Hierarchical Bi2O3 nanosheets and ZIF-8 derived porous nitrogen-doped carbon fibers as novel assembled nanocomposites for high-performance flexible supercapacitors.

The unique design of the core-shell heterostructure is significant for obtaining electrode materials with excellent electrochemical properties. In this paper, porous carbon nanofibers (NPC@PPZ) embedded with N-doped porous carbon nanoparticles are used to construct flexible electrodes (NPC@PPZ@Bi2O3). Zeolite imidazole skeleton (ZIF)-8 and poly(methyl methacrylate) (PMMA) derived porous carbon fibers and Bi2O3 nanosheets, were utilized as the porous core and multilayer shell, respectively. The unique core and shell result in abundant pores and channels for fast ion transport and storage, high specific surface area, and additional electroactive sites. This perfect structural design enables the NPC@PPZ@Bi2O3 composite electrode to have excellent electrochemical performance. The results show that this electrode can obtain a high specific capacitance of 697 F g-1 at a current density of 1 A g-1 and a stable cycling performance at a high current density of 5 A g-1. The strategy developed in this study provides a new approach for the design and fabrication of flexible supercapacitors by electrostatic spinning combined with hierarchical porous structures.

Rising frequency of ozone-favorable synoptic weather patterns contributes to 2015-2022 ozone increase in Guangzhou.

Objective weather classification methods have been extensively applied to identify dominant ozone-favorable synoptic weather patterns (SWPs), however, the consistency of different classification methods is rarely examined. In this study, we apply two widely-used objective methods, the self-organizing map (SOM) and K-means clustering analysis, to derive ozone-favorable SWPs at four Chinese megacities in 2015-2022. We find that the two algorithms are largely consistent in recognizing dominant ozone-favorable SWPs for four Chinese megacities. In the case of classifying six SWPs, the derived circulation fields are highly similar with a spatial correlation of 0.99 between the two methods, and the difference in the mean frequency of each SWP is less than 7%. The six dominant ozone-favorable SWPs in Guangzhou are all characterized by anomaly higher radiation and temperature, lower cloud cover, relative humidity, and wind speed, and stronger subsidence compared to climatology mean. We find that during 2015-2022, the occurrence of ozone-favorable SWPs days increases significantly at a rate of 3.2 day/year, faster than the increases in the ozone exceedance days (3.0 day/year). The interannual variability between the occurrence of ozone-favorable SWPs and ozone exceedance days are generally consistent with a temporal correlation coefficient of 0.6. In particular, the significant increase in ozone-favorable SWPs in 2022, especially the Subtropical High type which typically occurs in September, is consistent with a long-lasting ozone pollution episode in Guangzhou during September 2022. Our results thus reveal that enhanced frequency of ozone-favorable SWPs plays an important role in the observed 2015-2022 ozone increase in Guangzhou.

Co-doped cryptomelane-type manganese oxide in situ grown on a nickel foam substrate for high humidity ozone decomposition.

Monolithic catalysts with excellent O3 catalytic decomposition performance were prepared by in situ loading of Co-doped KMn8O16 on the surface of nickel foam. The triple-layer structure with Co-doped KMn8O16/Ni6MnO8/Ni foam was grown spontaneously on the surface of nickel foam by tuning the molar ratio of KMnO4 to Co(NO3)2·6H2O precursors. Importantly, the formed Ni6MnO8 structure between KMn8O16 and nickel foam during in situ synthesis process effectively protected nickel foam from further etching, which significantly enhanced the reaction stability of catalyst. The optimum amount of Co doping in KMn8O16 was available when the molar ratio of Mn to Co species in the precursor solution was 2:1. And the Mn2Co1 catalyst had abundant oxygen vacancies and excellent hydrophobicity, thus creating outstanding O3 decomposition activity. The O3 conversion under dry conditions and relative humidity of 65%, 90% over a period of 5 hr was 100%, 94% and 80% with the space velocity of 28,000 hr-1, respectively. The in situ constructed Co-doped KMn8O16/Ni foam catalyst showed the advantages of low price and gradual applicability of the preparation process, which provided an opportunity for the design of monolithic catalyst for O3 catalytic decomposition.

Enhanced VOC emission with increased temperature contributes to the shift of O3-precursors relationship and optimal control strategy.

Assessing the impact of anthropogenic volatile organic compounds (VOCs) on ozone (O3) formation is vital for the management of emission reduction and pollution control. Continuous measurement of O3 and the major precursors was conducted in a typical light industrial city in the YRD region from 1 May to 25 July in 2021. Alkanes were the most abundant VOC group, contributing to 55.0% of TVOCs concentration (56.43 ± 21.10 ppb). OVOCs, aromatics, halides, alkenes, and alkynes contributed 18.7%, 9.6%, 9.3%, 5.2% and 1.9%, respectively. The observational site shifted from a typical VOC control regime to a mixed regime from May to July, which can be explained by the significant increase of ROx production, resulting in the transition of environment from NOx saturation to radical saturation with respect to O3 production. The optimal O3 control strategy should be dynamically changed depending on the transition of control regime. Under NOx saturation condition, minimizing the proportion of NOx in reduction could lead to better achievement of O3 alleviation. Under mixed control regime, the cut percentage gets the top priority for the effectiveness of O3 control. Five VOCs sources were identified: temperature dependent source (28.1%), vehicular exhausts (19.9%), petrochemical industries (7.2%), solvent & gasoline usage (32.3%) and manufacturing industries (12.6%). The increase of temperature and radiation would enhance the evaporation related VOC emissions, resulting in the increase of VOC concentration and the change of ROx circulation. Our results highlight determination of the optimal control strategies for O3 pollution in a typical YRD industrial city.

Development and application of a nitrogen oxides analyzer based on the cavity attenuated phase shift technique.

Nitrogen oxides (NOx) are crucial in tropospheric photochemical ozone (O3) production and oxidation capacity. Currently, the widely used NOx measurement technique is chemiluminescence (CL) (CL-NOx), which tends to overestimate NO2 due to atmospheric oxidation products of NOx (i.e., NOz). We developed and characterized a NOx measurement system using the cavity attenuated phase shift (CAPS) technique (CAPS-NOx), which is free from interferences with nitrogen-containing species. The NOx measured by the CAPS-NOx and CL-NOx analyzers were compared. Results show that both analyzers showed consistent measurement results for NO, but the NO2 measured by the CAPS-NOx analyzer (NO2_CAPS) was mostly lower than that measured by the CL-NOx analyzer (NO2_CL), which led to the deviations in O3 formation sensitivity regime and Ox (= O3 + NO2) sources (i.e., regional background and photochemically produced Ox) determined by the ozone production efficiencies (OPE) calculated from NO2_CL and NO2_CAPS. Overall, OPE_CL exceeded OPE_CAPS by 18.9%, which shifted 3 out of 13 observation days from the VOCs-limited to the transition regime when judging using OPE_CL, as compared to calculations using OPE_CAPS. During the observation period, days dominated by regional background Ox accounted for 46% and 62% when determined using NO2_CL and NO2_CAPS, respectively. These findings suggest that the use of the CL-NOx analyzer tends to underestimate both the VOCs-limited regime and the regional background Ox dominated days. The newly built CAPS-NOx analyzer here can promote the accurate measurement of NO2, which is meaningful for diagnosing O3 formation regimes and Ox sources.

Quantitative impacts of meteorology and emissions on the long-term trend of O3 in the Yangtze River Delta (YRD), China from 2015 to 2022.

Extensive spatiotemporal analyses of long-trend surface ozone in the Yangtze River Delta (YRD) region and its meteorology-related and emission-related have not been systematically analyzed. In this study, by using 8-year-long (2015-2022) surface ozone observation data, we attempted to reveal the variation of multiple timescale components using the Kolmogorov-Zurbenko filter, and the effects of meteorology and emissions were quantitatively isolated using multiple linear regression with meteorological variables. The results showed that the short-term, seasonal, and long-term components accounted for daily maximum 8-hr average O3 (O3-8 hr) concentration, 46.4%, 45.9%, and 1.0%, respectively. The meteorological impacts account for an average of 71.8% of O3-8 hr, and the YRD's eastern and northern sections are meteorology-sensitive areas. Based on statistical analysis technology with empirical orthogonal function, the contribution of meteorology, local emission, and transport in the long-term component of O3-8 hr were 0.21%, 0.12%, and 0.6%, respectively. The spatiotemporal analysis indicated that a distinct decreasing spatial pattern could be observed from coastal cities towards the northwest, influenced by the monsoon and synoptic conditions. The central urban agglomeration north and south of the YRD was particularly susceptible to local pollution. Among the cities studied, Shanghai, Anqing, and Xuancheng, located at similar latitudes, were significantly impacted by atmospheric transmission-the contribution of Shanghai, the maximum accounting for 3.6%.

Effect of Metal Oxide Deposition on the Sensitivity and Resolution of E-Beam Photoresist.

Organic-inorganic hybrid resists offer a solution to the issue of low sensitivity in organic photoresists like poly(methyl methacrylate) (PMMA). In this study, an organic-inorganic hybrid resist (PMMA-Al2O3) with high sensitivity and resolution was prepared by depositing metal oxides into PMMA using sequential infiltration synthesis (SIS). PMMA-Al2O3 was prepared by precisely controlling the number of SIS cycles (<23) in various atomic layer deposition (ALD) processes to facilitate the growth of metal oxides within PMMA pores. The impact of different metal oxide contents and distributions on the sensitivity and resolution of electron beam exposure was investigated. Numerical simulations of the deposit formation within the PMMA pores were performed by solving the pore-scale ALD governing equations fed by the reactor-scale boundary conditions. The gradual pore constriction with SIS cycles was predicted and validated by the experimental charaterizations. The results demonstrated that PMMA-Al2O3 was prepared using 20 SIS cycles, which corresponds to the numerically predicted occurrence of the pore blockage at the upper region of the PMMA layer, exhibiting optimal electron beam (e-beam) resolution while enabling line exposure with a width of 50 nm. While the corresponding sensitivity was lower than those of the samples prepared using 5 and 10 SIS cycles, the degradation of the PMMA structure was affected under exposure. The pattern transfer results showed that the line width was well retained for 20 cycles of deposition because of the high etching resistance of Al2O3. This research is expected to provide an effective approach to developing next-generation high-performance photoresists.

Room-Temperature Flexible CNT/Fe2O3 Film Sensor for ppb-Level H2S Detection.

Carbon nanotubes (CNTs) had room temperature response, large surface area, and excellent mechanical properties, making them favorable for the design of flexible, wearable, and portable gas sensors. However, CNTs were lacking in response and selective response to different gases, such as H2S. Here, we demonstrated a flexible H2S ppb-level gas sensor based on a carbon nanotube/amorphous Fe2O3 (CNT/Fe2O3) film at room temperature, which was fabricated via a simple one-step solvent-thermal method. The CNT/Fe2O3 film gas sensor exhibited a high selective response to H2S (with a response of 55.1% to 100 ppb H2S), rapid reversible response at room temperature (with a response time of ∼127 s to 100 ppb H2S), and low limit of detection to about 2 ppb. Additionally, the CNT/Fe2O3 film maintained good sensing performance under various bending conditions and could be further fabricated into the fiber gas sensor device via wet stretching, retaining response at the ppb level (with a response of 18.6% to 100 ppb H2S). This research on a flexible gas sensor device based on the CNT film/fiber opened up new possibilities for wearable portable electronic device applications.

Engaging Indigenous communities in research to inform practice: The multisite implementation evaluation of Tribal home visiting.

Community engagement (CE) is widely acknowledged as a way to enhance the ethics, rigor, and impact of research. Additionally, CE is a demonstrated way to integrate Indigenous and colonial (western) research systems. For these reasons and others, designers of the Multi-site Implementation Evaluation of Tribal Home Visiting (MUSE) used a community-engaged approach to study the implementation of federally funded home-visiting programs across 17 Indigenous communities throughout the United States. This paper describes MUSE's community-engaged approach and its practical applications from the perspective of the MUSE study team. The paper highlights key outcomes attributable to CE, addresses barriers to CE, and details responses to these barriers and their impacts. Adding to the rich evidence base demonstrating the value of community-engaged approaches, MUSE demonstrates that in-depth CE is feasible and valuable in multisite studies done in partnership with Indigenous communities.

La incorporación de la comunidad es reconocida ampliamente como una manera de mejorar la ética, el rigor y el impacto de la investigación. Adicionalmente, la incorporación de la comunidad es una manera que ha demostrado la integración de los sistemas de investigación indígenas y coloniales (occidentales). Por estas y otras razones, quienes diseñaron el programa de Implementación de la Evaluación de Visitas a Casa en Múltiples Lugares Tribales (MUSE) hicieron uso de un acercamiento de participación de la comunidad para estudiar la implementación de programas de visitas a casa subvencionados federalmente a lo largo de 17 comunidades indígenas esparcidas dentro de los Estados Unidos. Este ensayo describe el acercamiento de participación comunitaria de MUSE y sus aplicaciones prácticas desde la perspectiva del equipo de estudio de MUSE. El estudio enfatiza los resultados claves atribuibles a la participación de la comunidad, aborda barreras relacionadas con la participación de la comunidad y detalla las respuestas a esas barreras y al impacto que ellas ejercen. Como un aporte más a la rica base de evidencias que demuestra el valor de los acercamientos de participación comunitaria, MUSE demuestra que una profunda participación de la comunidad es posible y de mucho valor en múltiples estudios realizados en conjunto con las comunidades indígenas.

Ultra-high PDCR(>109) of vacuum-UV photodetector based on Al-doped Ga2O3microbelts.

Al-doped Ga2O3 microbelts with widths ranging from 20 to 154 µm and lengths up to 2 mm were grown using carbothermal reduction. Based on these ultra-wide microbelts, single-microbelt (37µm wide) and double-microbelts(38 µm/42 µm wide) metal-semiconductor-metal (MSM) photoconductive ultraviolet (UV) detectors PDs were fabricated and their optoelectronic performances were investigated at Vacuum-UV (VUV) wavelengths of 185 nm. Under irradiation of 185 nm, the Al-doped Ga2O3 PD has a very-high photocurrent (Iph) of 192.07 µA and extremely low dark current (Id) of 156 fA at 10 V, and presents a ultra-high light-to-dark current ratio(PDCR) of 1.23× 10^9. The responsivity(R), external quantum efficiency (EQE), and detectivity (D*) of the double-microbelts detector device were 1920 A/W, 9.36× 10^5 %, and 8.6× 10^16 Jones, respectively. Since the bandgap of the Al-doped microbelts becomes wider, and the fabricated detector has weaker sensitivity to radiation in the 254/365 nm wavelengths. Compared with the 254nm and 365nm UV cases, the devices under 185 nm VUV show the excellent high selectivity ratios of 1.47× 10^6 and 1.7× 10^7, respectively. This paper should provide a new insight on the VUV photodetectors utilizing Ga2O3 microbelts. .

Construction of a In2O3/ultrathin g-C3N4 S-scheme heterojunction for sensitive photoelectrochemical aptasensing of diazinon.

A single semiconductor-based photoelectrochemical (PEC) aptasensor usually faces a challenge of low sensitivity due to poor solar energy utilization and a high photogenerated carrier recombination rate. Herein, an ultra-thin carbon nitride nanosheet-coated In2O3 (In2O3/CNS) S-type heterojunction-based PEC aptasensor has been established to achieve highly sensitive detection of diazinon (DZN) pesticide in water environment. Construction of S-type heterojunction induces a band shift and an electric field effect, enhancing light utilization and accelerating directional transmission of carriers, leading to outstanding PEC performance. The creation of internal electric field at interface ensures stable carrier transport. Additionally, ultrathin CNS structure can effectively shorten the transport path of carriers. The close coating of In2O3 and CNS promotes the transfer of charge. The synergistic effects amplify the sensor's response, ultimately enabling the effective detection of DZN residue over a wide detection range (0.98 âˆ¼ 980.0 pg mL-1), a low detection limit (0.33 pg mL-1, S/N = 3) and excellent accuracy in practical application (RSD < 5 %). This work provides a reference for the construction of a new S-type heterojunction-based PEC sensor.

Revealing Fast Negative Capacitance in PbZr0.2Ti0.8O3 Thin Film with Acicular Ferroelastic Domains.

Negative capacitance effects with fast response times hold great potential for reducing the power consumption in high-frequency nanoelectronics. Nevertheless, the negative capacitance effect faces considerable complexity arising from the dynamic interplay among electrostatic, nucleation energies, and domain evolution. This intricate balance poses a formidable challenge to achieving fast negative capacitance. Herein, we have achieved a fast negative capacitance time of ∼16.23 ns in PbZr0.2Ti0.8O3 (PZT) thin film, and our investigation confirms the presence of acicular ferroelastic domains within the PZT thin film. Under reversal electric fields, these acicular ferroelastic domains undergo a unique flipping process, transitioning through domain expansion and contraction. This distinct domain flipping manner accelerates the nucleation and growth of ferroelectric domains, thereby facilitating the observed fast negative capacitance. The realization of fast negative capacitance holds substantial promise for reducing operational time and power consumption, offering prospects for the design of nanoelectronics with significantly lower power requirements.

High Efficiency Alkaline Iodine Batteries with Multi-Electron Transfer Enabled by Bi/Bi2O3 Redox Mediator.

The multi-electron transfer I-/IO3- redox couple is attractive for high energy aqueous batteries. Shifting from an acidic to an alkaline electrolyte significantly enhances the IO3- formation kinetics due to the spontaneous disproportionation reaction, while the alkaline environment also offers more favorable Zn anode compatibility. However, sluggish kinetics during the reduction of IO3- persists in both acidic and alkaline electrolytes, compromising the energy efficiency of this glorious redox couple. Here, we establish the fundamental redox mechanism of the I-/IO3- couple in alkaline electrolytes for the first time and propose that Bi/Bi2O3 acts as a redox mediator (RM) to "catalyze" the reduction of IO3-. This mediation significantly reduces the voltage gap between charge/discharge from 1.6 V to 1 V with improved conversion efficiency and rate capability. By pairing the Zn anode and the Bi/Bi2O3 RM cathode, the full battery with I-/IO3- redox mechanism achieves high areal capacity of 12 mAh cm-2 and stable operation at 5 mAh cm-2 for over 400 cycles.

ZnO@In2O3 Core-Shell Heterojunctions Constructed With ZIF-8 and MIL-68 (In) for Improving Photogenerated Carrier Transfer Process.

The realization of fast carrier transport can effectively enhance photocatalytic performance. A core-shell structure of ZnO and In2O3 is successfully constructed by using MIL-68 (In) and ZIF-8 as a substrate, forming a heterojunction. This MOF-derived core-shell heterojunction inherits the advantages of ZIF-8, with pores facilitating carriers transfer to the surface for reactions and a large specific surface area providing more active sites. This Z-scheme heterojunction of ZnO and In2O3 can effectively separate and improve the utilization of photogenerated carriers. The well-designed interface of the core-shell structure achieves the rapid transfer of photogenerated carriers. The photocatalytic degradation capability of ZnO@ In2O3 is enhanced by the synergistic effect of Z-scheme heterojunction and core-shell structure. This work provides insight into the investigation of constructing core-shell heterojunctions.

Possibilities and power during early Head Start Home visits: Comparing family- and home visitor-opened decision-making.

Decision-making by families and professionals about how to support children's development is an integral aspect of home visits. This study investigated home visit decision-making in a US program for families experiencing poverty, Early Head Start (EHS), through the following questions: What types of decisions do home visitors and families make about children's development during EHS home visits? How and to what extent do home visitors and families participate during these decisions? A convergent mixed methods research design was implemented to investigate participation through frequency counts and discourse analysis of home visit transcripts. Home visitor participants were four women, three white and one Black. Twelve families participated (12 mothers, 2 fathers). Parents identified as white (n = 8), Black (n = 3), and multiracial (n = 3; Black and white). One parent was a bilingual Arabic and English speaker. A total of 66 decisions about children's development were identified, with 49 decisions initiated by home visitors and 17 initiated by families. Although families talked more and took on active roles when they initiated (i.e., opened) decisions, home visitors predominantly controlled decision-making. Quantitative and qualitative participation differed only in the beginning of family-opened decisions, and home visitors gradually took more control.

La toma de decisiones por parte de familias y profesionales acerca de cómo apoyar el desarrollo de los niños es un aspecto integral de las visitas a casa. Este estudio investigó la decisión de hacer visitas a casa en el programa de Estados Unidos para familias que viven en pobreza, "De un comienzo temprano" (Early Head Start), a través de las siguientes preguntas: ¿Qué tipo de decisiones toman las visitadoras a casa y las familias acerca del desarrollo de los niños durante las visitas a casa del programa "De un comienzo temprano?" ¿Cómo y hasta qué punto las visitadoras a casa y las familias participan durante la toma de estas decisiones? Se implementó un diseño convergente mixto de métodos de investigación para investigar la participación por medio de conteos frecuentes y análisis de las transcritas conversaciones de la visita a casa. Las visitadoras a casa que participaron fueron cuatro mujeres, tres blancas y una de raza negra. Doce familias participaron (12 mamás, 2 papás). Los progenitores se identificaron como blancos (n = 8), negros (n = 3) y multirraciales (n = 3, negros y blancos). Uno de los progenitores era hablante bilingüe de árabe e inglés. Se identificó un total de 66 decisiones acerca del desarrollo de los niños, de las cuales 49 fueron iniciadas por las visitadoras a casa y 17 por las familias. Aunque las familias hablaron más y asumieron un papel activo cuando hablaban primero sobre las decisiones (v.g., cuando abrían la conversación), las visitadoras a casa predominantemente controlaron la toma de decisiones. La participación cuantitativa y cualitativa difirió sólo al principio de las decisiones iniciadas por las familias y las visitadoras a casa gradualmente asumieron mayor control.

n-n type In2O3@-WO3 heterojunction nanowires: enhanced NO2 gas sensing characteristics for environmental monitoring.

Solvothermal synthesis of 1D n-In2O3@n-WO3 heterojunction nanowires (HNWs) and their NO2 gas sensing characteristics are reported. The n-In2O3@n-WO3 HNWs have been well-characterised using XRD, Raman spectroscopy, XPS, SEM and HRTEM analyses. The NO2 sensing performance of n-In2O3@n-WO3 HNWs showed superior performance compared with pristine WO3 NWs. Due to the distinctive configuration of WO3-In2O3 heterojunctions, the n-In2O3@n-WO3 HNWs demonstrated remarkable sensitivity reaching 182% in response towards 500 ppb of NO2 gas at operating temperature of 200°C which is nearly 3.5 times greater than the response observed with pristine WO3 (50%). Moreover, the n-In2O3@n-WO3 HNWs also exhibited fast response (8-13 s)/recovery (54-62 s) time characteristics. A plausible sensing mechanism has been discussed. The enhancement in sensor characteristics shows that n-In2O3@n-WO3 HNWs could serve as a promising material for high-performance NO2 gas sensors for real-time environmental monitoring applications. This work could provide new understandings of the sensing mechanism of n-In2O3@n-WO3-based heterojunction nanowires, which can be applied to the design of novel n-n type MOS heterojunction materials for the application of low-temperature real-time high-performance NO2 sensors.

Enlisting toddler cooperation through structure and autonomy support: The amplifying role of suboptimal relationship mutuality.

Regular repair of normative mother-toddler conflict is required for relational health; yet, we still need improved delineation of regulation strategies that can promote child cooperation. Contemporary conceptualizations of positive parenting propose that structure and autonomy support each facilitate children's optimal engagement; however, toddler studies rarely address their joint impact and conditional moderation. This observational study examined both dimensions in predicting cooperation among 106 U.S. 30-month-olds and their primarily European-American mothers during a demanding request situation. We also assessed mutuality, an indicator of mother-child relationship quality, from two situations with minimized power differentials to explore whether it moderated associations. Regression analyses confirmed the unique and additive impact of both maternal behavioral dimensions in predicting toddler cooperation and also an interaction effect such that the positive association between maternal autonomy support and toddlers' level of cooperation was accentuated depending on the dyads' mutuality. Results suggest that maternal structure and autonomy support may serve as effective approaches for enlisting or maintaining child cooperation during hierarchical negotiations, and that suboptimal relationship mutuality magnifies toddlers' responses to maternal levels of autonomy support. Findings are likely relevant to parenting programs that advance mother-child relational health during the transition from infancy to early childhood.

Para el bienestar de la relación se requiere una regular reparación del conflicto normativo entre madre­niño pequeñito; aun así, necesitamos mejorados delineamientos de las estrategias de regulación que puedan promover la cooperación del niño. Las conceptualizaciones contemporáneas de una crianza positiva proponen que tanto el apoyo de la estructura como de la autonomía facilitan por su parte la participación óptima de los niños; sin embargo, los estudios sobre niños pequeñitos raramente abordan su impacto conjunto y la moderación condicional. Este estudio observacional examinó ambas dimensiones en cuanto a predecir la cooperación entre 106 niños de 30 meses de edad, de Estados Unidos, y sus primariamente euroamericanas mamás durante una pedida situación exigente. También evaluamos la mutualidad, un indicador de la calidad de la relación madre­niño, a partir de dos situaciones con diferenciales de poder minimizados para explorar si la ésta moderaba las asociaciones. Los análisis de regresión confirmaron el singular y agregado impacto de ambas dimensiones del comportamiento materno para predecir la cooperación del niño pequeñito y también un efecto de interacción de manera que la asociación positiva entre el apoyo de autonomía materna y el nivel de cooperación de los niños pequeñitos se acentuó dependiendo de la mutualidad de las díadas. Los resultados sugieren que el apoyo de estructura y autonomía materno pudiera servir como acercamiento efectivo para conseguir y mantener la cooperación del niño durante negociaciones jerárquicas y que la mutualidad subóptima de la relación ensancha las respuestas de los niños pequeñitos a los niveles maternos de apoyo de autonomía. Las recomendaciones son probablemente relevantes para programas de crianza que llevan adelante el bienestar de la relación madre­niño durante la transición de la infancia a la niñez. Consistent with self­determination theory, maternal structuring and autonomy­supportive strategies made unique contributions to positively predicting toddler cooperation suggesting they may serve as effective and joint approaches for enlisting or maintaining cooperation during difficult request situations. As caregiver structuring is likely needed for many toddlers to accomplish multifaceted tasks, its positive association with cooperation was not altered by dyadic mutuality, an indicator of mother­child relationship history. Suboptimal relationship mutuality magnified the positive association between autonomy support and cooperation suggesting that mothers from dyads with low mutuality should be aware that their toddlers' cooperation may be especially sensitive to varying levels of autonomy support.

Antiferromagnetic Nanoscale Bit Arrays of Magnetoelectric Cr2O3 Thin Films.

Magnetism of oxide antiferromagnets (AFMs) has been studied in single crystals and extended thin films. The properties of AFM nanostructures still remain underexplored. Here, we report on the fabrication and magnetic imaging of granular 100 nm-thick magnetoelectric Cr2O3 films patterned in circular bits with diameters ranging from 500 down to 100 nm. With the change of the lateral size, the domain structure evolves from a multidomain state for larger bits to a single domain state for the smallest bits. Based on spin-lattice simulations, we show that the physics of the domain pattern formation in granular AFM bits is primarily determined by the energy dissipation upon cooling, which results in motion and expelling of AFM domain walls of the bit. Our results provide a way toward the fabrication of single domain AFM-bit-patterned memory devices and the exploration of the interplay between AFM nanostructures and their geometric shape.

Proteomics Reveals Divergent Cardiac Inflammatory and Metabolic Responses After Inhalation of Ambient Particulate Matter With or Without Ozone.

Inhalation of ambient particulate matter (PM) and ozone (O3) has been associated with increased cardiovascular morbidity and mortality. However, the interactive effects of PM and O3 on cardiac dysfunction and disease have not been thoroughly examined, especially at a proteomic level. The purpose of this study was to identify and compare proteome changes in spontaneously hypertensive (SH) rats co-exposed to concentrated ambient particulates (CAPs) and O3, with a focus on investigating inflammatory and metabolic pathways, which are the two major ones implicated in the pathophysiology of cardiac dysfunction. For this, we measured and compared changes in expression status of 9 critical pro- and anti-inflammatory cytokines using multiplexed ELISA and 450 metabolic proteins involved in ATP production, oxidative phosphorylation, cytoskeletal organization, and stress response using two-dimensional electrophoresis (2-DE) and mass spectrometry (MS) in cardiac tissue of SH rats exposed to CAPs alone, O3 alone, and CAPs + O3. Proteomic expression profiling revealed that CAPs alone, O3 alone, and CAPs + O3 differentially altered protein expression patterns, and utilized divergent mechanisms to affect inflammatory and metabolic pathways and responses. Ingenuity Pathway Analysis (IPA) of the proteomic data demonstrated that the metabolic protein network centered by gap junction alpha-1 protein (GJA 1) was interconnected with the inflammatory cytokine network centered by nuclear factor kappa beta (NF-kB) potentially suggesting inflammation-induced alterations in metabolic pathways, or vice versa, collectively contributing to the development of cardiac dysfunction in response to CAPs and O3 exposure. These findings may enhance understanding of the pathophysiology of cardiac dysfunction induced by air pollution and provide testable hypotheses regarding mechanisms of action.

In Situ Generatable and Recyclable Oxygen Vacancy-Modified Fe2O3-Decorated WO3 Nanowires with Super Stability for ppb-Level H2S Sensing.

Detecting hydrogen sulfide (H2S) odor gas in the environment at parts-per-billion-level concentrations is crucial. However, a significant challenge is the rapid deactivation caused by SO42- deposition. To address this issue, we developed a sensing material comprising Fe2O3-decorated WO3 nanowires (FWO) with strong interfacial interaction. During the H2S sensing process, important oxygen vacancies (OVs) are generated in situ and are recyclable on the surface of the Fe2O3 cluster. This sensor achieves a response of 140 (Ra/Rg) toward 50 ppm of H2S at 250 °C, with an experimentally measured detection limit of 1 ppb. It also exhibits remarkable stability, with no significant change observed over a long period of 150 days. Based on a combination of in situ DRIFT and DFT calculations, we have identified that the overactivation of O2 is the key step in the formation of SO42-. This overactivation can be partially modulated by the synergistic effect of Fe2O3 decoration and the in situ generated OVs, regulating the oxidation product to SO2 rather than the toxic SO42-. Furthermore, the continuous generation of OVs compensates for the loss of active sites pertaining to SO42- deposition, thereby contributing to the excellent stability of the sensor. This study underscores the beneficial impact of in situ OV generation in FWO for H2S sensing, offering a dynamic strategy to enhance sensor performance, particularly in terms of stability.