Tuning the surface reactivity of oxides by peroxide species.

The Mars-van Krevelen mechanism is the foundation for oxide-catalyzed oxidation reactions and relies on spatiotemporally separated redox steps. Herein, we demonstrate the tunability of this separation with peroxide species formed by excessively adsorbed oxygen, thereby modifying the catalytic activity and selectivity of the oxide. Using CuO as an example, we show that a surface layer of peroxide species acts as a promotor to significantly enhance CuO reducibility in favor of H2 oxidation but conversely as an inhibitor to suppress CuO reduction against CO oxidation. Together with atomistic modeling, we identify that this opposite effect of the peroxide on the two oxidation reactions stems from its modification on coordinately unsaturated sites of the oxide surface. By differentiating the chemical functionality between lattice oxygen and peroxide, these results are closely relevant to a wide range of catalytic oxidation reactions using excessively adsorbed oxygen to activate lattice oxygen and tune the activity and selectivity of redox sites.

Atomistic Origins of Reversible Noncatalytic Gas-Solid Interfacial Reactions.

Noncatalytic gas-solid reactions are a large group of heterogeneous reactions that are usually assumed to occur irreversibly because of the strong driving force to favor the forward direction toward the product formation. Using the example of Ni oxidation into NiO with CO2, herein, we demonstrate the existence of the reverse element that results in the NiO reduction from the countering effect of the gaseous product of CO. Using in situ electron microscopy observations and atomistic modeling, we show that the oxidation process occurs via preferential CO2 adsorption along step edges that results in step-flow growth of NiO layers, and the presence of Ni atoms on the flat NiO surface promotes the nucleation of NiO layers. Simultaneously, the NiO reduction happens via preferential step-edge adsorption of CO that leads to the receding motion of atomic steps, and the presence of Ni vacancies in the NiO surface facilitates the CO-adsorption-induced surface pitting. Temperature and CO2 pressure effect maps are constructed to illustrate the spatiotemporal dynamics of the competing NiO redox reactions. These results demonstrate the rich gas-solid surface reaction dynamics induced by the coexisting forward and reverse reaction elements and have practical applicability in manipulating gas-solid reactions via controlling the gas environment or atomic structure of the solid surface to steer the reaction toward the desired direction.

Communication Overload in Hospitals: Exploring Organizational Safety Communication, Worker Job Attitudes, and Communication Efficacy.

Hospitals represent complex organizations where a range of hospital workers, from physicians to administrators, encounter a deluge of information they must quickly process and act upon. New technologies implemented to streamline patient care, like electronic health records and wearable technologies, have both enhanced and complicated communicative exchanges between hospital workers and their organizations. Hospital workers feeling over saturated with workplace communication, and thus unable to effectively manage or interpret workplace messages, experience what has been labeled communication overload, which can negatively impact worker productivity and concentration. This study examines hospital workers (N = 303) in a Midwestern U.S. healthcare network, and uses structural equation modeling to offer a preliminary theoretical model that demonstrates the effects and outcomes of communication overload in high-risk organizations. The model offers theoretical implications through depicting communication overload as indirectly related to burnout, job satisfaction, and organizational identification through participation in decision-making and organizational safety climate. Results suggest that even if communication overload is an expected state in high-risk organizations, managers can prevent its negative effects on workers' job attitudes by providing workers opportunities to get involved in organizational decision-making and constructing a robust organizational safety climate. Finally, we suggest pairings of organizational safety communication channels and sources through which high quantities of safety information can be communicated without communicatively overloading workers.

COVID-19 Message Fatigue: How Does It Predict Preventive Behavioral Intentions and What Types of Information are People Tired of Hearing About?

This study examines the impact of message fatigue and what makes people fatigued in the context of the COVID-19 pandemic. Data collected with a Qualtrics panel (N = 744) showed that both active (i.e., reactance) and passive (i.e., inattention) resistance in message processing mediated the relationships between message fatigue and intentions to follow three types of preventive behaviors against COVID-19 (i.e., wearing masks, social distancing, and washing hands). The indirect effect of message fatigue on intention to seek COVID-19 information was explained by inattention but not reactance. Analyses of open-ended responses identified 18 types of COVID-related information that individuals were tired of hearing about. About 73.38% of participants (n = 546) reported that they were tired of hearing about at least one type of information about COVID-19, with mask-wearing being the most frequently mentioned (21.91%). The results extend existing research on message fatigue-evoked resistance to persuasion and provide practical implications for public health message design.

Oxidative Roles of Polystyrene-Based Nanoplastics in Inducing Manganese Oxide Formation under Light Illumination.

Every year, large quantities of plastics are produced and used for diverse applications, growing concerns about the waste management of plastics and their release into the environment. Plastic debris can break down into millions of pieces that adversely affect natural organisms. In particular, the photolysis of micro/nanoplastics can generate reactive oxygen species (ROS). However, their oxidative roles in initiating redox chemical reactions with heavy and transition metals have received little attention. In this study, we investigated whether the photolysis of polystyrene (PS) nanoplastics can induce the oxidation of Mn2+(aq) to Mn oxide solids. We found that PS nanoplastics not only produced peroxyl radicals (ROO•) and superoxide radicals (O2•-) by photolysis, which both play a role in unexpected Mn oxidation, but also served as a substrate for facilitating the heterogeneous nucleation and growth of Mn oxide solids and controlling the formation rate and crystalline phases of Mn oxide solids. These findings help us to elucidate the oxidative roles of nanoplastics in the oxidation of redox-active metal ions. The production of ROS from nanoplastics in the presence of light can endanger marine life and human health, and affect the mobility of the nanoplastics in the environment via redox reactions, which in turn may negatively impact their environmental remediation.

Photochemical reactions of dissolved organic matter and bromide ions facilitate abiotic formation of manganese oxide solids.

Manganese (Mn) oxide solids are ubiquitous in nature, acting as both electron donors and acceptors in diverse redox reactions in the environment. Reactions of Mn(III/IV) oxides with dissolved natural organic matter (DOM) are commonly described as reductive dissolutions that generate Mn2+(aq). In this study, we investigated the role of photochemical reactions of DOM in Mn2+(aq) oxidation and the resulting formation of Mn oxide solids. During the photolysis of DOM, reactive intermediates can be generated, including excited triplet state DOM (3DOM*), hydroxyl radicals (•OH), superoxide radicals (O2•-), hydrogen peroxide, and singlet oxygen. Among these, we found that O2•- radicals were mainly responsible for Mn oxidation. The solution pH controlled the formation of Mn oxide solids by affecting both Mn2+ oxidation by O2•- during photolysis of DOM and reductive dissolutions of Mn oxide solids by DOM. Further, with the addition of bromide ions (Br-), reactions between 3DOM* and Br-, together with reactions between •OH and Br-, can form reactive bromide radicals. The formed Br radicals also promoted Mn oxide formation. In DOM with more aromatic functional groups, more Mn2+ was oxidized to Mn oxide solids. This enhanced oxidation could be the result of promoted pathways from charge-transfer state DOM (DOM•+/•-) to O2•-. These new observations advance our understanding of natural Mn2+ oxidation and Mn(III/IV) oxide formation and highlight the underappreciated oxidative roles of DOM in the oxidation of metal ions in surface water illuminated by sunlight.

In Situ Monitoring of H2-Induced Nonstoichiometry in Cu2O.

Using ambient-pressure X-ray photoelectron spectroscopy and Auger electron spectroscopy to monitor the reduction of Cu2O in H2, we identify the formation of an intermediate, oxygen-deficient Cu2O phase and its progressive inward growth into the deeper region of the oxide. Complemented by atomistic modeling, we show that the oxygen-deficient Cu2O formation occurs via molecular H2 adsorption at the Cu2O surface, which results in the loss of lattice oxygen from the formation of H2O molecules that desorb spontaneously from the oxide surface. The resulting oxygen-deficient Cu2O is a stable intermediate that persists before the Cu2O is fully reduced to metallic Cu. The oxygen vacancy-induced charge of the coordinating Cu atoms results in a satellite feature in Cu LMM, which can be used as a fingerprint to identify nonstoichiometry in oxides and local charge transfer induced by the nonstoichiometry.

Process-Specific Effects of Sulfate on CaCO3 Formation in Environmentally Relevant Systems.

Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO3's formation and is seldom found to significantly affect multiple CaCO3 formation processes. Here, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO3 precursors and nuclei, promoting CaCO3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO3. Meanwhile, adsorbed sulfate on CaCO3 nuclei may poison the surface of smaller CaCO3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.

Revealing an Intermediate Cu-O/OH Superstructure on Cu(110).

Identifying the atomic structure and formation mechanism of intermediates during chemical transformations is challenging because of their short-lived nature. With a combination of microscopic and spectroscopic measurements and first-principles calculations, herein we report the formation of a metastable intermediate Cu-O/OH superstructure during the reaction of hydrogen with oxygen-covered Cu(110). This superstructure resembles the parent c(6 × 2)-O phase and can be termed as c(6 × 2)-(4O+2OH) with OH groups occupying the missing Cu sites between isolated Cu atoms. Using atomistic calculations, we elucidate the reaction pathways leading to the c(6 × 2)-(4O+2OH) formation via both molecular and dissociative H2 adsorption. These results demonstrate the complex surface dynamics resulting from the parallel reaction pathways and may open up the possibility of directing the reaction dynamics by deliberately manipulating transient surface structure and composition.

Classical and Nonclassical Nucleation and Growth Mechanisms for Nanoparticle Formation.

All solid materials are created via nucleation. In this evolutionary process, nuclei form in solution or at interfaces, expand by monomeric growth and oriented attachment, and undergo phase transformation. Nucleation determines the location and size of nuclei, whereas growth controls the size, shape, and aggregation of newly formed nanoparticles. These physical properties of nanoparticles can affect their functionalities, reactivities, and porosities, as well as their fate and transport. Recent advances in nanoscale analytical technologies allow in situ real-time observations, enabling us to uncover the molecular nature of nuclei and the critical controlling factors for nucleation and growth. Although a single theory cannot yet fully explain such evolving processes, we have started to better understand how both classical andnonclassical theories can work together, and we have begun to recognize the importance of connecting these theories. This review discusses the recent convergence of knowledge about the nucleation and growth of nanoparticles.

Generic Mechanism for Waveform Regulation and Synchronization of Oscillators: An Application for Robot Behavior Diversity Generation.

While nonlinear oscillators have been widely used for central pattern generators to produce basic rhythmic signals for robot locomotion control, methods to shape and regulate the signal waveform without changing the characteristics of the oscillators have not been fully investigated, especially during the network synchronization process. To illustrate the principle and process of waveform regulation of nonlinear oscillators in detail and ensure that the influence can be controlled, we present a method for waveform regulation and synchronization and analyze the relationship of different factors (e.g., initial conditions, network parameters, phase, and waveform regulation factors) in synchronization deviation. Then, the method is indicated to be effective in other commonly used nonlinear oscillators and neural oscillators. As an example application, a three-layer behavioral control architecture for a legged robot is constructed based on the proposed method. Modules for the body behavior, leg coordination, and single-leg adjustment are established to realize diverse robot behaviors. The effectiveness of the method is validated by a series of experiments. The results prove that the method performs well in terms of signal control accuracy, behavior pattern diversity, and smooth motion transition.

A Biosynthetic Hybrid Spidroin-Amyloid-Mussel Foot Protein for Underwater Adhesion on Diverse Surfaces.

Strong underwater adhesives are attractive materials for biomedical healing and underwater repair, but their success in applications has been limited, owing to challenges with underwater setting and with balancing surface adhesion and cohesion. Here, we applied synthetic biology approaches to overcome these challenges through design and synthesis of a novel hybrid protein consisting of the zipper-forming domains of an amyloid protein, flexible spider silk sequences, and a dihydroxyphenylalanine (DOPA)-containing mussel foot protein (Mfp). This partially structured, hybrid protein can self-assemble into a semi-crystalline hydrogel that exhibits high strength and toughness as well as strong underwater adhesion to a variety of surfaces, including difficult-to-adhere plastics, tendon, and skin. The hydrogel allows selective debonding by oxidation or iron-chelating treatments. Both the material design and the biosynthetic approach explored in this study will inspire future work for a wide range of hybrid protein-based materials with tunable properties and broad applications.

Microbial production of megadalton titin yields fibers with advantageous mechanical properties.

Manmade high-performance polymers are typically non-biodegradable and derived from petroleum feedstock through energy intensive processes involving toxic solvents and byproducts. While engineered microbes have been used for renewable production of many small molecules, direct microbial synthesis of high-performance polymeric materials remains a major challenge. Here we engineer microbial production of megadalton muscle titin polymers yielding high-performance fibers that not only recapture highly desirable properties of natural titin (i.e., high damping capacity and mechanical recovery) but also exhibit high strength, toughness, and damping energy - outperforming many synthetic and natural polymers. Structural analyses and molecular modeling suggest these properties derive from unique inter-chain crystallization of folded immunoglobulin-like domains that resists inter-chain slippage while permitting intra-chain unfolding. These fibers have potential applications in areas from biomedicine to textiles, and the developed approach, coupled with the structure-function insights, promises to accelerate further innovation in microbial production of high-performance materials.

Microbially Synthesized Polymeric Amyloid Fiber Promotes ß-Nanocrystal Formation and Displays Gigapascal Tensile Strength.

The ability of amyloid proteins to form stable ß-sheet nanofibrils has made them potential candidates for material innovation in nanotechnology. However, such a nanoscale feature has rarely translated into attractive macroscopic properties for mechanically demanding applications. Here, we present a strategy by fusing amyloid peptides with flexible linkers from spidroin; the resulting polymeric amyloid proteins can be biosynthesized using engineered microbes and wet-spun into macroscopic fibers. Using this strategy, fibers from three different amyloid groups were fabricated. Structural analyses unveil the presence of ß-nanocrystals that resemble the cross-ß structure of amyloid nanofibrils. These polymeric amyloid fibers have displayed strong and molecular-weight-dependent mechanical properties. Fibers made of a protein polymer containing 128 repeats of the FGAILSS sequence displayed an average ultimate tensile strength of 0.98 ± 0.08 GPa and an average toughness of 161 ± 26 MJ/m3, surpassing most recombinant protein fibers and even some natural spider silk fibers. The design strategy and the biosynthetic approach can be expanded to create numerous functional materials, and the macroscopic amyloid fibers will enable a wide range of mechanically demanding applications.

Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution.

Unveiling the effects of an environmental abundant anion "sulfate" on the formation of calcium carbonate (CaCO3) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate-CaCO3 interactions at the explicit first step of CaCO3 formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO3 nucleation is monitored in real time as a function of sulfate concentrations (0-10 mM Na2SO4) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO3 nucleation rate, causing a 120% increase in the CaCO3 nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO3 and finds a non-linear trend, suggesting that CaCO3 heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO3 interfacial energies, a key step toward achieving natural and engineered controls on CaCO3 nucleation.

A Social Ties-based Approach to Breast Cancer Patients' Quality of Life: Examining Group Ties and Individual Ties across Offline and Online Settings.

Supportive social ties positively impact cancer patients' health; however, little is known about the intertwined links between both offline and online ties, and individual and group ties. Using the common-identity/common-bond approach, we empirically tested the critical difference that individual and group ties exert on health across offline and online settings. Results from 356 female breast cancer patients showed group ties affect quality of life through sequential group identification and social support, while individual ties affect quality of life through sequential interpersonal bonds and social support. Offline group and online individual ties are stronger predictors of quality of life than online group and offline individual ties. A cluster analysis categorized participants into four distinguishable segments. People with stronger offline interpersonal bonds and online group identification reported a better quality of life. This offers insight into the social dynamics that are most consequential for health, and the potential theoretical pathways through which they operate.

Sending and Receiving Safety and Risk Messages in Hospitals: An Exploration into Organizational Communication Channels and Providers' Communication Overload.

This study explores hospital workers' experiences with workplace communication overload and its implications for effective safety and risk messaging in hospital organizations. We use a multi-step thematic analysis of interview (N = 12) and focus group (N = 8, 28 participants) data collected from hospital workers to analyze how they describe specific organizational communication channels influencing their communication overload. We specifically examine how workers' socially constructed channel affordances and constraints for sending/receiving safety information provide meaning to their communicatively overloaded states. Hospital workers explained that asynchronous channels such as e-mail and voicemail aggravated communication overload, while synchronous channels such as team huddles alleviated it. We discuss the implications of these results for the communication overload model by pointing to violations of communication channel preference and literature on the social affordances of communication channels. Study limitations and future directions are offered.

Quality change mechanism and drinking safety of repeatedly-boiled water and prolonged-boil water: a comparative study.

Quality, safety and potability of repeatedly-boiled water (RBW) and prolonged-boil water (PBW) lead to concern and even misgivings in the public from time to time, especially in China, and other societies have a habit of drinking boiled water, with improvements of living standards and owing to increasing concerns for human health. This phenomenon is mainly attributed to the fact that the conclusions drawn from existing scientific experiments could not respond well to the concerns. In order to make up for this deficiency, tap water was selected to carry out RBW and PBW experiments independently. The quality changes of RBW and PBW show very similar trends that are not as great as might be imagined, and both are impacted by the tap water quality and the physiochemical effects. The dominating physiochemical effects are the water evaporation and the resulting concentration of unreactive components (most dissolved components), which can be easily explained by the existing evaporation-concentration theory. The results show that tap water will be still safe and potable after being frequently boiled or after having undergone prolonged boiling, as long as it satisfies the sanitary standards of drinking water prior to heating. Therefore, there is no need to worry about drinking RBW or PBW in daily life.

Measuring Charge Transfer between Adsorbate and Metal Surfaces.

Charge transfer between dissimilar atoms is an essential step for many chemical processes such as corrosion and heterogeneous catalysis, but directly probing the charge transfer has been a challenge. Using the oxygen-copper system as an example, we show that synchrotron-based ambient pressure X-ray photoelectron spectroscopy can be employed to monitor the charge transfer between adsorbates and metal surfaces. It is shown that oxygen chemisorption on Cu surfaces results in an Auger process that differs from the photoexcitation-induced Coster-Kroning transition and can be used to derive the degree of charge transfer in combination with ab initio calculations. The identified chemisorption-induced Auger process may have broader implications for its use as a fingerprint to monitor bond formation and charge transfer between dissimilar atoms.