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Enamine and imine represent two of the most common reaction intermediates in syntheses, and the imine intermediates containing α -hydrogen often exhibit the similar reactivity to enamines due to their rapid tautomerization to enamine tautomers. Herein, we report that the minor structural difference between the enamine and the enamine tautomer derived from imine tautomerization results in the different chemo- and regioselectivity in the reaction of cyclohexanones, amines and TEMPO: the reaction of primary amines furnishes the formal oxygen 1,2-migration product, α -amino-enones, while the reaction of secondary amines under similar conditions generates exclusively arylamines via consecutive dehydrogenation on the cyclohexyl rings. The 18 O-labeling experiment for α -amino-enone formation revealed that TEMPO served as oxygen transfer reagent. Experimental and computational studies of reaction mechanisms revealed that the difference in chemo- and regioselectivity could be ascribed to the flexible imine-enamine tautomerization of the imine intermediate containing an α -hydrogen. Tautomerization of imines into enamines is the basis of their similar reactivity; however, minor structural changes may lead to different outcomes. Here, the authors show that the reaction of cyclohexanone and amines in presence of TEMPO affords either α-amino-enones or arylamines depending on the intermediate imine structure.

Electrochemical conversion of carbon dioxide (CO 2 ) to higher-value products provides a forward-looking way to solve the problems of environmental pollution and energy shortage. However, the low solubility of CO 2 in aqueous electrolytes, sluggish kinetics, and low selectivity hamper the efficient conversion of CO 2 . Here, we report a Au-based hybrid nanomaterial by modifying Au nanoparticles (NPs) with the macrocyclic molecule cucurbit[6]uril (Au@CB[6]). Au@CB[6] displays the optimal selectivity of CO, with the highest CO Faraday efficiency (FE CO ) reaching 99.50% at −0.6 V vs. reversible hydrogen electrode (RHE). The partial current density of CO formed by Au@CB[6] increases dramatically, as 3.18 mA/cm 2 at −0.6 V, which is more than ten times as that of oleylamine-coated Au NPs (Au@OAm, 0.31 mA/cm 2 ). Operando electrochemical measurement combined with density functional theory (DFT) calculations reveals that CB[6] can gather CO 2 and lead the increased local CO 2 concentration near metal interface, which realizes significantly enhanced electrochemical CO 2 reduction reaction (CO 2 RR) performance.

Aberrant topological organization of whole-brain networks has been inconsistently reported in studies of patients with major depressive disorder (MDD), reflecting limited sample sizes. To address this issue, we utilized a big data sample of MDD patients from the REST-meta-MDD Project, including 821 MDD patients and 765 normal controls (NCs) from 16 sites. Using the Dosenbach 160 node atlas, we examined whole-brain functional networks and extracted topological features (e.g., global and local efficiency, nodal efficiency, and degree) using graph theory-based methods. Linear mixed-effect models were used for group comparisons to control for site variability; robustness of results was confirmed (e.g., multiple topological parameters, different node definitions, and several head motion control strategies were applied). We found decreased global and local efficiency in patients with MDD compared to NCs. At the nodal level, patients with MDD were characterized by decreased nodal degrees in the somatomotor network (SMN), dorsal attention network (DAN) and visual network (VN) and decreased nodal efficiency in the default mode network (DMN), SMN, DAN, and VN. These topological differences were mostly driven by recurrent MDD patients, rather than first-episode drug naive (FEDN) patients with MDD. In this highly powered multisite study, we observed disrupted topological architecture of functional brain networks in MDD, suggesting both locally and globally decreased efficiency in brain networks.

Rational design of efficient pH‐universal hydrogen evolution reaction catalysts to enable large‐scale hydrogen production via electrochemical water splitting is of great significance, yet a challenging task. Herein, Ru atoms in the Ru2P structure were replaced with M = Co, Ni, or Mo to produce M2−xRuxP nanocrystals. The metals show strong site preference, with Co and Ni occupying the tetrahedral sites and Ru the square pyramidal sites of the CoRuP and NiRuP Ru2P‐type structures. The presence of Co or Ni in the tetrahedral sites leads to charge redistribution for Ru and, according to density functional theory calculations, a significant increase in the Ru d‐band centers. As a result, the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru2P in both acidic and alkaline media. The effect is not observed for MoRuP, in which Mo prefers to occupy the pyramidal sites. In particular, CoRuP shows state‐of‐the‐art activity, outperforming Ru2P with Pt‐like activity in 0.5 M H2SO4 (η10 = 12.3 mV; η100 = 52 mV; turnover frequency (TOF) = 4.7 s−1). It remains extraordinarily active in alkaline conditions (η10 = 12.9 mV; η100 = 43.5 mV) with a TOF of 4.5 s−1, which is 4x higher than that of Ru2P and 10x that of Pt/C. Further increase in the Co content does not lead to drastic loss of activity, especially in alkaline medium, where, for example, the TOF of Co1.9Ru0.1P remains comparable to that of Ru2P and higher than that of Pt/C, highlighting the viability of the adopted approach to prepare cost‐efficient catalysts. A facile synthesis approach to drive Ru‐based bimetallic phosphides MRuP (M = Co, Ni, and Mo) that adapt the same crystal structure has been developed, allowing to understand the possible synergism between metals toward hydrogen evolution reaction. Among them, CoRuP exhibits outstanding performance, outperforming Pt/C in alkaline medium and comparable to it in acidic medium, thanks to the induced charge redistribution according to X‐ray photoelectron spectroscopy and density functional theory analysis.

This paper examines the relationship between the voluntary disclosure of intangible assets and financing constraints using a sample of 2850 listed companies from 2017 to 2021. Additionally, we examine the moderating effects of prudence in accounting and the attention given to the disclosures by analysts from both an internal and an external perspective. The results show that voluntarily disclosing intangible assets helps to alleviate a firm’s financing constraints, with more significant effects observed in state-owned enterprises and companies listed on the Growth Enterprise Market index than for private enterprises and those listed on the main board of the Chinese capital market. Further, conservatism in accounting and attention given by financial analysts both positively moderate this relationship. The theoretical and empirical insights provided by this study should help listed companies in China to enhance the quality of their voluntary intangible asset disclosures, while also helping to mitigate financing constraints.

Immune checkpoint inhibitors (ICIs) have revolutionized cancer management and have been widely applied; however, they still have some limitations in terms of efficacy and toxicity. There are multiple treatment regimens in Traditional Chinese Medicine (TCM) that play active roles in combination with Western medicine in the field of oncology treatment. TCM with ICIs works by regulating the tumor microenvironment and modulating gut microbiota. Through multiple targets and multiple means, TCM enhances the efficacy of ICIs, reverses resistance, and effectively prevents and treats ICI-related adverse events based on basic and clinical studies. However, there have been few conclusions on this topic. This review summarizes the development of TCM in cancer treatment, the mechanisms underlying the combination of TCM and ICIs, existing studies, ongoing trials, and prospects for future development.

Nonalcoholic fatty liver disease (NAFLD) represents one of the most prevalent chronic liver conditions worldwide. Previous studies have highlighted an association between circulating growth differentiation factor 15 (GDF-15) levels and NAFLD, as well as the involvement of immune cells in its pathogenesis and progression. However, the causal relationships remain unclear. We obtained summary-level data for circulating GDF-15 levels, NAFLD, and 731 immune cell phenotypes from large-scale genome-wide association studies (GWAS) and the FinnGen database. Mendelian randomization (MR) analysis was employed to explore the causal relationship between circulating GDF-15 levels and NAFLD. Additionally, a two-step MR approach was utilized to identify and assess the mediatory role of immune cells in this association. Finally, single-cell RNA sequencing analysis (scRNA-seq) was performed to validate the proportions of CD123 dendritic cell (DC) subsets in NAFLD progression. Two-sample MR analysis revealed that elevated levels of GDF-15 are associated with an increased risk of NAFLD (OR = 1.16; 95% confidence interval [CI] = 1.03-1.30; =0.017), and replication analysis further confirmed the stability of these findings (OR = 1.10; 95% CI = 1.01-1.20; =0.037). Mediation analysis identified that CD123 on plasmacytoid DCs (DCs), CD123 on CD62L+ plasmacytoid DCs, CD80 on plasmacytoid DCs, and CD80 on CD62L+ plasmacytoid DCs mediate the causal effect of GDF-15 on NAFLD. Sensitivity analyses and bidirectional MR further ensured the robustness of these findings. Single-cell analysis further validated these results. Our findings propose a causal relationship between GDF-15 and NAFLD mediated by DCs, offering novel insights for potential therapeutic and preventive strategies for NAFLD.

BackgroundWhile trait emotional intelligence (EI) has been found to be related to young adolescents’ affect, the underlying mechanisms need to be further explored. Previous findings are also limited by common method problems arising from the use of cross-sectional design involving single-wave data capture.ObjectiveThe study aims to clarify the relation between trait EI and young adolescents’ positive and negative affect by further exploring the mediating roles of personal resilience, social support, and prosocial behavior.MethodWe conducted a three-wave survey among 714 Chinese junior high school students (mean age of 11.11 years) with temporal separations of the research measures to reduce common method variance. Trait EI was measured at the beginning of Grade 6; personal resilience, social support, and prosocial behavior were measured at the end of Grade 6; positive and negative affect were measured at the end of Grade 7.ResultsTrait EI at the beginning of Grade 6 was positively related to positive affect and negatively related to negative affect by the end of Grade 7. The influence of trait EI on positive affect was fully mediated by personal resilience, social support, and prosocial behavior at the end of Grade 6. Its influence on negative affect was also fully mediated by social support.ConclusionsThe findings clarify the mechanisms underlying the trait EI effect and highlight the importance of future youth programs targeting mediation mechanisms. In particular, we suggest the worth of utilizing trait EI to better facilitate personal and social resources when facing difficulties, and to help others in appropriate and effective ways.

We prepared a double-crystal LiTaO 3 (LT) electro-optic (EO) Q-switch and investigated its overall Q-switching performances. The LT EO Q-switch is fabricated from two x -cut LT crystals to utilize the maximum effective EO coefficient. The static and dynamic quarter-wave voltage were measured to be 1200 V and 950 V respectively, which are both considerably lower than those of other commercial EO Q-switches. Besides, the LT Q-switch can operate at a wide temperature range with high temperature stability. The dynamic-to-static ratios at sub-freezing temperatures were up to 80 percent of that at room temperature. Furthermore, the piezoelectric ringing in the LT Q-switch was found to be comparable to that of RTP Q-switches, and it had been successfully operated at a repetition rate of 1 kHz with stable Q-switched laser output. The only disadvantage is the low extinction ratio which is mainly caused by the optical inhomogeneity and can be improved by improving the optical quality of LT crystals. The double-crystal LT EO Q-switches are particularly attractive for Q-switched lasers because of their excellent comprehensive performances.

Landslide is one of the most damaging natural hazards, causing extensive damage to the infrastructure and threatening human life. Although advances have been made in landslide susceptibility assessment by objective explainable machine learning, the interpretability robustness of traditional single landslide susceptibility model is still low. The proposed interpretable hybrid model in this study overcomes these challenges and aims to enhance the stability of landslide susceptibility interpretability. The model integrates three base machine learning models—LightGBM, XGBoost, and Random Forest—using a heterogeneous category strategy, thereby enhancing the robustness of model interpretability. The hybrid model is interpreted using SHAP (Shapley Additive Explanations) values, which quantify feature contributions. A 10-fold cross-validation with the coefficient of variation (CV) metric reveals that the hybrid model outperforms individual base models in terms of interpretive robustness, yielding a lower CV value of 0.175 compared to 0.208 for LightGBM, 0.240 for XGBoost, and 0.207 for the Random Forest model. Although predictive accuracy remains comparable to the baseline models, the hybrid model provides more stable and reliable interpretability results for landslide susceptibility. It identifies the slope, elevation, and LS factor as the three most important factors for landslide susceptibility in Xi’an city. Furthermore, the quantitative nonlinear relationships between these predisposing factors and susceptibility were identified, providing empowering knowledge for the landslides risk prevention and urban planning in the regions vulnerable to landslides.