Tailoring atomic chemistry to refine reaction pathway for the most enhancement by magnetization in water oxidation.

Water oxidation on magnetic catalysts has generated significant interest due to the spin-polarization effect. Recent studies have revealed that the disappearance of magnetic domain wall upon magnetization is responsible for the observed oxygen evolution reaction (OER) enhancement. However, an atomic picture of the reaction pathway remains unclear, i.e., which reaction pathway benefits most from spin-polarization, the adsorbent evolution mechanism, the intermolecular mechanism (I2M), the lattice oxygen-mediated one, or more? Here, using three model catalysts with distinguished atomic chemistries of active sites, we are able to reveal the atomic-level mechanism. We found that spin-polarized OER mainly occurs at interconnected active sites, which favors direct coupling of neighboring ligand oxygens (I2M). Furthermore, our study reveals the crucial role of lattice oxygen participation in spin-polarized OER, significantly facilitating the coupling kinetics of neighboring oxygen radicals at active sites.

Breaking the cycle: Reforming pesticide regulation to protect pollinators.

Over decades, pesticide regulations have cycled between approval and implementation, followed by the discovery of negative effects on nontarget organisms that result in new regulations, pesticides, and harmful effects. This relentless pattern undermines the capacity to protect the environment from pesticide hazards and frustrates end users that need pest management tools. Wild pollinating insects are in decline, and managed pollinators such as honey bees are experiencing excessive losses, which threatens sustainable food security and ecosystem function. An increasing number of studies demonstrate the negative effects of field-realistic exposure to pesticides on pollinator health and fitness, which contribute to pollinator declines. Current pesticide approval processes, although they are superior to past practices, clearly continue to fail to protect pollinator health. In the present article, we provide a conceptual framework to reform cyclical pesticide approval processes and better protect pollinators.

Conjugated Nickel Phthalocyanine Derivatives for Heterogeneous Electrocatalytic H2 O2 Synthesis.

Electrocatalytic hydrogen peroxide (H2 O2 ) production has emerged as a promising alternative to the chemical method currently used in industry, due to its environmentally friendly conditions and potential for higher activity and selectivity. Heterogeneous molecular catalysts are promising in this regard, as their active site configurations can be judiciously designed, modified, and tailored with diverse functional groups, thereby tuning the activity and selectivity of the active sites. In this work, nickel phthalocyanine derivatives with various conjugation degrees are synthesized and identified as effective pH-universal electrocatalysts for H2 O2 production after heterogenized on nitrogen-decorated carbon, with increased conjugation degrees leading to boosted selectivity. This is explained by the regulated d-band center, which optimized the binding energy of the reaction intermediate, reducing the energy barrier for oxygen reduction and leading to optimized H2 O2 selectivity. The best catalyst, NiPyCN/CN, exhibits a high H2 O2  electrosynthesis activity with ≈95% of H2 O2 faradic efficiency in an alkaline medium, demonstrating its potential for H2 O2 production.

The origin of magnetization-caused increment in water oxidation.

Magnetization promoted activity of magnetic catalysts towards the oxygen evolution reaction (OER) has attracted great attention, but remains a puzzle where the increment comes from. Magnetization of a ferromagnetic material only changes its magnetic domain structure. It does not directly change the spin orientation of unpaired electrons in the material. The confusion is that each magnetic domain is a small magnet and theoretically the spin-polarization promoted OER already occurs on these magnetic domains, and thus the enhancement should have been achieved without magnetization. Here, we demonstrate that the enhancement comes from the disappeared domain wall upon magnetization. Magnetization leads to the evolution of the magnetic domain structure, from a multi-domain one to a single domain one, in which the domain wall disappears. The surface occupied by the domain wall is reformatted into one by a single domain, on which the OER follows the spin-facilitated pathways and thus the overall increment on the electrode occurs. This study fills the missing gap for understanding the spin-polarized OER and it further explains the type of ferromagnetic catalysts which can give increment by magnetization.

Light-Activated Interface Charge-Alternating Interaction on an Extended Gate Photoelectrode: A New Sensing Strategy for EGFET-Based Photoelectrochemical Sensors.

Integration of extended gate field-effect transistors (EGFET) and photoelectrochemical (PEC) measurement to construct highly sensitive sensors is an innovative research field that was proven feasible by our previous work. However, it remains a challenge on how to adjust the interaction between the extended gate and the analyte and study its influence on EGFET-based PEC sensors. Herein, a new sensing strategy was proposed by a mutual electrostatic interaction. Three-dimensional TiO2 and g-C3N4 core-shell heterojunction on flexible carbon cloth (TCN) was designed as the extended sensing gate. Tetracycline (TC) was also used as a model analyte, and it contains electron-donating groups (-NH2 and -OH) with negative charge. The designed TCN-extended sensing gate was negatively charged in the dark by introducing carbon vacancies with oxygen doping in the g-C3N4 shell, while it was positively charged under illustration due to the aggregation of photogenerated holes on the surface. Therefore, a light-activated PEC sensing platform for the sensitive and selective determination of tetracycline (TC) was demonstrated. Such a PEC sensor exhibited wide linear ranges within 100 pM to 1 µM and 1-100 µM with a low detection limit of 0.42 pM. Furthermore, the sensing platform possessed excellent selectivity, good reproducibility, and stability. The proposed sensing strategy in this work can expand the paradigm for developing a light-regulated FET-based PEC sensor by mutual electrostatic interaction, and we believe that this work will offer a new perspective for the design of interface interaction in PEC devices.

Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation.

Water electrolysis is a promising technique for carbon neutral hydrogen production. A great challenge remains at developing robust and low-cost anode catalysts. Many pre-catalysts are found to undergo surface reconstruction to give high intrinsic activity in the oxygen evolution reaction (OER). The reconstructed oxyhydroxides on the surface are active species and most of them outperform directly synthesized oxyhydroxides. The reason for the high intrinsic activity remains to be explored. Here, a study is reported to showcase the unique reconstruction behaviors of a pre-catalyst, thiospinel CoFe2 S4 , and its reconstruction chemistry for a high OER activity. The reconstruction of CoFe2 S4 gives a mixture with both Fe-S component and active oxyhydroxide (Co(Fe)Ox Hy ) because Co is more inclined to reconstruct as oxyhydroxide, while the Fe is more stable in Fe-S component in a major form of Fe3 S4 . The interface spin channel is demonstrated in the reconstructed CoFe2 S4 , which optimizes the energetics of OER steps on Co(Fe)Ox Hy species and facilitates the spin sensitive electron transfer to reduce the kinetic barrier of O-O coupling. The advantage is also demonstrated in a membrane electrode assembly (MEA) electrolyzer. This work introduces the feasibility of engineering the reconstruction chemistry of the precatalyst for high performance and durable MEA electrolyzers.

Suicidal behaviors in the entertainment industry: a preliminary exploration of the interplay between work scheduling, social support, and wellbeing in Australia.

OBJECTIVE: Workers of the Australian entertainment industry exhibit disproportionately high rates of impaired psychological wellbeing and suicidal behaviors, with such rates being exacerbated by the negative impact of working long and odd hours (Work Scheduling Impact; WSI). Nonetheless, stable and secure social support networks may buffer the risks associated with such systemic difficulties. METHODS: The responses of 1302 Australian entertainment industry workers (50.3% females, Mage 38.39 years) on the Multidimensional Scale of Perceived Social Support, the Short Form Health Survey, WSI, and suicidal behaviors questions were examined via moderation analyses. RESULTS: Higher social support and lower WSI appeared to reduce the suicidal ideation of those experiencing poorer mental health, while lower WSI further enhanced social support's positive effect. CONCLUSIONS: Findings highlight the likely detrimental effect of WSI regarding the suicidal ideation reported by vulnerable Australian entertainment industry workers and stress the importance of the social support they experience. PUBLIC HEALTH IMPLICATIONS: Interventions attempting to increase social support could improve inherent conditions associated with the Australian entertainment industry. Similarly, the negative effect of working long and odd hours on workers' mental health and suicidal behaviors indicates the need to regulate the industry appropriately.

The effect of the hydroxyl group position on the electrochemical reactivity and product selectivity of butanediol electro-oxidation.

This article presents a study on the effect of the hydroxyl group position on the electro-oxidation of butanediols, including 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 1,4-butanediol. The effect of the hydroxyl group position in butanediols on their electro-oxidation reactivities is investigated by cyclic voltammetry, linear sweep voltammetry, chronopotentiometry and chronoamperometry in 1.0 M KOH. The results show that the closer the two hydroxyl groups are, the higher the reactivity, and the lower the anodic potential butanediol has. Moreover, the oxidation products from chronoamperometry are analyzed by means of HPLC and NMR. Some value-added products, such as 3-hydroxypropionic acid/3-hydroxypropionate, are produced. The DFT calculation indicates that the oxidation of vicinal diols responds to the conversion from a hydroxyl group to a carboxylate group, followed by C-C bond cleavage, where the carbon charge decreases. These results provide an insight into reactant selection for the electrochemical synthesis of value-added chemicals.

Enhanced oxygen evolution over dual corner-shared cobalt tetrahedra.

Developing efficient catalysts is of paramount importance to oxygen evolution, a sluggish anodic reaction that provides essential electrons and protons for various electrochemical processes, such as hydrogen generation. Here, we report that the oxygen evolution reaction (OER) can be efficiently catalyzed by cobalt tetrahedra, which are stabilized over the surface of a Swedenborgite-type YBCo4O7 material. We reveal that the surface of YBaCo4O7 possesses strong resilience towards structural amorphization during OER, which originates from its distinctive structural evolution toward electrochemical oxidation. The bulk of YBaCo4O7 composes of corner-sharing only CoO4 tetrahedra, which can flexibly alter their positions to accommodate the insertion of interstitial oxygen ions and mediate the stress during the electrochemical oxidation. The density functional theory calculations demonstrate that the OER is efficiently catalyzed by a binuclear active site of dual corner-shared cobalt tetrahedra, which have a coordination number switching between 3 and 4 during the reaction. We expect that the reported active structural motif of dual corner-shared cobalt tetrahedra in this study could enable further development of compounds for catalyzing the OER.

Global application of an unoccupied aerial vehicle photogrammetry protocol for predicting aboveground biomass in non-forest ecosystems.

Non-forest ecosystems, dominated by shrubs, grasses and herbaceous plants, provide ecosystem services including carbon sequestration and forage for grazing, and are highly sensitive to climatic changes. Yet these ecosystems are poorly represented in remotely sensed biomass products and are undersampled by in situ monitoring. Current global change threats emphasize the need for new tools to capture biomass change in non-forest ecosystems at appropriate scales. Here we developed and deployed a new protocol for photogrammetric height using unoccupied aerial vehicle (UAV) images to test its capability for delivering standardized measurements of biomass across a globally distributed field experiment. We assessed whether canopy height inferred from UAV photogrammetry allows the prediction of aboveground biomass (AGB) across low-stature plant species by conducting 38 photogrammetric surveys over 741 harvested plots to sample 50 species. We found mean canopy height was strongly predictive of AGB across species, with a median adjusted R 2 of 0.87 (ranging from 0.46 to 0.99) and median prediction error from leave-one-out cross-validation of 3.9%. Biomass per-unit-of-height was similar within but different among, plant functional types. We found that photogrammetric reconstructions of canopy height were sensitive to wind speed but not sun elevation during surveys. We demonstrated that our photogrammetric approach produced generalizable measurements across growth forms and environmental settings and yielded accuracies as good as those obtained from in situ approaches. We demonstrate that using a standardized approach for UAV photogrammetry can deliver accurate AGB estimates across a wide range of dynamic and heterogeneous ecosystems. Many academic and land management institutions have the technical capacity to deploy these approaches over extents of 1-10 ha-1. Photogrammetric approaches could provide much-needed information required to calibrate and validate the vegetation models and satellite-derived biomass products that are essential to understand vulnerable and understudied non-forested ecosystems around the globe.

Decomposing biophotovoltaic current density profiles using the Hilbert-Huang transform reveals influences of circadian clock on cyanobacteria exoelectrogenesis.

Electrons from cyanobacteria photosynthetic and respiratory systems are implicated in current generated in biophotovoltaic (BPV) devices. However, the pathway that electrons follow to electrodes remains largely unknown, limiting progress of applied research. Here we use Hilbert-Huang Transforms to decompose Synechococcus elongatus sp. PCC7942 BPV current density profiles into physically meaningful oscillatory components, and compute their instantaneous frequencies. We develop hypotheses for the genesis of the oscillations via repeat experiments with iron-depleted and 20% CO[Formula: see text] enriched biofilms. The oscillations exhibit rhythms that are consistent with the state of the art cyanobacteria circadian model, and putative exoelectrogenic pathways. In particular, we observe oscillations consistent with: rhythmic D1:1 (photosystem II core) expression; circadian-controlled glycogen accumulation; circadian phase shifts under modified intracellular %ATP; and circadian period shortening in the absence of the iron-sulphur protein LdpA. We suggest that the extracted oscillations may be used to reverse-identify proteins and/or metabolites responsible for cyanobacteria exoelectrogenesis.

Optimized Artificial Neural Network for Evaluation: C4 Alkylation Process Catalyzed by Concentrated Sulfuric Acid.

In this work, an artificial neural network was first achieved and optimized for evaluating product distribution and studying the octane number of the sulfuric acid-catalyzed C4 alkylation process in the stirred tank and rotating packed bed. The feedstock compositions, operating conditions, and reactor types were considered as input parameters into the artificial neural network model. Algorithm, transfer function, and framework were investigated to select the optimal artificial neural network model. The optimal artificial neural network model was confirmed as a network topology of 10-20-30-5 with Bayesian Regularization backpropagation and tan-sigmoid transfer function. Research octane number and product distribution were specified as output parameters. The artificial neural network model was examined, and 5.8 × 10-4 training mean square error, 8.66 × 10-3 testing mean square error, and ±22% deviation were obtained. The correlation coefficient was 0.9997, and the standard deviation of error was 0.5592. Parameter analysis of the artificial neural network model was employed to investigate the influence of operating conditions on the research octane number and product distribution. It displays a bright prospect for evaluating complex systems with an artificial neural network model in different reactors.

Disability organizations as empowering settings: Challenging stigmatization, promoting emancipation.

This study investigated how a local disability organization in Yogyakarta Province, Indonesia, has functioned as an empowering setting for its members. This article discusses, in particular, the context specific features that have enabled members of this organization to resist the pervasive stigmatization commonly imposed upon people with disabilities. The research data was collected through interviews with 18 members of the organization and analyzed using the method of constructivist grounded theory. The findings suggest that this organization exists as an empowering setting because it functions as a mindset changer, an alternative resource center, and fosters supportive and courageous allies. Through this empowerment, members can challenge the normalized stigmatization and promote more emancipatory identities, particularly in a rural context where some socio-cultural aspects may further complicate the disadvantages of people with disabilities. Implications for future research and disability interventions are discussed.

Groundwater remediation using Magnesium-Aluminum alloys and in situ layered doubled hydroxides.

In situ remediation of groundwater by zerovalent iron (ZVI)-based technology faces the problems of rapid passivation, fast agglomeration, limited range of pollutants and secondary contamination. Here a new concept of Magnesium-Aluminum (Mg-Al) alloys and in situ layered double hydroxides on is proposed for the degradation and removal of a wide variety of inorganic and organic pollutants from groundwater. The Mg-Al alloy provides the electrons for the chemical reduction and/or the degradation of pollutants while released Mg2+, Al3+ and OH- ions react to generate in situ LDH precipitates, incorporating other divalent and trivalent metals and oxyanions pollutants and further adsorbing the micropollutants. The Mg-Al alloy outperforms ZVI for treating acidic, synthetic groundwater samples contaminated by complex chemical mixtures of heavy metals (Cd2+, Cr6+, Cu2+, Ni2+ and Zn2+), nitrate, AsO33-, methyl blue, trichloroacetic acid and glyphosate. Specifically, the Mg-Al alloy achieves removal efficiency ≥99.7% for these multiple pollutants at concentrations ranging between 10 and 50 mg L-1 without producing any secondary contaminants. In contrast, ZVI removal efficiency did not exceed 90% and secondary contamination up to 220 mg L-1 Fe was observed. Overall, this study provides a new alternative approach to develop efficient, cost-effective and green remediation for water and groundwater.

Lattice site-dependent metal leaching in perovskites toward a honeycomb-like water oxidation catalyst.

Metal leaching during water oxidation has been typically observed in conjunction with surface reconstruction on perovskite oxide catalysts, but the role of metal leaching at each geometric site has not been distinguished. Here, we manipulate the occurrence and process of surface reconstruction in two model ABO3 perovskites, i.e., SrSc0.5Ir0.5O3 and SrCo0.5Ir0.5O3, which allow us to evaluate the structure and activity evolution step by step. The occurrence and order of leaching of Sr (A-site) and Sc/Co (B-site) were controlled by tailoring the thermodynamic stability of B-site. Sr leaching from A-site mainly generates more electrochemical surface area for the reaction, and additional leaching of Sc/Co from B-site triggers the formation of a honeycomb-like IrOxHy phase with a notable increase in intrinsic activity. A thorough surface reconstruction with dual-site metal leaching induces an activity improvement by approximately two orders of magnitude, which makes the reconstructed SrCo0.5Ir0.5O3 among the best for water oxidation in acid.

The active ingredients of a mitotoxic fungicide negatively affect pollen consumption and worker survival in laboratory-reared honey bees (Apis mellifera).

Recent observations of many sublethal effects of pesticides on pollinators have raised questions about whether standard short-term laboratory tests of pesticide effects on survival are sufficient for pollinator protection. The fungicide Pristine® and its active ingredients (25.2% boscalid, 12.8% pyraclostrobin) have been reported to have low acute toxicity to caged honey bee workers, but many sublethal effects at field-relevant doses have been reported and Pristine® was recently found to increase worker pollen consumption, reduce worker longevity and colony populations at field relevant concentrations (Fisher et al. 2021). To directly compare these whole-colony field results to more standard laboratory toxicology tests, the effects of Pristine®, at a range of field-relevant concentrations, were assessed on the survival and pollen consumption of honey bee workers 0-14 days of age. Also, to separate the effects of the inert and two active ingredients, bees were fed pollen containing boscalid, pyraclostrobin, or pyraclostrobin plus boscalid, at concentrations matching those in the Pristine® treatments. Pyraclostrobin significantly reduced pollen consumption across the duration of the experiment, and dose-dependently reduced pollen consumption on days 12-14. Pristine® and boscalid significantly reduced pollen feeding rate on days 12-14. Boscalid reduced survival in a dose-dependent manner. Consumption of Pristine® or pyraclostrobin plus boscalid did not affect survival, providing evidence against strong negative effects of the inert ingredients in Pristine® and against negative synergistic effects of boscalid and pyraclostrobin. The stronger toxic effects of Pristine® observed in field colonies compared to this laboratory test, and the opposite responses of pollen consumption in the laboratory and field to Pristine®, show that standard laboratory toxicology tests can fail to predict responses of pollinators to pesticides and to provide protection.

Active Phase on SrCo1-x Fe x O3-δ (0 ≤ x ≤ 0.5) Perovskite for Water Oxidation: Reconstructed Surface versus Remaining Bulk.

Perovskite oxides based on earth-abundant transition metals have been extensively explored as promising oxygen evolution reaction (OER) catalysts in alkaline media. The (electro)chemically induced transformation of their initially crystalline surface into an amorphous state has been reported for a few highly active perovskite catalysts. However, little knowledge is available to distinguish the contribution of the amorphized surface from that of the remaining bulk toward the OER. In this work, we utilize the promoting effects of two types of Fe modification, i.e., bulk Fe dopant and Fe ions absorbed from the electrolyte, on the OER activity of SrCoO3-δ model perovskite to identify the active phase. Transmission electron microscopy and X-ray photoelectron spectroscopy confirmed the surface amorphization of SrCoO3-δ as well as SrCo0.8Fe0.2O3-δ after potential cycling in Fe-free KOH solution. By further cycling in Fe-spiked electrolyte, Fe was incorporated into the amorphized surface of SrCoO3-δ (SrCoO3-δ + Fe3+), yielding approximately sixfold increase in activity. Despite the difference in remaining perovskites, SrCoO3-δ + Fe3+ and SrCo0.8Fe0.2O3-δ exhibited remarkably similar activity. These results reflect that the in situ developed surface species are directly responsible for the measured OER activity, whereas the remaining bulk phases have little impact.

A common fungicide, Pristine®, impairs olfactory associative learning performance in honey bees (Apis mellifera).

Although fungicides were previously considered to be safe for important agricultural pollinators such as honey bees, recent evidence has shown that they can cause a number of behavioral and physiological sublethal effects. Here, we focus on the fungicide Pristine® (active ingredients: 25.2% boscalid, 12.8% pyraclostrobin), which is sprayed during the blooming period on a variety of crops and is known to affect honey bee mitochondria at field-relevant levels. To date, no study has tested the effects of a field-relevant concentration of a fungicide on associative learning ability in honey bees. We tested whether chronic, colony-level exposure at field-relevant and higher concentrations of Pristine® impairs performance on the proboscis extension reflex (PER) paradigm, an associative learning task. Learning performance was reduced at higher field-relevant concentrations of Pristine®. The reductions in learning performance could not be explained by effects on hunger or motivation, as sucrose responsiveness was not affected by Pristine® exposure. To determine whether Pristine®'s negative effects on learning performance were mediated at a specific life stage, we conducted a cross-fostering experiment that exposed bees to the fungicide either only as larvae, only as adults, or during both stages. We found that exposure across the entire life was necessary to significantly reduce learning performance, although non-significant reductions occurred when bees were exposed during just one stage. Our study provides strong evidence that Pristine® has significant sublethal effects on learning performance. As associative learning is a necessary ability for foraging, our results raise concerns that Pristine® could impair foraging abilities and substantially weaken colony health.

Spin pinning effect to reconstructed oxyhydroxide layer on ferromagnetic oxides for enhanced water oxidation.

Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER, to manipulate the spin ordering of ferromagnetic OER catalysts (e.g., by magnetization) can reduce the kinetic barrier. However, most active OER catalysts are not ferromagnetic, which makes the spin manipulation challenging. In this work, we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning, simple magnetization further increases the spin alignment and thus the OER activity, which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1st dehydrogenation to reduce the barrier for subsequent O-O coupling.