Impact of professional identity on learner well-being of undergraduate nursing students of "double tops" universities: Mediating effect of self-regulated learning.

OBJECTIVES: The pressure of internal competition at the college level has increased in recent years in China with an impact on nursing students' learning and well-being. This study aimed to investigate the current situation and factors affecting professional identity, learner well-being and self-regulated learning of undergraduate nursing students in the Neijuan ecology of the "double tops" universities, and to explore the relationships between these three variables. METHODS: A cross-sectional design was adopted to conduct an online survey of 322 Chinese undergraduate nursing students from seven "double tops" universities. The survey included socio-demographics characteristics, students' professional identity, learner well-being, and self-regulated learning. RESULTS: Results of Pearson correlation analysis showed that professional identity was significantly and positively correlated with learner well-being (R = 0.795, p < 0.001); professional identity was significantly and positively correlated with self-regulated learning (R = 0.843, p < 0.001); and, self-regulated learning was significantly and positively correlated with learner well-being (R = 0.852, p < 0.001). After mediation effect testing, self-regulated learning had a mediating effect between professional identity and learner well-being (95 % CI 0.366-0.548, p < 0.001). Professional identity had a positive predictive effect on self-regulated learning (a = 0.570, p < 0.001), and self-regulated learning also had a positive predictive effect on learner well-being (b = 0.798, p < 0.001). The direct effect of professional identity on learner well-being (0.225) and its mediating effect (0.455) account for 33.1 % and 66.9 % of the total effect (0.680), respectively. CONCLUSIONS: The learner well-being of undergraduate Chinese nursing students is in the middle to upper range, and it is crucial to enhance professional identity and develop students' self-regulated learning to improve their learner well-being. This study provides empirical evidence to support the mediating effect of self-regulated learning on the relationship between professional identity and learner well-being among undergraduate nursing students in "double tops" universities. Universities are expected to strengthen career planning guidance and professional competence training for students as early as possible in order to develop quality nursing education programs that produce graduates who enter and remain in the workforce.

Computational screening of transition metal atom doped ZnS and ZnSe nanostructures as promising bifunctional oxygen electrocatalysts.

The design of bifunctional oxygen electrocatalysts showing high catalytic performance for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is of great significance for developing new renewable energy storage and conversion technologies. Herein, based on the first principles calculations, we systematically explored the electrocatalytic activity of a series of transition metal atom (Fe, Co, Ni, Cu, Pd and Pt)-doped ZnS and ZnSe nanostructures for OER and ORR. The calculated results revealed that Ni- and Pt-doped ZnS and ZnSe nanostructures exhibit promising electrocatalytic performance for both OER and ORR in comparison to the pristine ZnS and ZnSe nanostructures. Especially, the OER/ORR overpotentials of Ni-doped ZnS and ZnSe nanostructures are estimated to be 0.28/0.30 and 0.31/0.31 V, respectively, disclosing their great potential as bifunctional oxygen electrocatalysts. Moreover, it is found that Ni-doped ZnS and ZnSe nanostructures for OER and ORR are on the top of the volcano plots, evincing promising catalytic performance. Our results provide theoretical insights into a feasible strategy to synthesize highly efficient ZnS- and ZnSe-based bifunctional oxygen electrocatalysts in the future.

Metal-free alkyne annulation enabling π-extension of boron-doped polycyclic aromatic hydrocarbons.

A C-H functionalizing annulation reaction of boron-doped polycyclic aromatic hydrocarbons (PAHs) with alkynes is described. This metal-free π-extension provides a new synthetic route to fusion atom B-doped polycyclic aromatic hydrocarbons (PAHs) that is demonstrated with the synthesis of a family of new, functionalized, structurally constrained 6a,15a-diborabenzo[tuv]naphtho[2,1-b]picenes. These annulation products exhibit deep LUMO energy levels, strong visible-range absorptions, and sterically accessible π-systems that can adopt herringbone or π-stacked solid-state structures based on choice of substituents. From regioselectivity and DFT calculations, we propose an annulation mechanism involving intramolecular electrophilic aromatic substitution of a zwitterionic intermediate.

An unprotected vulnerable relict subtropical conifer-Keteleeria evelyniana: Its forests, populations, growth and endangerment by invasive alien plant species in China.

Relict subtropical coniferous forests in China face severe fragmentation, resulting in declining populations, and some are under significant threat from invasive alien species. Despite the crucial importance of understanding forest dynamics, knowledge gaps persist, particularly regarding the impact of invasive plants on vulnerable natives like Keteleeria evelyniana. In this study, we investigated the impact of invasive plants on the regeneration of forests dominated by K. evelyniana, a subtropical relict species in southwestern China. For this purpose, we characterized forest dynamics of 160 forest plots featuring K. evelyniana as the primary dominant species and determined whether the presence of invasive plants was correlated with regeneration of K. evelyniana. We identified four distinct forest types in which K. evelyniana was dominant. We found that radial growth of K. evelyniana trees is faster in younger age-classes today than it was for older trees at the same age. The population structure of K. evelyniana in each forest type exhibited a multimodal age-class distribution. However, three forest types lacked established saplings younger than 10 years old, a situation attributed to the dense coverage of the invasive alien Ageratina adenophora. This invasive species resulted in a reduction of understory species diversity. Additionally, our analysis uncovered a significant negative correlation in phylogenetic relatedness (net relatedness index) between native and invasive alien plant species in eastern Yunnan. This suggests closely related invasive species face heightened competition, hindering successful invasion. Taken together, our findings indicate that successful establishment and habitat restoration of K. evelyniana seedling/saplings require effective measures to control invasive plants.

Advanced AI and renewable energy sources for unified rotor angle stability control.

Maintaining a reliable electricity supply amidst the integration of diverse energy sources necessitates optimizing the stability of power systems. This paper introduces a groundbreaking method to enhance the efficiency and resilience of power grids. The increasing dependence on renewable energy sources poses significant challenges to traditional power networks, thereby demanding innovative solutions to uphold their stability and security. To address these challenges, we propose an architecture that seamlessly unifies dynamic, transient, and static rotor angle stability (RAS) controls into a single, streamlined system. Utilizing reinforcement learning and real-time decision-making, we present Lazy Deep Q Networks (LDQNs) as a novel approach to RAS control. LDQNs provide real-time rotor angle instructions to RAS devices, enabling precise and efficient stability management. The incorporation of mass-distributed energy storage further augments the system's responsiveness and flexibility, mitigating fluctuations and promoting overall stability. This study advances the application of AI methods to RAS control, building on prior research in frequency and voltage stability frameworks. The proposed system outperforms conventional RAS control methods by integrating LDQNs with mass-distributed energy storage, offering superior performance and adaptability. Case studies validate the effectiveness of the unified RAS framework, demonstrating its advantages over traditional approaches across various power system configurations.

Chiral Brønsted Acid-Catalyzed Intramolecular Asymmetric Dearomatization Reaction of Indoles with Cyclobutanones via Cascade Friedel-Crafts/Semipinacol Rearrangement.

The highly efficient synthesis of chiral indolines fused with an azabicyclo[2.2.1]heptanone moiety is achieved by an asymmetric dearomatization reaction of indoles with cyclobutanones. A new chiral imidodiphosphorimidate (IDPi) catalyst is synthesized and exhibits extraordinary activity in promoting a cascade Friedel-Crafts/semipinacol rearrangement. Target molecules are prepared in good yields (up to 95%) with excellent enantioselectivity (up to 98% ee) with operational convenience. Combined experimental and computational studies provide detailed mechanistic insights into the energy landscape and origin of the stereochemical induction of the reaction.

All-cause and suicide mortality after first psychiatric admission in adolescents and young adults: A longitudinal follow-up study.

BACKGROUND: This study investigated all-cause and suicide mortality rates in adolescents and young adults following an initial psychiatric admission to elucidate the long-term outcomes for this vulnerable group by focusing on the risks associated with various psychiatric diagnostic categories. METHODS: This study involved 9762 adolescents and young adults discharged from their first psychiatric admission and matched 1:1 with 9762 individuals discharged following a diagnosis of appendicitis on the basis of birth year and sex by using Taiwan's National Health Insurance Research Database. Both stratified (model 1) and standard (model 2) Cox regression analyses were conducted to assess variations in all-cause and suicide mortality between the groups. RESULTS: Over the 15-year follow-up period, the adolescents and young adults discharged from their first psychiatric admission exhibited an approximately 3-fold increased risk of death from any cause (hazard ratio [HR]: 2.97 in model 1, 2.83 in model 2) and an approximately ten times higher risk of suicide (11.13 in model 1, 9.23 in model 2) compared with those discharged with a diagnosis of appendicitis. Those discharged with alcohol use disorder or major depressive disorder exhibited higher hazard ratios for both all-cause and suicide compared with the reference group. CONCLUSIONS: The findings reveal a considerable risk of all-cause and suicide mortality in adolescents and young adults following discharge from their first psychiatric admission. These results highlight an urgent need for tailored interventions and continued support for this demographic.

The Inhibiting Effect of GB-2, (+)-Catechin, Theaflavin, and Theaflavin 3-Gallate on Interaction between ACE2 and SARS-CoV-2 EG.5.1 and HV.1 Variants.

The ongoing COVID-19 pandemic, caused by SARS-CoV-2, continues to pose significant global health challenges. The results demonstrated that GB-2 at 200 µg/mL effectively increased the population of 293T-ACE2 cells with low RBD binding for both SARS-CoV-2 Omicron EG.5.1 and HV.1 variants by dual-color flow cytometry, indicating its ability to inhibit virus attachment. Further investigation revealed that (+)-catechin at 25 and 50 µg/mL did not significantly alter the ACE2-RBD interaction for the EG.5.1 variant. In contrast, theaflavin showed inhibitory effects at both 25 and 50 µg/mL for EG.5.1, while only the higher concentration was effective for HV.1. Notably, theaflavin 3-gallate exhibited a potent inhibition of ACE2-RBD binding for both variants at both concentrations tested. Molecular docking studies provided insight into the binding mechanisms of theaflavin and theaflavin 3-gallate with the RBD of EG.5.1 and HV.1 variants. Both compounds showed favorable docking scores, with theaflavin 3-gallate demonstrating slightly lower scores (-8 kcal/mol) compared to theaflavin (-7 kcal/mol) for both variants. These results suggest stable interactions between the compounds and key residues in the RBD, potentially explaining their inhibitory effects on virus attachment. In conclusion, GB-2, theaflavin, and theaflavin 3-gallate demonstrate significant potential as inhibitors of the ACE2-RBD interaction in Omicron variants, highlighting their therapeutic promise against COVID-19. However, these findings are primarily based on computational and in vitro studies, necessitating further in vivo research and clinical trials to confirm their efficacy and safety in humans.

Chiral Bis(binaphthyl) Cyclopentadienyl Ligands for Rhodium-Catalyzed Desymmetrization of Diarylmethanes via Selective Arene Coordination.

Owing to substantial advances in the past several decades, transition-metal-catalyzed asymmetric reactions have garnered considerable attention as pivotal methods for constructing chiral molecules from abundant, readily available achiral counterparts. These advances are largely attributed to the development of chiral ligands that control stereochemistry through steric repulsion and other noncovalent interactions between the ligands and functional groups or prochiral centers on the substrates. However, stereocontrol weakens dramatically with increasing distance between the reaction site and the functional group or prochiral center. Herein, we report a symphonic strategy for remote stereocontrol of Rh(III)-catalyzed asymmetric benzylic C-H bond addition reactions of diarylmethanes in which the two aryl motifs differ at the meta and/or para position. Specifically, catalysts bearing a new type of chiral cyclopentadienyl (Cp) ligand differentiate between the two aromatic rings of the diarylmethane by arene-selective η6 coordination, setting up an opportunity for ligand-controlled stereoselective benzylic deprotonation and subsequent stereoselective addition to the 1,1-bis(arylsulfonyl)ethylene.

Asymmetric Allylic Amination of Alkyl-Substituted Allylic Carbonates with Pyridones Catalyzed by the Krische Iridium Complex.

An efficient Ir-catalyzed asymmetric allylic amination reaction of alkyl-substituted allylic carbonates is disclosed. With the Krische iridium complex as the catalyst, asymmetric allylic amination of alkyl-substituted allylic carbonates with pyridones proceeds effectively, affording pyridone derivatives containing a stereocenter α to the nitrogen atom in excellent yields and enantioselectivity (up to 99% yield, 95% ee). This catalytic system broadens the substrate scope of the reaction compared with that of the known catalytic systems. This reaction can also be conducted on a gram scale, further enhancing its potential for synthetic application.

Interaction between the albumin-bilirubin score and nutritional risk index in the prediction of post-hepatectomy liver failure.

BACKGROUND: Post-hepatectomy liver failure (PHLF) is the most common postoperative complication and the leading cause of death after hepatectomy. The albumin-bilirubin (ALBI) score and nutritional risk index (NRI) have been shown to assess end-stage liver disease and predict PHLF and patient survival. We hypothesized that the ALBI score and NRI interact in the prediction of PHLF. AIM: To analyze the interaction between the ALBI score and NRI in PHLF in patients with hepatocellular carcinoma. METHODS: This retrospective study included 186 patients who underwent hepatectomy for hepatocellular carcinoma at the Affiliated Hospital of Youjiang Medical University for Nationalities between January 2020 and July 2023. Data on patient characteristics and laboratory indices were collected from their medical records. Univariate and multivariate logistic regression were performed to determine the interaction effect between the ALBI score and NRI in PHLF. RESULTS: Of the 186 patients included in the study, PHLF occurred in 44 (23.66%). After adjusting for confounders, multivariate logistic regression identified ALBI grade 2/3 [odds ratio (OR) = 73.713, 95% confidence interval (CI): 9.175-592.199] and NRI > 97.5 (OR = 58.990, 95%CI: 7.337-474.297) as risk factors for PHLF. No multiplicative interaction was observed between the ALBI score and NRI (OR = 0.357, 95%CI: 0.022-5.889). However, the risk of PHLF in patients with ALBI grade 2/3 and NRI < 97.5 was 101 times greater than that in patients with ALBI grade 1 and NRI ≥ 97.5 (95%CI: 56.445-523.839), indicating a significant additive interaction between the ALBI score and NRI in PHLF. CONCLUSION: Both the ALBI score and NRI were risk factors for PHLF, and there was an additive interaction between the ALBI score and NRI in PHLF.

Nutritional support clinical efficacy in tuberculosis: quasi-experimental study.

OBJECTIVE: This study aimed to investigate the impact of nutritional support on the clinical efficacy in hospitalised tuberculosis patients with nutritional risk. METHODS: We selected a total of 266 eligible patients with tuberculosis for the experimental and 190 patients for control groups. The patients in intervention group received adjusted dietary structure, enteral nutrition via oral intake or gastric tube, total parenteral nutrition and combined enteral and parenteral nutrition. We recorded various factors, including age, sex, underlying disease, tuberculosis type, nutritional risk at admission, serum albumin (ALB), body mass index, complications during hospitalisation, nutritional support status, serum ALB before discharge and length of hospital stay. RESULTS: The incidences of nutritional risk in the control and experimental groups were 64.41% and 64.72%, respectively, with no statistically significant differences in baseline characteristics. The occurrence rates of complications and secondary infections in the experimental group were 57.89% and 51.5%, respectively, which were significantly lower than the control group's rates of 70.00% and 56.31%. These differences were statistically significant. The experimental group had a significantly shorter hospital stay (16.5±7.54 days) compared with the control group (19.55±7.33 days). Furthermore, the serum ALB levels of patients in the experimental group were higher on discharge than at admission. CONCLUSION: Hospitalised patients with tuberculosis often face a high incidence of nutritional risk. However, the implementation of standardised nutritional support treatment has shown promising results in improving the nutritional status of tuberculosis patients with nutritional risk. This approach not only helps reduce the occurrence of complications but also enhances short-term prognosis and improves overall clinical efficacy.

The association between diverse psychological protocols and the efficacy of psilocybin-assisted therapy for clinical depressive symptoms: a Bayesian meta-analysis.

Objective: Psilocybin-assisted therapy has shown promising efficacy on clinical depressive symptoms. However, diverse psychological support or psychotherapy was performed with psilocybin treatment. This study aimed to explore the association of psychological protocols with the efficacy of psilocybin-assisted therapy for depressive symptoms. Method: Five major databases were systemic searched for clinical trials addressing psilocybin-assisted therapy for patients with clinical depressive symptoms. A Bayesian random-effects meta-analysis and meta-regression were performed. The effect size was mean difference (with 95% credible interval) measured by 17-Item Hamilton Depression Rating Scale. Results: There were 10 eligible studies including 515 adult patients with clinically diagnosed depression. The psychological protocols could be categorized into four types: (i) manualized directive psychotherapy(k=1); (ii) manualized nondirective psychological support(k=3), (iii) non-manualized nondirective psychological support(k=5); and (iv) non-manualized supportive psychotherapy(k=1). The pooled standard mean difference of psilocybin-assisted therapy was 10.08 (5.03-14.70). Conclusion: Compared with manualized nondirective psychological support, the other three psychological approaches did not differ significantly. The improvement of depressive symptoms was not associated with the psychological protocols in adult patients receiving psilocybin-assisted therapy. Systemic review registration: Open Science Framework: identifier (osf.io/3YUDV).

RNA nanotherapeutics with fibrosis overexpression and retention for MASH treatment.

Metabolic dysfunction-associated steatohepatitis (MASH) poses challenges for targeted delivery and retention of therapeutic proteins due to excess extracellular matrix (ECM). Here we present a new approach to treat MASH, termed "Fibrosis overexpression and retention (FORT)". In this strategy, we design (1) retinoid-derivative lipid nanoparticle (LNP) to enable enhanced mRNA overexpression in fibrotic regions, and (2) mRNA modifications which facilitate anchoring of therapeutic proteins in ECM. LNPs containing carboxyl-retinoids, rather than alcohol- or ester-retinoids, effectively deliver mRNA with over 10-fold enhancement of protein expression in fibrotic livers. The carboxyl-retinoid rearrangement on the LNP surface improves protein binding and membrane fusion. Therapeutic proteins are then engineered with an endogenous collagen-binding domain. These fusion proteins exhibit increased retention in fibrotic lesions and reduced systemic toxicity. In vivo, fibrosis-targeting LNPs encoding fusion proteins demonstrate superior therapeutic efficacy in three clinically relevant male-animal MASH models. This approach holds promise in fibrotic diseases unsuited for protein injection.

Risk of Dementia in Different Types of Cancer Survivors: A Nationwide Cohort Study.

OBJECTIVES: The association between specific types of malignancies and the subsequent risk of dementia remains unknown. DESIGN: A retrospective population-based cohort study based on data from Taiwan National Health Insurance Research Database. SETTING AND PARTICIPANTS: We recruited 32,250 patients who survived malignancies and 322,500 controls between 1998 and 2011 and followed them up until the end of 2013. MEASUREMENTS: Diagnoses of dementia (including Alzheimer's disease (AD), vascular dementia (VaD), and unspecified dementia) was made during the follow-up period. Cox regression analyses were performed after adjusting for potential confounders. A sensitivity analysis was conducted to exclude patients with prodromal dementia. RESULTS: Cancer survivors were more likely to develop AD (hazard ratio [HR]: 1.68, 95% confidence interval [CI]: 1.38-2.06), unspecified dementia (HR: 1.19, 95% CI: 1.07-1.32), and any dementia (HR: 1.26, 95% CI: 1.16-1.37) compared with controls after adjusting for potential confounders. Importantly, cancers of the digestive and genitourinary organs seem to be associated with AD, unspecified dementia, and any dementia, whereas only malignant neoplasms of the brain are more likely to develop into VaD. Sensitivity analyses after exclusion of the first three or five years of observation and after exclusion of case enrollment before 2009 or 2007 showed consistent findings. CONCLUSION: Cancer survivors are at higher risk of subsequent dementia. Different types of cancer survivors may contribute to variable risks of specific dementias. Further studies are necessary to investigate the underlying mechanisms in cancer survivors and patients with dementia.

Glucose metabolism disorder related to follicular fluid exosomal miR-122-5p in cumulus cells of endometriosis patients.

In Brief: Elevated expression of miR-122-5p in exosomes in the follicular fluid of patients with endometriosis impairs glucose metabolism in cumulus cells and may further impair oocyte quality. Abstract: Endometriosis (EMs) affects fertility in women of childbearing age in many ways. The underlying mechanisms, including the decrease in oocyte quality, require further investigation. Exosomes, small vesicles responsible for intercellular information exchange, have been found to be involved in many biological events, including follicle development and oocyte meiosis recovery. From the perspective of follicular fluid exosomes, this study aimed to elucidate the mechanisms involved in EMs-related oocyte quality decline. Follicular fluid was collected from three groups of women: the untreated EMs group (EMs_UT), the satisfactorily treated EMs group (EMs_ST), and the control group (Ctrl). Mouse cumulus-oocyte complexes (COCs) were co-cultured with exosomes extracted from follicular fluid during in vitro maturation. Oocyte quality and cumulus cell function were assessed. High-throughput sequencing of miRNA in exosomes was conducted. The function of differentially expressed miRNAs was studied by using SVOG human ovarian granulosa cells transfected with an miRNA mimic and inhibitor. It was found that the follicular fluid exosomes from patients with untreated EMs reduced both the rate of maturation and the quality of mouse oocytes. Overexpression of miR-122-5p in untreated EMs inhibited the translation of key aldolase enzymes related to glucose metabolism and partly impaired glucose metabolism in the cumulus cells of patients with endometriosis. miR-122-5p was also observed to reduce proliferation and increase apoptosis after cell transfection with an miR-122-5p mimic and inhibitor. Further experiments are needed to determine whether there are additional small molecules in the follicular fluid of patients with endometriosis that could be involved in damaging oocyte quality and to identify where harmful substances in follicular fluid exosomes are loaded.

Single-Cell RNA Sequencing Deconstructs the Distribution of Immune Cells Within Abdominal Aortic Aneurysms in Mice.

BACKGROUND: Inflammation is a key component in the development of abdominal aortic aneurysm (AAA), yet insights into the roles of immune cells and their interactions in this process are limited. METHODS: Using single-cell RNA transcriptomic analysis, we deconstructed the CD45+ cell population in elastase-induced murine AAA at the single-cell level. We isolated each group of immune cells from murine AAA tissue at different time points and divided them into several subtypes, listed the remarkable differentially expressed genes, explored the developmental trajectories of immune cells, and demonstrated the interactions among them. RESULTS: Our findings reveal significant differences in several immune cell subsets, including macrophages, dendritic cells, and T cells, within the AAA microenvironment compared with the normal aorta. Especially, conventional dendritic cell type 1 exclusively existed in the AAA tissue rather than the normal aortas. Via CellChat analysis, we identified several intercellular communication pathways like visfatin, which targets monocyte differentiation and neutrophil extracellular trap-mediated interaction between neutrophils and dendritic cells, which might contribute to AAA development. Some of these pathways were validated in human AAA. CONCLUSIONS: Despite the absence of external pathogenic stimuli, AAA tissues develop a complex inflammatory microenvironment involving numerous immune cells. In-depth studies of the inflammatory network shall provide new strategies for patients with AAA.

Single-cell RNA sequencing uncovers cellular heterogeneity and the progression of heterotopic ossification of the elbow.

Heterotopic ossification of the elbow (HOE) is a complicated pathologic process characterized by extra bone formation in the elbow. Bone formation is a complex developmental process involving the differentiation of mesenchymal stem cells into osteoblasts. The aim of this study was to explore the cellular origin and progression of HOE by single-cell RNA sequencing. We identified 13 clusters of cells in HOE and further analyzed the subclusters for 4 of the main cell types. Six subclusters of osteoblasts, nine subclusters of chondrocytes, six subclusters of fibroblasts, and five subclusters of mononuclear phagocytes (MPs) were identified and analyzed. The new findings on osterix (OSX) and SOX9 expression in osteoblast subclusters and chondrocyte subclusters indicate that HOE is mediated through endochondral ossification. Further identification of the corresponding signature gene sets of distinct subclusters indicated that subclusters of osteoblasts_3, osteoblasts_4, osteoblasts_5, and osteoblasts_6 are relatively more mature during the osteoblastic progression of HOE. The trajectory analysis of the osteoblasts demonstrated that some genes were gradually downregulated, such as CRYAB, CCL3, SFRP4, WIF1, and IGFBP3, while other critical genes were upregulated, such as VCAN, IGFBP4, FSTL1, POSTN, MDK, THBS2, and ALPL, suggesting that these factors may participate in HOE progression. Cell-cell communication networks revealed extensive molecular interactions among the 13 HOE clusters. Ligand-receptor pairs for IL6, COL24A1, COL22A1, VWF, FZD6, FGF2, and NOTCH1 were identified, suggesting that multiple signaling pathways may be involved in HOE. In conclusion, this study provided the cellular atlas for HOE. We have established a greater extent of the heterogeneity of HOE cells than previously known through transcriptomic analysis at the single-cell level. We have observed gradual patterns of signature gene expression during the differentiation and maturation progression of osteoblasts from stem cells in HOE with higher resolution. The cell heterogeneity of HOE deserves further investigation to pave the way for identification of potential targets for HOE early diagnosis and therapeutic treatment.

Electrophile-Arene Affinity: An Energy Scale for Evaluating the Thermodynamics of Electrophilic Dearomatization Reactions.

Rational design and development of organic reactions are lofty goals in synthetic chemistry. Quantitative description of the properties of molecules and reactions by physical organic parameters plays an important role in this regard. In this Article, we report an energy scale, namely, electrophile-arene affinity (EAA), for evaluating the thermodynamics of electrophilic dearomatization reactions, a class of important transformations that can rapidly build up molecular complexity and structural diversity by converting planar aromatic compounds into three-dimensional cyclic molecules. The acquisition of EAA data can be readily achieved by theoretically calculating the enthalpy changes (ΔH) of the hypothetical reactions of various (cationic) electrophiles with aromatic systems (taking the 1-methylnaphthalen-2-olate ion as an example in this study). Linear correlations are found between the calculated ΔH values and established physical organic parameters such as the percentage of buried volume %VBur (steric effect), Hammett's σ or Brown's σ+ (electronic effect), and Mayr's E (reaction kinetics). Careful analysis of the ΔH values leads to the rational design of a dearomative alkynylation reaction using alkynyl hypervalent iodonium reagents as the electrophiles.