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Background: Apoptosis has been recognized as a critical pathophysiological process during cerebral ischemia. The neuroprotective effect of CART on ischemic brain injury is determined. However, there is little research on the protective effect of CART on neural stem cells (NSCs). Methods: Primary cultured rat NSCs were utilized as the research subject. In vitro oxygen glucose deprivation (OGD) treatment was employed, and NSCs were extracted from SD pregnant rats following previous experimental protocols and identified through cell immunofluorescence staining. The appropriate concentration of CART affecting OGD NSCs was initially screened using Cell Counting Kit-8 (CCK-8) and Lactate Dehydrogenase (LDH) assays. EdU staining and Western blotting (WB) techniques were employed to assess the impact of the suitable CART concentration on the proliferation and apoptosis of OGD NSCs. Finally, Western blot analysis was conducted to investigate the cAMP-response element binding protein (CREB) pathway and expression levels of related proteins after KG-501 treatment in order to elucidate the mechanism underlying apoptosis and proliferation regulation in OGD NSCs. Results: CCK-8 and LDH assays indicated that a concentration of 0.8 nM CART may be the optimal concentration for modulating the proliferation of OGD NSCs. Subsequently, cellular immunofluorescence and EdU detection experiments further confirmed the findings obtained from CCK-8 analysis. Western blot analysis of apoptosis-related protein expression also demonstrated that an appropriate concentration of CART could suppress the apoptosis of OGD NSCs. Finally, Western blotting was conducted to examine the CREB pathway and related protein expression after treatment with KG-501, revealing that an appropriate concentration of CART regulated both apoptosis and proliferation in OGD NSCs through CREB signaling. Conclusion: The concentration of CART at 0.8 nM may be deemed appropriate for inhibiting apoptosis and promoting proliferation in OGD NSCs in vitro. The mechanism maybe through activating the CREB pathway.

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The miniaturization and widespread deployment of electronic devices across diverse environments have heightened their vulnerability to corrosion, particularly affecting copper traces within printed circuit boards (PCBs). Conventional protective methods, such as conformal coatings, face challenges including the necessity for a critical thickness to ensure effective barrier properties and the requirement for multiple steps of drying and curing to eliminate solvent entrapment within polymer coatings. This study investigates cold atmospheric plasma (CAP) as an innovative technique for directly depositing ultrathin silicon oxide (SiOx) coatings onto copper surfaces to enhance corrosion protection in PCBs. A systematic investigation was undertaken to examine how the scanning speed of the CAP deposition head impacts the film quality and corrosion resistance. The research aims to determine the optimal scanning speed of the CAP deposition head that achieves complete surface coverage while promoting effective cross-linking and minimizing unreacted precursor entrapment, resulting in superior electrical barrier and mechanical properties. The CAP coating process demonstrated the capability of depositing SiOx onto copper surfaces at various thicknesses ranging from 70 to 1110 nm through a single deposition process by simply adjusting the scanning speed of the plasma head (5-75 mm/s). Evaluation of material corrosion barrier characteristics revealed that scanning speeds of 45 mm/s of the plasma deposition head provided an effective coating thickness of 140 nm, exhibiting superior corrosion resistance (30-fold) compared to that of uncoated copper. As a proof of concept, the efficacy of CAP-deposited SiOx coatings was demonstrated by protecting an LED circuit in saltwater and by coating printed circuits for potential agricultural sensor applications. These CAP-deposited coatings offer performance comparable to or superior to traditional conformal polymeric coatings. This research presents CAP-deposited SiOx coatings as a promising approach for effective and scalable corrosion protection in miniaturized electronics.

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Objective: This study aimed to investigate the use of radiomics features and clinical information by four machine learning algorithms for predicting the prognosis of patients with hepatocellular carcinoma (HCC) who have been treated with transarterial chemoembolization (TACE). Methods: A total of 105 patients with HCC treated with TACE from 2002 to 2012 were enrolled retrospectively and randomly divided into two cohorts for training (n = 74) and validation (n = 31) according to a ratio of 7:3. The Spearman rank, random forest, and univariate Cox regression were used to select the optimal radiomics features. Univariate Cox regression was used to select clinical features. Four machine learning algorithms were used to develop the models: random survival forest, eXtreme gradient boosting (XGBoost), gradient boosting, and the Cox proportional hazard regression model. The area under the curve (AUC) and C-index were devoted to assessing the performance of the models in predicting HCC prognosis. Results: A total of 1,834 radiomics features were extracted from the computed tomography images of each patient. The clinical risk factors for HCC prognosis were age at diagnosis, TNM stage, and metastasis, which were analyzed using univariate Cox regression. In various models, the efficacy of the combined models generally surpassed that of the radiomics and clinical models. Among four machine learning algorithms, XGBoost exhibited the best performance in combined models, achieving an AUC of 0.979 in the training set and 0.750 in the testing set, demonstrating its strong prognostic prediction capability. Conclusion: The superior performance of the XGBoost-based combined model underscores its potential as a powerful tool for enhancing the precision of prognostic assessments for patients with HCC.

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Background: Pollen allergies have a high prevalence in northern China, whereas, the types of pollen allergens and population characteristics among different regions remain unclear. Objective: To study the species and temporal distribution of the main allergenic pollen, as well as the characteristics of patients with pollen-related allergic rhinitis (AR) in different cities in northern China. Methods: Pollen data were obtained from pollen-monitoring stations in 13 cities of northern China between 2020 and 2021. Questionnaire surveys and allergen testing were conducted in 494 patients with pollen-related allergies from Beijing in Central, Shenyang in Northeast, and Xi'an in Northwest China. Results: In 13 cities of northern China, the main sources of pollen were cypress, poplar, elm, pine, birch and ash in spring, and mugwort, goosefoot, hop and ragweed in autumn. In Northwest China, the spring and autumn pollen periods started earlier and lasted longer than that in Central and Northeast China, and the pollen counts in autumn in was significantly higher than that in Central and Northeast China. Furthermore, the nasal, ocular and respiratory symptom and quality of life scores of AR patients in Northwest China were significantly higher than that in Central and Northeast China. 69.32-73.28% of patients had annual cost of anti-allergic medication between 500-5000 yuan. However, 40.93-48.86% of patients reported minor control of symptoms. Conclusion: Our results can be used as a basis for developing effective prevention and management measures for patients with pollen-related allergy in these regions, including timely pollen monitoring, patient guidance on protective measures, early intervention, and specific immunotherapy, to improve pollen-related allergy management.

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BACKGROUND: This longitudinal study assessed the prospective link between childhood maltreatment and sleep quality in adulthood, with a specific focus on examining whether different coping style tendencies influence these associations. METHODS: The baseline sample included 1600 adult participants, with 1140 participants successfully followed up 5 years later. The key variables were measured using the Childhood Trauma Questionnaire (CTQ), Simplified Coping Style Questionnaire (SCSQ), and Pittsburgh Sleep Quality Index (PSQI). Generalized linear mixed models were employed to estimate unstandardized ß estimates and 95 % confidence intervals (95%CIs). Structural equation modeling was used to test the mediation model. RESULTS: Individuals reported childhood maltreatment at baseline were at an increased risk for sleep disturbances at follow-up. Childhood maltreatment negatively predicted the baseline coping style tendency (ß = -0.29, P < 0.001), the baseline coping style tendencies negatively predicted the follow-up sleep quality (ß = -0.10, P < 0.001), and childhood maltreatment positively predicted the follow-up sleep quality (ß = 0.42, P < 0.01). The mediating effect of baseline coping style tendencies between childhood maltreatment and the follow-up sleep quality was significant, with an effect value of 0.03. LIMITATIONS: First, the sample was from a single province (Shandong), which limits the generalizability of the findings. Second, recall bias was unavoidable in this adult sample study. CONCLUSIONS: Developing positive coping strategies is an important way to reduce the risk of sleep problems in adults with a history of childhood maltreatment.

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In chemical research, it is a common practice to carry out quantum chemical calculations and analyze the canonical molecular orbitals (CMOs) obtained to study electronic structures of chemical systems. However, extensive orbital mixing of CMOs especially in molecular clusters significantly complicates our understanding of the electronic structures. In this paper, we have developed an innovative tool called fragment aligned molecular orbital (FAMO) analysis, which reconstructs our modular chemical picture by making use of the Procrustes analysis in statistical theory to align the occupied molecular orbitals of a molecular species against the occupied (molecular) orbitals of the constituting fragments of the cluster, and results in a set of chemically intuitive semilocalized orbitals. This alignment technique minimizes the extensive orbital mixing, thus allowing precise observation of bonding interactions in complex chemical systems. A few representative clusters have been selected as showcase examples to demonstrate the advantage of FAMO analysis in deciphering the distinct bonding interactions in cluster compounds.

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BACKGROUND: Airborne pollen is a crucial risk factor in allergic rhinitis (AR). The severity of AR symptoms can vary based on pollen type and concentration. This study aimed to estimate the association between exposure to different pollen types and AR risk. METHODS: We obtained data from patients admitted to the Beijing Tongren Hospital for AR, and data on pollen concentration, meteorological factors, and fine particulate matter (PM2.5) from 13 districts in Beijing from 2016 to 2019. We used a time-stratified case-crossover study design and calculated odds ratios (ORs) related to the risk of AR associated with a 10 grain/1000 mm2 increase in total pollen concentrations for specific pollen types. A stratified analysis was conducted to assess whether the associations were varied by age and sex. RESULTS: The OR of AR associated with a 10 grain/1000 mm2 increase in the 7-day average pollen concentration was 1.014 (95% CI: 1.014, 1.015), 1.076 (95% CI: 1.070, 1.082), 1.024 (95% CI: 1.023, 1.025), 1.042 (95% CI: 1.039, 1.045), 1.142 (95% CI: 1.137, 1.147), 1.092 (95% CI: 1.088, 1.097), 1.046 (95% CI: 1.035, 1.058), and 1.026 (95% CI: 1.024, 1.028) for total pollen, Ulmus, Cupressaceae, Populus, Fraxinus, Pinus, Betula, and Artemisia, respectively. Both tree pollen (Ulmus, Cupressaceae, Populus, Fraxinus, Betula, and Pinus) and weed pollen (Artemisia, Chenopodium, and Humulus) were correlated with an increased risk of AR. These associations remained consistent across distinct subgroups defined by both age and sex. CONCLUSION: Exposure to pollen from trees and weeds might be associated with an increased risk of AR. This research provides valuable scientific support for both clinical practitioners and patients with AR regarding the hazards of pollen exposure.

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Rapid expansion in urban areas has engendered a superfluity of municipal solid waste (MSW) stemming from contemporary civilization, encompassing commercial sectors and human undertakings. Kerbside waste, a type of MSW, has the potential for recycling and reuse at the end of its first life cycle, but is often limited to a linear cycle. This study aimed to assess the life cycle costs of different separation and recycling methods for handling kerbside waste. A new life cycle cost model, drawing from the circular economy's value retention process (VRP) model, has been created and applied to assess the continuous recycling of kerbside glass. The study investigates two key separation techniques, kerbside recycling mixed bin recycling (KRMB) kerbside glass recycling separate bin (KGRSB) and analyses their impact on the life cycle cost of the recycling process. Additionally, the research explores two approaches of recycling and downcycling: closed-loop recycling, which pertains to the recycling of glass containers, and open-looped recycling, which involves the use of recycled glass in asphalt. The results showed when use annually collected waste as the functional unit, the KRMB model incurred lower costs compared to the KGRSB model due to its lower production output. However, when evaluated over a 1-ton production of glass container and asphalt, the KGRSB method demonstrated superior cost performance with a 40-50% reduction compared to the KRMB method. The open-loop recycling method (asphalt) incurred a higher cost compared to the closed-loop recycling method due to its larger production volume over a 21-year period.

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According to classical immunology theory, immunoglobulin (Ig) is exclusively produced by differentiated B lymphocytes, which exhibit a typical tetrapeptide chain structure and are predominantly present on the surface of B cells and in bodily fluids. B-Ig is one of the critical effector molecules for humoral immune responses specifically recognising antigens and eliminating them. However, mounting evidence has demonstrated that Ig is widely expressed in non B lineage cells, especially malignant ones (referred to as non B-Ig). Interestingly, non B-Ig mainly resides in the cytoplasm and secretion, but to some extent on the cell surface. Furthermore non B-Ig not only displays a tetrapeptide chain structure but also shows free heavy chains and free light chains (FLCs). Additionally, Ig derived from non B cancer cell typically displays unique glycosylation modifications. Functionally, non B-Ig demonstrated diversity and versatility, showing antibody activity and cellular biological activity, such as promoting cell proliferation and survival, and it is implicated in cancer progression and some immune-related diseases, such as renal diseases.

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Objective: This research aims to develop and assess the performance of interpretable machine learning models for diagnosing three histological subtypes of non-small cell lung cancer (NSCLC) utilizing CT imaging data. Methods: A retrospective cohort of 317 patients diagnosed with NSCLC was included in the study. These individuals were randomly segregated into two groups: a training set comprising 222 patients and a validation set with 95 patients, adhering to a 7:3 ratio. A comprehensive extraction yielded 1,834 radiomic features. For feature selection, statistical methodologies such as the Mann-Whitney U test, Spearman's rank correlation, and one-way logistic regression were employed. To address data imbalance, the Synthetic Minority Over-sampling Technique (SMOTE) was utilized. The study designed three distinct models to predict adenocarcinoma (ADC), squamous cell carcinoma (SCC), and large cell carcinoma (LCC). Six different classifiers, namely Logistic Regression, Support Vector Machine, Decision Tree, Random Forest, eXtreme Gradient Boosting (XGB), and LightGBM, were deployed for model training. Model performance was gauged through accuracy metrics and the area under the receiver operating characteristic (ROC) curves (AUC). To interpret the diagnostic process, the Shapley Additive Explanations (SHAP) approach was applied. Results: For the ADC, SCC, and LCC groups, 9, 12, and 8 key radiomic features were selected, respectively. In terms of model performance, the XGB model demonstrated superior performance in predicting SCC and LCC, with AUC values of 0.789 and 0.848, respectively. For ADC prediction, the Random Forest model excelled, showcasing an AUC of 0.748. Conclusion: The constructed machine learning models, leveraging CT imaging, exhibited robust predictive capabilities for SCC, LCC, and ADC subtypes of NSCLC. These interpretable models serve as substantial support for clinical decision-making processes.

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A generalized reliability model comprising the objective, constraint, and judgment functions is established for the reliability index approach (RIA), taking parameters' properties of engineering practice and negative reliability index into consideration. Based on this, the reliability-based design (RBD) problem with multiple design variables is translated into the solution to the nonlinear equations, and a simplified method consisting of a simple variant of the Newton iteration method and the finite difference method (FDM) is proposed. Numerical examples are presented to verify the efficiency of the proposed reliability approach and to determine the incremental step size for FDM. RBD of a simply supported beam is illustrated and the variabilities of design variables are investigated considering the uncertainties in the manufacturing process and practical operations. Results reveal that the variations of the design variables should not be ignored. Moreover, analysis results show that the design value might not intuitively increase with the increase of its coefficient of variation (CoV), and it might not increase with the increasing reliability requirement for problems involving multiple variables. The reasons for this phenomenon are very complicated, and it is a systematic problem. One should be aware of this phenomenon, and specific analysis is required for specific problems.

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Background: Patent foramen ovale (PFO) has been associated with migraine, cryptogenic stroke (CS), and hypoxemia. However, which examination method is most reliable remains controversial. This study sought to investigate the diagnostic value of contrast-enhanced ultrasonography (cU), including contrast-enhanced transcranial Doppler (cTCD), contrast transthoracic echocardiography (cTTE), and contrast transesophageal echocardiography (cTEE), for PFO; and to determine the best diagnostic strategy. Methods: This retrospective observational study included a total of 147 consecutive patients suspected PFO at The First Hospital of Shanxi Medical University between October 2019 and January 2022. The patients also underwent cTCD, cTTE, and cTEE examinations. The standard for the diagnosis of PFO was confirmation of the presence of PFO by color Doppler flow signals or contrast microbubbles (MBs) passing through the foramen ovale. Results: A total of 123 patients were diagnosed with PFO and 24 patients without PFO during the study period. The detectable rates of cTCD, cTTE, and cTEE were 120 (97.56%), 110 (89.43%), and 121 (98.37%), respectively. The sensitivity between cTCD and cTEE for PFO were comparable [97.56%, 95% confidence interval (CI): 92.5% to 99.4% vs. 98.37%, 95% CI: 93.7% to 99.7%; P>0.99], and the sensitivity of both were higher than that of cTTE (89.43%, 95% CI: 82.3% to 94.0%; P=0.02 and P=0.001, respectively). In addition, the specificity of cTEE for PFO was significantly higher than that of cTCD (100%, 95% CI: 82.3% to 100.0% vs. 75.00%, 95% CI: 53.0% to 89.4%; P<0.001) and cTTE (100%, 95% CI: 82.3% to 100.0% vs. 75.00%, 95% CI: 53.0% to 89.4%; P<0.001). Further, the semi-quantitative classification ability of cTCD for PFO with right-to-left shunt (RLS) was significantly higher than that of cTTE and cTEE (P=0.02 and P<0.001, respectively), and that of cTTE was significantly higher than that of cTEE (P=0.01). The Spearman analysis showed that the degree of RLS was positively correlated with the inner diameter of the PFO (r=0.695, P<0.001). Conclusions: The combination of cTCD and cTEE may provide a favorable strategy for the diagnosis of PFO.

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Atherosclerosis (AS) is the common pathophysiological basis of various cardiovascular diseases and the leading cause of death from cardiovascular disease worldwide. When the body is in a hypoxic environment, enhanced oxidative stress and significant accumulation of reactive oxygen species (ROS) in tissue cells exacerbate the inflammatory response, resulting in increased release of myeloperoxidase (MPO), catalyzing the formation of large quantities of hypochlorous acid (HOCl), further oxidative modification of low-density lipoprotein (LDL), and exacerbating the formation and progression of atherosclerotic plaques. The MAPK signaling pathway is important in oxidative stress-mediated promotion of atherogenesis. MPO -/- mice were used in this study to establish a hypoxia model simulating 5000 m altitude and a Western high-fat diet-induced atherosclerosis model for 12 weeks. Exploring the role of MPO in the atherosclerotic process in hypoxic mice by observing the MAPK signaling pathway to provide a therapeutic target for the prevention and treatment of hypoxic atherosclerotic disease in the plateau. We found that hypoxia promotes the formation of atherosclerosis in mice, and the mechanism may be that increased MPO in vivo promotes an inflammatory response, which plays a crucial role in the formation of atherosclerosis. In addition, hypoxia further exacerbates plaque instability by activating the MAPK signaling pathway to upregulate vascular endothelial growth factor (VEGF) and matrix metalloproteinase-9 (MMP9), which in turn promotes angiogenesis within the plaque. Therefore, a potential target for preventing and treating hypoxic atherosclerotic disease is the inhibition of MPO.

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HYPOTHESIS: Hydrophilic cationic drugs such as mitoxantrone hydrochloride (MTO) pose a significant delivery challenge to the development of nanodrug systems. Herein, we report the use of a hydrophobic ion-pairing strategy to enhance the nano-assembly of MTO. EXPERIMENTS: We employed biocompatible sodium cholesteryl sulfate (SCS) as a modification module to form stable ion pairs with MTO, which balanced the intermolecular forces and facilitated nano-assembly. PEGylated MTO-SCS nanoassemblies (pMS NAs) were prepared via nanoprecipitation. We systematically evaluated the effect of the ratio of the drug module (MTO) to the modification module (SCS) on the nanoassemblies. FINDINGS: The increased lipophilicity of MTO-SCS ion pair could significantly improve the encapsulation efficiency (∼97 %) and cellular uptake efficiency of MTO. The pMS NAs showed prolonged blood circulation, maintained the same level of tumor antiproliferative activity, and exhibited reduced toxicity compared with the free MTO solution. It is noteworthy that the stability, cellular uptake, cytotoxicity, and in vivo pharmacokinetic behavior of the pMS NAs increased in proportion to the molar ratio of SCS to MTO. This study presents a self-assembly strategy mediated by ion pairing to overcome the challenges commonly associated with the poor assembly ability of hydrophilic cationic drugs.

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We report on the development and performance evaluation of an ultra-stable laser for an 27Al+ optical clock. After a series of noise suppressions, especially the vibrational and temperature fluctuation noise, the 30 cm long cavity stabilized laser obtains a frequency instability of 1.3 × 10-16 @1 s. This result is predicted by noise summation and confirmed by the three-cornered hat method. The 27Al+ optical clock transition is also used to characterize the laser frequency noise, and consistent results are yielded. This is the first reported instance of using single ion optical clocks to measure the frequency noise of ultra-stable lasers, as far as we know. With the implementation of the ultra-stable clock laser, an ultra-narrow linewidth clock transition of 2.8 Hz is obtained.

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Density functional theory (DFT) characterizations were employed to resolve the structural and energetic aspects and product selectivities along the mechanistic reaction paths of the nickel-catalyzed three-component unsymmetrical bis-allylation of alkynes with alkenes. Our putative mechanism initiated with the in situ generation of the active catalytic species [Ni(0)L2] (L = NHC) from its precursors [Ni(COD)2, NHC·HCl] to activate the alkyne and alkene substrates to form the final skipped trienes. This proceeds via the following five sequential steps: oxidative addition (OA), ß-F elimination, ring-opening complexation, C-B cleavage and reductive elimination (RE). Both the OA and RE steps (with respective free energy barriers of 24.2 and 24.8 kcal·mol-1) contribute to the observed reaction rates, with the former being the selectivity-controlling step of the entire chemical transformation. Electrophilic/nucleophilic properties of selected substrates were accurately predicted through dual descriptors (based on Hirshfeld charges), with the chemo- and regio-selectivities being reasonably predicted and explained. Further distortion/interaction and interaction region indicator (IRI) analyses for key stationary points along reaction profiles indicate that the participation of the third component olefin (allylboronate) and tBuOK additive played a crucial role in facilitating the reaction and regenerating the active catalyst, ensuring smooth formation of the skipped triene product under a favorably low dosage of the Ni(COD)2 catalyst (5 mol%).

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Massive increases in the risks of depressive disorders and the ensuing suicide have become the overarching menace for children/adolescents. Despite global consensus to instigate psychological healthcare policy for these children/adolescents, their effects remain largely unclear neither from a small amount of official data nor from small-scale scientific studies. More importantly, in underprivileged children/adolescents in lower-middle-economic-status countries/areas, the data collection may not be as equally accessible as in developed countries/areas, thus resulting in underrepresented observations. To address these challenges, we released a large-scale and multi-center cohort dataset (n = 249,772) showing the effects of primary psychological healthcare on decreasing depression and suicidal ideation in these children/adolescents who were underrepresented in previous studies or current healthcare systems, including unattended children/adolescents, orphans, children/adolescents in especially difficult circumstances, and "left-behind" and "single-parenting" children/adolescents. We provided all individual data recording the depressive symptoms and suicide ideation that had been collected at baseline (Oct 2022) and half-year follow-up (May 2023) from practicing this psychological healthcare system.

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BACKGROUND: This study extends from the 2015 Shandong Province Epidemiological Survey of Mental Disorders in adults aged 18 and above. Over five years, it investigates pain characteristics and influencing factors in individuals with depressive disorders in Shandong Province. METHODS: The study encompasses 871 individuals who met DSM-IV criteria for depressive disorders in 2015. Using 1:1:1 matching by gender, age, and residence, 825 non-afflicted individuals were selected as high-risk controls, and 825 screening-negative individuals became low-risk controls. A follow-up study in 2020 involved 1848 participants. Survey tools included a general information questionnaire, General Health Questionnaire-12 (GHQ-12), SCID-I/P, Global Pain Scale (GPS), Quality of Life Questionnaire (QLQ), PSQI, MoCA, and clinical data questionnaire. RESULTS: GPS scores in the current depressive group were higher than in non-current depressive group (Z = 14.36, P < 0.01). GPS scores in study group exceeded those in high-risk and low-risk control groups (H = 93.71, P < 0.01). GPS scores in non-remission group were higher than in the remission group (Z = 8.90, P < 0.01). Regression analysis revealed positive correlations between GPS scores and physical illnesses, current depression, incumbency, GHQ-12 total score, and PSQI total score. Negative correlations were observed with QLQ total score and MoCA total score. LIMITATIONS: The study could not assess pain during the 2015 survey, limiting controlled pain analysis before and after five years. CONCLUSION: Depression sufferers may experience prolonged heightened pain, potentially relieved when depression subsides. Individual pain is influenced by depression, physical illnesses, sleep quality, quality of life, cognitive function, gender, residence, and occupation.

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The palladium-catalyzed sequential cross-coupling/annulation of ortho-vinyl bromobenzenes with aryl bromides generating phenanthrenes was characterized by density functional theory (DFT). The Pd(II)-Pd(IV) pathway (Path V) is shown to be less probable than the bimetallic pathway (Path I), the latter proceeding via the following six steps: oxidative addition, vinyl-C(sp2)-H activation, Pd(II)-Pd(II) transmetalation, C-C coupling, aryl-C(sp2)-H activation, and reductive elimination. The aryl-C(sp2)-H activation process acts as the rate-determining step (RDS) of the entire chemical transformation, with an activation free energy barrier of ca. 27.4-28.8 kcal·mol-1, in good agreement with the corresponding experimental data (phenanthrenes' yields of ca. 65-90% at 130 °C after 5 h of reaction). The K2CO3 additive effectively reduces the activation free energy barrier of the RDS through direct participation in the reaction while preferentially modulating the charge distributions and increasing the stability of corresponding intermediates and complexes along the reaction path. Furthermore, bonding and electronic structure analyses of the key structures indicate that the chemo- and regioselectivities of the reaction are strongly influenced by both electronic effects and steric hindrance.

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Molecules with high point-group symmetry are interesting prototype species in the textbook. As transition metal-centered boron clusters tend to have highly symmetric structures to fulfill multicenter bonding and high stability, new boron clusters with rare point-group symmetry may be viable. Through in-depth scrutiny over the structures of experimentally already observed transition metal-centered boron-wheel complexes, geometric and electronic design principles are summarized, based on which we studied M©B11k- (M = Y, La; Zr, Hf; k = 1, 2) clusters and found that a Y©B112- boron-wheel complex has an unprecedented D11h point-group symmetry. The remarkable stability of the planar Y©B112- complex is illustrated via extensive global-minimum structural search as well as comprehensive chemical bonding analyses. Similar to other boron-wheel complexes, the Y©B112- complex is shown to possess σ and π double aromaticity, indeed following the electronic design principle previously summarized. This new compound is expected to be experimentally identified, which will extend the currently known largest possible planar molecular symmetry and enrich the metal-centered boron-wheel class.