where arbitrary and easily programmed shapes are needed.

3D Printing of Metformin HCl PVA Tablets by Fused Deposition Modeling: Drug Loading, Tablet Design, and Dissolution Studies.

The main aim of this work was to 3D print metformin HCl-loaded PVA (ML-PVA) tablets by fused deposition modeling. A modified solvent diffusion approach was used to improve drug loading. PVA filaments were placed in metformin HCl solution in ethanol containing low water content (10%(v/v)) to enhance the drug's solubility. The physicochemical properties of ML-PVA filaments were characterized before and after printing. Lastly, ML-PVA filaments were printed into channeled tablet designs to increase their surface area available for dissolution. The loading of metformin HCl onto PVA filament has significantly increased from 0.08 ± 0.02% in metformin HCl solution in absolute ethanol to 1.40 ± 0.02% in ethanol-water (9:1). The IR spectra of PVA filament soaked in ethanol-water depicted higher peak intensity at 1138 cm-1, indicating higher degree of crystallinity. Thermal analysis of the soaked PVA filaments showed higher melting enthalpies yet lower melting temperature (Tm) compared to unprocessed PVA. ML-PVA filaments were successfully printed into round-channeled tablets (10% infill) with higher surface area and area/volume ratios compared with the solid ones. The inclusion of channels in the tablet design modified their printing pattern causing an unexpected increase in their mass. The dissolution profiles of ML-PVA tablets were mainly dependent on their area/mass ratios. Our results show a simple approach to increase metformin HCl loading onto PVA and reveal the significance of tablet design, infill percentage, and printing pattern as they dictate the area, volume, and the mass of the tablet which impact its dissolution rate.

An Evaluation of Provincial Infectious Disease Surveillance Reports in Ontario.

CONTEXT: Public Health Ontario (PHO) publishes various infectious disease surveillance reports, but none have yet been formally evaluated. OBJECTIVE: PHO evaluated its monthly and annual infectious disease surveillance reports to assess public health stakeholders' current perception of the products and to develop recommendations for improving future products. DESIGN: An evaluation consisting of an online survey and a review of public Web sites of other jurisdictions with similar annual reports. SETTING: For the online survey, stakeholder organizations targeted were the 36 local public health units and the Health health ministry in Ontario, Canada. PARTICIPANTS: Survey participants included epidemiologists, managers, directors, and other public health practitioners from participating organizations. MAIN OUTCOME MEASURES: Online survey respondents' awareness and access to the reports, their rated usefulness of reports and subsections, and suggestions for improving usefulness; timeliness of select annual reports from other jurisdictions based on the period from data described to report publication. RESULTS: Among 57 survey respondents, between 74% and 97% rated each report as useful; the most common use was for situational awareness. Respondents ranked timeliness as the most important attribute of surveillance reports, followed by data completeness. Among 6 annual reports reviewed, the median time to publication was 11.5 months compared with 23.2 months for PHO. CONCLUSION: Recommendations based on this evaluation have already been applied to the monthly report (eg, focusing on the most useful sections) and have become key considerations when developing future annual reports and other surveillance reporting tools (eg, need to provide more timely reports). Other public health organizations may also use this evaluation to inform aspects of their surveillance report development and evaluation. The evaluation results have provided PHO with direction on how to improve its provincial infectious disease surveillance reporting moving forward, and formed a basis for future work in surveillance product development and evaluation.

Oversampling for Enhanced Spatial Resolution of Zebrafish by Top-Hat IR-MALDESI-MSI.

Mass spectrometry imaging (MSI) has become a significant tool for measuring chemical species in biological tissues, where much of the impact of these platforms lies in their capability to report the spatial distribution of analytes for correlation to sample morphology. As a result, enhancement of spatial resolution has become a frontier of innovation in the field, and necessary developments are dependent on the ionization source. More particularly, laser-based imaging sources may require modifications to the optical train or alternative sampling techniques. These challenges are heightened for systems with infrared (IR) lasers, as their operating wavelength generates spot sizes that are inherently larger than their ultraviolet counterparts. Recently, the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source has shown the utility of a diffractive optical element (DOE) to produce square ablation patterns, termed top-hat IR-MALDESI. If the DOE optic is combined with oversampling methods, smaller ablation volumes can be sampled to render higher spatial resolution imaging experiments. Further, this approach enables reproducible spot sizes and ablation volumes for better comparison between scans. Herein, we investigate the utility of oversampling with top-hat IR-MALDESI to enhance the spatial resolution of measured lipids localized within the head of sectioned zebrafish tissue. Four different spatial resolutions were evaluated for data quality (e.g., mass measurement accuracy, spectral accuracy) and quantity of annotations. Other experimental parameters to consider for high spatial resolution imaging are also discussed. Ultimately, 20 µm spatial resolution was achieved in this work and supports feasibility for use in future IR-MALDESI studies.

Enabling Solution Processable COFs through Suppression of Precipitation during Solvothermal Synthesis.

Covalent organic frameworks (COFs) are crystalline, nanoporous materials of interest for various applications, but current COF synthetic routes lead to insoluble aggregates which precludes processing for practical implementation. Here, we report a COF synthesis method that produces a stable, homogeneous suspension of crystalline COF nanoparticles that enables the preparation of COF monoliths, membranes, and films using conventional solution-processing techniques. Our approach involves the use of a polar solvent, diacid catalyst, and slow reagent mixing procedure at elevated temperatures which altogether enable access to crystalline COF nanoparticle suspension that does not aggregate or precipitate when kept at elevated temperatures. On cooling, the suspension undergoes a thermoreversible gelation transition to produce crystalline and highly porous COF materials. We further show that the modified synthesis approach is compatible with various COF chemistries, including both large- and small-pore imine COFs, hydrazone-linked COFs, and COFs with rhombic and hexagonal topologies, and in each case, we demonstrate that the final product has excellent crystallinity and porosity. The final materials contain both micro- and macropores, and the total porosity can be tuned through variation of sample annealing. Dynamic light scattering measurements reveal the presence of COF nanoparticles that grow with time at room temperature, transitioning from a homogeneous suspension to a gel. Finally, we prepare imine COF membranes and measure their rejection of polyethylene glycol (PEG) polymers and oligomers, and these measurements exhibit size-dependent rejection and adsorption of PEG solutes. This work demonstrates a versatile processing strategy to create crystalline and porous COF materials using solution-processing techniques and will greatly advance the development of COFs for various applications.

Landscape Topography and Regional Drought Alters Dust Microbiomes in the Sierra Nevada of California.

Dust provides an ecologically significant input of nutrients, especially in slowly eroding ecosystems where chemical weathering intensity limits nutrient inputs from underlying bedrock. In addition to nutrient inputs, incoming dust is a vector for dispersing dust-associated microorganisms. While little is known about dust-microbial dispersal, dust deposits may have transformative effects on ecosystems far from where the dust was emitted. Using molecular analyses, we examined spatiotemporal variation in incoming dust microbiomes along an elevational gradient within the Sierra Nevada of California. We sampled throughout two dry seasons and found that dust microbiomes differed by elevation across two summer dry seasons (2014 and 2015), which corresponded to competing droughts in dust source areas. Dust microbial taxa richness decreased with elevation and was inversely proportional to dust heterogeneity. Likewise, dust phosphorus content increased with elevation. At lower elevations, early season dust microbiomes were more diverse than those found later in the year. The relative abundances of microbial groups shifted during the summer dry season. Furthermore, mutualistic fungal diversity increased with elevation, which may have corresponded with the biogeography of their plant hosts. Although dust fungal pathogen diversity was equivalent across elevations, elevation and sampling month interactions for the relative abundance, diversity, and richness of fungal pathogens suggest that these pathogens differed temporally across elevations, with potential implications for humans and wildlife. This study shows that landscape topography and droughts in source locations may alter the composition and diversity of ecologically relevant dust-associated microorganisms.

Bursal Acromial Reconstruction (BAR) Using an Acellular Dermal Allograft as a Surgical Solution for the Treatment of Massive Irreparable Rotator Cuff Tears.

Massive, irreparable rotator cuff tears in patients without severe signs of osteoarthritis remains a major challenge for orthopaedic surgeons. These can be a source of significant pain and functional loss occurring most commonly in a relatively frail, elderly patient population. A plethora of surgical techniques covering minimally invasive, arthroscopic techniques and open, salvage procedures have been described for this challenging patient cohort. Continuous evolvement of arthroscopic techniques has led to all-arthroscopic superior capsular reconstruction techniques using allografts, thereby reducing donor side morbidity along with decreased soft tissue dissection. However, conventional superior capsular reconstruction is noted to be a technically complex, time-consuming, and high-cost surgery, which may put this technique beyond the confidence of many shoulder surgeons. The subacromial balloon spacer has emerged as a potential solution in these patients, providing interposition between the humeral head and acromion. However, the subacromial balloon biodegrades rapidly and its effect is only temporary. Thus this technique article presents using an acellular human dermal allograft to reconstruct the bursal layer, which is normally interposed between the humeral head and the acromion. The proposed technique provides a permanent interposition graft preventing humeral acromial contact, which does not undergo rapid biodegradation. The surgical technique is technically feasible, both minimizing surgical time and therefore operative risk to the patient.

Depth dependence of climatic controls on soil microbial community activity and composition.

Subsoil microbiomes play important roles in soil carbon and nutrient cycling, yet our understanding of the controls on subsoil microbial communities is limited. Here, we investigated the direct (mean annual temperature and precipitation) and indirect (soil chemistry) effects of climate on microbiome composition and extracellular enzyme activity throughout the soil profile across two elevation-bioclimatic gradients in central California, USA. We found that microbiome composition changes and activity decreases with depth. Across these sites, the direct influence of climate on microbiome composition and activity was relatively lower at depth. Furthermore, we found that certain microbial taxa change in relative abundance over large temperature and precipitation gradients only in specific soil horizons, highlighting the depth dependence of the climatic controls on microbiome composition. Our finding that the direct impacts of climate are muted at depth suggests that deep soil microbiomes may lag in their acclimation to new temperatures with a changing climate.

Corrosion Resistance of Sulfur-Selenium Alloy Coatings.

Despite decades of research, metallic corrosion remains a long-standing challenge in many engineering applications. Specifically, designing a material that can resist corrosion both in abiotic as well as biotic environments remains elusive. Here a lightweight sulfur-selenium (S-Se) alloy is designed with high stiffness and ductility that can serve as an excellent corrosion-resistant coating with protection efficiency of ≈99.9% for steel in a wide range of diverse environments. S-Se coated mild steel shows a corrosion rate that is 6-7 orders of magnitude lower than bare metal in abiotic (simulated seawater and sodium sulfate solution) and biotic (sulfate-reducing bacterial medium) environments. The coating is strongly adhesive, mechanically robust, and demonstrates excellent damage/deformation recovery properties, which provide the added advantage of significantly reducing the probability of a defect being generated and sustained in the coating, thus improving its longevity. The high corrosion resistance of the alloy is attributed in diverse environments to its semicrystalline, nonporous, antimicrobial, and viscoelastic nature with superior mechanical performance, enabling it to successfully block a variety of diffusing species.

Reactive 3D Printing of Shape-Programmable Liquid Crystal Elastomer Actuators.

3D printed, stimuli-responsive materials that reversibly actuate between programmed shapes are promising for applications ranging from biomedical implants to soft robotics. However, current 3D printing of reversible actuators significantly limits the range of possible shapes and/or shape responses because they couple the print path to mathematically determined director profiles to elicit a desired shape change. Here, we report a reactive 3D-printing method that decouples printing and shape-programming steps, enabling a broad range of complex architectures and virtually any arbitrary shape changes. This method involves first printing liquid crystal elastomer (LCE) precursor solution into a catalyst bath, producing complex architectures defined by printing. Shape changes are then programmed through mechanical deformation and UV irradiation. Upon heating and cooling, the LCE reversibly shape-shifts between printed and programmed shapes, respectively. The potential of this method was demonstrated by programming a variety of arbitrary shape changes in a single printed material, producing auxetic LCE structures and symmetry-breaking shape changes in LCE sheets.

Endophyte-Promoted Phosphorus Solubilization in Populus.

Phosphorus is one of the essential nutrients for plant growth, but it may be relatively unavailable to plants because of its chemistry. In soil, the majority of phosphorus is present in the form of a phosphate, usually as metal complexes making it bound to minerals or organic matter. Therefore, inorganic phosphate solubilization is an important process of plant growth promotion by plant associated bacteria and fungi. Non-nodulating plant species have been shown to thrive in low-nutrient environments, in some instances by relying on plant associated microorganisms called endophytes. These microorganisms live within the plant and help supply nutrients for the plant. Despite their potential enormous environmental importance, there are a limited number of studies looking at the direct molecular impact of phosphate solubilizing endophytic bacteria on the host plant. In this work, we studied the impact of two endophyte strains of wild poplar (Populus trichocarpa) that solubilize phosphate. Using a combination of x-ray imaging, spectroscopy methods, and proteomics, we report direct evidence of endophyte-promoted phosphorus uptake in poplar. We found that the solubilized phosphate may react and become insoluble once inside plant tissue, suggesting that endophytes may aid in the re-release of phosphate. Using synchrotron x-ray fluorescence spectromicroscopy, we visualized the nutrient phosphorus inside poplar roots inoculated by the selected endophytes and found the phosphorus in both forms of organic and inorganic phosphates inside the root. Tomography-based root imaging revealed a markedly different root biomass and root architecture for poplar samples inoculated with the phosphate solubilizing bacteria strains. Proteomics characterization on poplar roots coupled with protein network analysis revealed novel proteins and metabolic pathways with possible involvement in endophyte enriched phosphorus uptake. These findings suggest an important role of endophytes for phosphorus acquisition and provide a deeper understanding of the critical symbiotic associations between poplar and the endophytic bacteria.

Multifunctional Bio-Nanocomposite Coatings for Perishable Fruits.

Hunger and chronic undernourishment impact over 800 million people, which translates to ≈10.7% of the world's population. While countries are increasingly making efforts to reduce poverty and hunger by pursuing sustainable energy and agricultural practices, a third of the food produced around the globe still is wasted and never consumed. Reducing food shortages is vital in this effort and is often addressed by the development of genetically modified produce or chemical additives and inedible coatings, which create additional health and environmental concerns. Herein, a multifunctional bio-nanocomposite comprised largely of egg-derived polymers and cellulose nanomaterials as a conformal coating onto fresh produce that slows down food decay by retarding ripening, dehydration, and microbial invasion is reported. The coating is edible, washable, and made from readily available inexpensive or waste materials, which makes it a promising economic alternative to commercially available fruit coatings and a solution to combat food wastage that is rampant in the world.

Temporal aspects of the visuotactile congruency effect.

We report an experiment designed to investigate the temporal dynamics of the visuotactile crossmodal congruency effect. Vibrotactile targets were presented randomly to the index finger (top side of a hand-held cube) or thumb (bottom side) of either hand while visual distractors were presented randomly from one of the same four possible locations. The stimulus onset asynchrony (SOA) between the vibrotactile target and the visual distractor was varied on a trial-by-trial basis. Participants made speeded discrimination responses regarding the elevation of the vibrotactile targets (i.e., upper versus lower) while trying to ignore the visual distractors. The largest crossmodal congruency effects (defined as the difference in performance between incongruent and congruent elevation distractor trials) were obtained when the visual distractor preceded the vibrotactile target by 50-100 ms, although significant effects were also reported when the distractor followed the target by as much as 100 ms. These results are discussed in terms of the conjoint influence of response competition, crossmodal perceptual interactions (i.e., the ventriloquism effect), and exogenous spatial attention on the crossmodal congruency effect. The distinct temporal signatures of each of these effects are also highlighted.