Operando Mössbauer Spectroscopic Tracking the Metastable State of Atomically Dispersed Tin in Copper Oxide for Selective CO2 Electroreduction.

Metastable state is the most active catalyst state that dictates the overall catalytic performance and rules of catalytic behaviors; however, identification and stabilization of the metastable state of catalyst are still highly challenging due to the continuous evolution of catalytic sites during the reaction process. In this work, operando 119Sn Mössbauer measurements and theoretical simulations were performed to track and identify the metastable state of single-atom Sn in copper oxide (Sn1-CuO) for highly selective CO2 electroreduction to CO. A maximum CO Faradaic efficiency of around 98% at -0.8 V (vs. RHE) over Sn1-CuO was achieved at an optimized Sn loading of 5.25 wt. %. Operando Mössbauer spectroscopy clearly identified the dynamic evolution of atomically dispersed Sn4+ sites in the CuO matrix that enabled the in situ transformation of Sn4+-O4-Cu2+ to a metastable state Sn4+-O3-Cu+ under CO2RR conditions. In combination with quasi in situ X-ray photoelectron spectroscopy, operando Raman and attenuated total reflectance surface enhanced infrared absorption spectroscopies, the promoted desorption of *CO over the Sn4+-O3 stabilized adjacent Cu+ site was evidenced. In addition, density functional theory calculations further verified that the in situ construction of Sn4+-O3-Cu+ as the true catalytic site altered the reaction path via modifying the adsorption configuration of the *COOH intermediate, which effectively reduced the reaction free energy required for the hydrogenation of CO2 and the desorption of the *CO, thereby greatly facilitating the CO2-to-CO conversion. This work provides a fundamental insight into the role of single Sn atoms on in situ tuning the electronic structure of Cu-based catalysts, which may pave the way for the development of efficient catalysts for high-selectivity CO2 electroreduction.

Circumventing CO2 Reduction Scaling Relations Over the Heteronuclear Diatomic Catalytic Pair.

In the electrochemical CO2 reduction reaction (CO2RR), CO2 activation is always the first step, followed by the subsequent hydrogenation. The catalytic performance of CO2RR is intrinsically restricted by the competition between molecular CO2 activation and CO2 reduction product release. Here, we design a heteronuclear Fe1-Mo1 dual-metal catalytic pair on ordered porous carbon that features a high catalytic performance for driving electrochemical CO2 reduction to CO. Combining real-time near-ambient pressure X-ray photoelectron spectroscopy, operando 57Fe Mössbauer spectroscopy, and in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements with density functional theory calculations, chemical adsorption of CO2 is observed on the Fe1-Mo1 catalytic pair through a bridge configuration, which prompts the bending of the CO2 molecule for CO2 activation and then facilitates the subsequent hydrogeneration reaction. More importantly, the dynamic adsorption configuration transition from the bridge configuration of CO2 on Fe1-Mo1 to the linear configuration of CO on the Fe1 center results in breaking the scaling relationship in CO2RR, simultaneously promoting the CO2 activation and the CO release.

Associations between social capital and maternal depression: results from a follow-up study in China.

BACKGROUND: This study aims to investigate the association between social capital (SC) and depressive symptoms among Chinese primiparas at different time-points from their late pregnancy to postpartum. METHODS: A total of 450 primiparas were recruited for the current study. The assessments were conducted at three different time-points: T1 - while the participants were recruited at their 30-36 weeks of pregnancy in the antenatal clinic in the maternity hospital in Zhejiang, China; T2 - at their 2nd or 3rd days in the wards after delivery; T3 - at week 6 to 8 after the delivery in the postpartum examination clinic. SC was measured by the 29-item SC scale; while depressive symptoms were measured by the Edinburgh Postnatal Depression Scale. The relationships between SC and depressive symptoms were explored separately at each of the three time-points. RESULTS: The prevalence of depression among the primiparas was 25% at T1, 13.5% at T2 and 20.8% at T3, respectively. However, the score of SC and its components at three time-points followed an opposite 'V' direction, with the highest score at T2, following by T3 and T1. At T1, the analysis suggested that depressive symptoms among the primiparas were negatively correlated with their social trust and social network levels. At T2, only social trust was negatively associated with depression. While at T3, it is social trust and social participations that were significantly negatively associated with depression. CONCLUSIONS: SC was associated with depression at all three time-points during and after pregnancy. More attention should be given to SC in the maternal health promotion programs of community pregnancy health care management.

Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate.

Electrochemical carbon dioxide/carbon monoxide reduction reaction offers a promising route to synthesize fuels and value-added chemicals, unfortunately their activities and selectivities remain unsatisfactory. Here, we present a general surface molecular tuning strategy by modifying Cu2O with a molecular pyridine-derivative. The surface modified Cu2O nanocubes by 4-mercaptopyridine display a high Faradaic efficiency of greater than 60% in electrochemical carbon monoxide reduction reaction to acetate with a current density as large as 380 mA/cm2 in a liquid electrolyte flow cell. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveals stronger *CO signal with bridge configuration and stronger *OCCHO signal over modified Cu2O nanocubes by 4-mercaptopyridine than unmodified Cu2O nanocubes during electrochemical CO reduction. Density function theory calculations disclose that local molecular tuning can effectively regulate the electronic structure of copper catalyst, enhancing *CO and *CHO intermediates adsorption by the stabilization effect through hydrogen bonding, which can greatly promote asymmetric *CO-*CHO coupling in electrochemical carbon monoxide reduction reaction.

Atomic high-spin cobalt(II) center for highly selective electrochemical CO reduction to CH3OH.

In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co2+ can enhance the electron backdonation via the dxz/dyz-2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.

Relationship between PSD of Park Green Space and Attention Restoration in Dense Urban Areas.

Research shows that stress, a common problem in densely populated cities, can be relieved by exposure to the natural environment. As great significance has been attached to the relationship between the urban environment and public health, this paper aims to study the relationship and interaction between the perceived sensory dimensions of urban park green space, attention restoration, and state empathy. Therefore, we conducted an on-site questionnaire (PSD Scale) survey in four typical parks in Chengdu and recorded age, sex, daily stress, frequency of visits to parks, and other basic information from the respondents. In the survey and visit, we found that the group structure in the recreation area comprises chiefly of a few transient unfamiliar travelers and most long-haul neighborhood sightseers. Among long-haul vacationers, the greater part of them are moderately aged and older individuals in the encompassing local locations, whose lives are, for the most part, quick and proficient. Hence, to mirror the populace attributes of high-thickness metropolitan parks and to feature the agent bunches that have lived in the parks from here onward, indefinitely quite a while, the chosen bunches are somewhere in the range of 35 and 65 years old (half male and half female), so make sure there are no ailments, no drinking, and no late evenings in the earlier days, so a specific actual fundamental belief is kept up with. The main part of the exercise focused on the perceived dimension, state empathy, and attention restoration. The software SPSS24.0 was applied to the test of the validity and reliability of the perceived sensory dimension (PSD) Scale, and then the important correlation between the perceived sensory dimensions in the parks and visitors' attention restoration was analyzed through multiple linear regression. Finally, the moderating effect of state empathy was tested by PROCESS. The findings show that (1) only seven dimensions in the PSD Scale are effective; (2) Serene and Refuge in the perceived sensory dimensions have a significant effect on the restorative components of attention. (3) Except for the dimensions of Rich in Species and Refuge, empathy enhanced the moderation effect in the interaction between the other five dimensions of the Perceived Restorative Scale (PRS), especially in the interaction between the Social and PRS dimensions. However, this topic needs to be further explored to provide a scientific basis and design strategy for research on the restoration potential of urban park green space in high-density urban areas.

Accuracy of breath test for diabetes mellitus diagnosis: a systematic review and meta-analysis.

The review aimed to investigate the accuracy of breath tests in the diagnosis of diabetes mellitus, identify exhaled volatile organic compounds with the most evidence as potential biomarkers, and summarize prospects and challenges in diabetic breath tests. Databases including Medline, PubMed, EMBASE, Cochrane Library and Science Citation Index Expanded were searched. Human studies describing diabetic breath analysis with more than 10 subjects as controls and patients were included. Population demographics, breath test conditions, biomarkers, analytical techniques and diagnostic accuracy were extracted. Quality assessment was performed with the Standards for Reporting Diagnostic Accuracy and a modified QUADAS-2 (Quality Assessment of Diagnostic Accuracy Studies 2). Forty-four research with 2699 patients with diabetes were included for qualitative data analysis and 14 eligible studies were used for meta-analysis. Pooled analysis of type 2 diabetes breath test exhibited sensitivity of 91.8% (95% CI 83.6% to 96.1%), specificity of 92.1% (95% CI 88.4% to 94.7%) and area under the curve (AUC) of 0.96 (95% CI 0.94 to 0.97). Isotopic carbon dioxide (CO2) showed the best diagnostic accuracy with pooled sensitivity of 0.949 (95% CI 0.870 to 0.981), specificity of 0.946 (95% CI 0.891 to 0.975) and AUC of 0.98 (95% CI 0.97 to 0.99). As the most widely reported biomarker, acetone showed moderate diagnostic accuracy with pooled sensitivity of 0.638 (95% CI 0.511 to 0.748), specificity of 0.801 (95% CI 0.691 to 0.878) and AUC of 0.79 (95% CI 0.75 to 0.82). Our results indicate that breath test is a promising approach with acceptable diagnostic accuracy for diabetes mellitus and isotopic CO2 is the optimal breath biomarker. Even so, further validation and standardization in subject control, breath sampling and analysis are still required.

Self-Assembled Lecithin/Chitosan Nanoparticles Based on Phospholipid Complex: A Feasible Strategy to Improve Entrapment Efficiency and Transdermal Delivery of Poorly Lipophilic Drug.

PURPOSE: Lecithin/chitosan nanoparticles have shown great promise in the transdermal delivery of therapeutic agents. Baicalein, a natural bioactive flavonoid, possesses multiple biological activities against dermatosis. However, its topical application is limited due to its inherently poor hydrophilicity and lipophilicity. In this study, the baicalein-phospholipid complex was prepared to enhance the lipophilicity of baicalein and then lecithin/chitosan nanoparticles loaded with the baicalein-phospholipid complex were developed to improve the transdermal retention and permeability of baicalein. METHODS: Lecithin/chitosan nanoparticles were prepared by the solvent-injection method and characterized in terms of particle size distribution, zeta potential, and morphology. The in vitro release, the ex vivo and in vivo permeation studies, and safety evaluation of lecithin/chitosan nanoparticles were performed to evaluate the effectiveness in enhancing transdermal retention and permeability of baicalein. RESULTS: The lecithin/chitosan nanoparticles obtained by the self-assembled interaction of chitosan and lecithin not only efficiently encapsulated the drug with high entrapment efficiency (84.5%) but also provided sustained release of baicalein without initial burst release. Importantly, analysis of the permeation profile ex vivo and in vivo demonstrated that lecithin/chitosan nanoparticles prolonged the retention of baicalein in the skin and efficiently penetrated the barrier of stratum corneum without displaying skin irritation. CONCLUSION: These results indicate the potential of drug-phospholipid complexes in enhancing the entrapment efficiency and self-assembled lecithin/chitosan nanoparticles based on phospholipid complexes in the design of a rational transdermal delivery platform to improve the efficiency of transdermal therapy by enhancing its percutaneous retention and penetration in the skin.

Comparative study of mucoadhesive and mucus-penetrative nanoparticles based on phospholipid complex to overcome the mucus barrier for inhaled delivery of baicalein.

Efficient mucosal delivery remains a major challenge for the reason of the respiratory tract mucus act as a formidable barrier to nanocarriers by trapping and clearing foreign particulates. The surface property of nanoparticles determines their retention and penetration ability within the respiratory tract mucus. However, the interaction between nanoparticles and mucus, and how these interactions impact distribution has not been extensively investigated. In this study, polymeric nanoparticles loaded with a baicalein-phospholipid complex were modified with two kinds of polymers, mucoadhesive and mucus-penetrative polymer. Systematic investigations on the physicochemical property, mucus penetration, transepithelial transport, and tissue distribution were performed to evaluate the interaction of nanoparticles with the respiratory tract. Both nanoparticles had a similar particle size and good biocompatibility, exhibited a sustained-release profile, but showed a considerable difference in zeta potential. Interestingly, mucus-penetrative nanoparticles exhibited a higher diffusion rate in mucus, deeper penetration across the mucus layer, enhanced in vitro cellular uptake, increased drug distribution in airways, and superior local distribution and bioavailability as compared to mucoadhesive nanoparticles. These results indicate the potential of mucus-penetrative nanoparticles in design of a rational delivery system to improve the efficiency of inhaled therapy by promoting mucus penetration and increasing local distribution and bioavailability.

Social capital and antenatal depression among Chinese primiparas: A cross-sectional survey.

The aim of this study is to investigate the associations between social capital and antenatal depression among Chinese primiparas. A cross-sectional design was used and a questionnaire survey was conducted with 1471 participants using the intercept method at the provincial hospital in Zhejiang in 2016. Antenatal depression was evaluated using the Edinburgh Postnatal Depression Scale (EPDS) and social capital was assessed by the Chinese version of Social Capital Assessment Questionnaire (C-SCAQ). The prevalence of antenatal depression was assessed among Chinese primiparas in their third trimesters. The antenatal depression prevalence among sub-groups with lower social trust (ST), social reciprocity (SR), social network (SN), and social participation (SP) were significantly higher than those among higher score sub-groups. In the fully adjusted model, primiparas' antenatal depression was significantly associated with ST, SR, SN, and SP. Compared to the structural social capital, the cognitive social capital was a more crucial dimension to the prevalence of antenatal depression. For future community pregnancy health care management programs in China, it might be beneficial to add more social capital related intervention.