Cooperative Photoredox and N-Heterocyclic Carbene Catalysis Suzuki-Miyaura-Type Reaction: Radical Coupling of Aroyl Fluorides and Alkyl Boronic Acids.

An intermolecular Suzuki-Miyaura-type reaction of benzoyl fluorides with alkyl boronic acids to synthetic ketone was revealed by cooperative N-heterocyclic carbene (NHC) and photoredox catalysis. Various alkyl boric acids can be converted into alkyl radicals without external oxidants or activators. Moreover, the catalytic system was feasible for the difunctionalization of styrenes via a radical relay process. Mechanistic experiments suggested that the benzoate anion intermediate might play a unique role in this reaction system.

Analysis of Online Recruitment Intention Among 543 Hospitals: A Comprehensive Investigation of Influencing Factors and Current Situation.

Objective: The primary objective of this study was to investigate the current state of online recruitment intention among hospitals and identify its key influencing factors. This research aims to provide valuable insights that can guide the development of recruitment and employment strategies for hospital departments and student management. Methods: This study employed a cross-sectional survey approach involving 543 hospitals. Data collection utilized both convenient offline recruitment methods and online recruitment information platforms. A total of 543 questionnaires were distributed, resulting in the collection of 543 valid responses. The participating hospitals comprised 225 tertiary hospitals and 318 secondary hospitals. Additionally, the sample included 430 general hospitals, 113 psychiatric hospitals, dental hospitals, and 406 specialized hospitals. Geographically, 137 hospitals were located in urban counties or towns. Furthermore, 333 hospitals targeted undergraduate graduates, while 210 focused on graduate students. Results: The analysis of the data revealed several significant findings. Among the included hospitals in the sample, 19.71% expressed online recruitment intention for candidates with neurasthenia. Factors contributing to a higher online recruitment intention among hospitals included a preference for recruiting undergraduates (P = .011), the belief that online recruitment is suitable for clinical positions (P = .002), challenges in assessing candidates' expertise online (P = .002), concerns about dishonesty in online recruitment (P = .028), and the perception that online recruitment requires less technical expertise for hospitals (P < .001). Conclusions: This study highlights the multifaceted nature of online recruitment intention within hospitals. The identified influential factors emphasize the need for customized strategies in recruitment and employment. Medical university recruitment and employment departments should adopt tailored measures that align with the unique dynamics of online recruitment to address these factors effectively. In this way, hospitals can enhance their recruitment processes and ensure the selection of candidates that meet their specific requirements.

The association between blood heavy metals and gallstones: A cross-sectional study.

BACKGROUND AND AIMS: Exposure to heavy metals has been widely recognized as a risk factor for human health. However, there is limited information on the effects of blood heavy metals on gallstones. This study aims to investigate the relationship between blood heavy metals and gallstones using data from the National Health and Nutrition Examination Survey (NHANES). METHODS: 7192 participants aged 20 years or older with complete information were included in the study. Serum concentrations of heavy metals were determined by inductively coupled plasma kinetic reaction cell mass spectrometry. Gallstones were presented by standard questionnaires. Logistic regression, nonlinear, subgroup, and sensitivity analyses were used to estimate the association between blood heavy metals and gallstones. RESULTS: Multivariate logistic regression showed that the highest quintile of blood selenium (Se) was associated with a higher risk of gallstones compared with the lowest quintile (OR = 1.66, 95% CI: 1.16-2.36), particularly in individuals who were under 65 years of age, females, non-Hispanic Whites, non-drinkers, obese, and had a college education or higher. There was no correlation between blood cadmium (Cd), mercury (Hg), lead (Pb), manganese (Mn), and gallstones in the total population. Restricted cubic spline curves showed that a negative correlation was observed between blood Cd (OR = 0.84, 95% CI: 0.710-1.00), Hg (OR = 0.87, 95% CI: 0.78-0.97) and gallstones when Cd < 0.302 µg/L and Hg < 3.160 µg/L. CONCLUSIONS: Blood Se was an independent risk factor for gallstones, particularly in individuals under 65 years old, females, non-Hispanic Whites, non-drinkers, obese, and had a college education or higher. Furthermore, blood Cd and Hg were associated with a reduced risk of gallstones within a certain range.

Ketone Synthesis via Irradiation-Induced Generation of a Persistent Ketyl Radical from Acyl Azolium Salts.

A novel three-component α-acylated difunctionalization of alkenes strategy has been developed on the basis of a direct hydrogen atom transfer (HAT) process of photoinduced acyl azolium salts. With simple irradiation without the catalyst, a variety of olefins can be directly converted into ketone derivatives, including 1,4-dione, ß-silyl ketone, 1,5-dione, etc. Mechanistic investigations indicated that the unique reactivity of the acyl azonium triplet excited state is crucial to the strategy's success.

Bone mineral density and its influential factors in Chinese patients with newly diagnosed Crohn's disease.

OBJECTIVES: Bone loss is a common morbidity in patients with inflammatory bowel disease (IBD). Bone mineral density (BMD) measurement is recommended for IBD patients at a high risk of osteoporosis. However, there is a lack of evidence in the need of BMD measurement in patients who are young at the first disease onset. In this study we aimed to investigate the prevalence of low BMD in patients with newly diagnosed Crohn's disease (CD) at 20-50 years of age and the potential risk factors. METHODS: A single-center, retrospective cross-sectional study was conducted. Medical records of the patients were reviewed and their demographics, clinical characteristics and laboratory test results were collected. Dual energy X-ray absorptiometry (DEXA) scan was performed for BMD measurements; low BMD was defined as Z-score or T-score <-1.0 standard deviation (SD). Univariate and multivariate logistic regression analyses were used to determine the risk factors for low BMD. RESULTS: A total of 221 patients with CD were included; osteopenia and osteoporosis were identified in 23.1% and 8.6%, and 39.4% and 7.2% of the patients using Z-score and T-score, respectively. Female gender and a higher BMI at diagnosis were protective factors for low BMD. CONCLUSIONS: Low BMD is common in patients with newly diagnosed CD aged 20-50 years. Female gender and a higher BMI at diagnosis might protect CD patients from bone loss. Therefore, BMD measurement and early intervention with calcium and vitamin D are recommended for these patients.

3D Lanthanide Neodymium Porphyrin Metal-Organic Framework for Photocatalytic Oxidation of Styrene.

A novel three-dimensional lanthanide porphyrin-based MOF (Nd-PMOFs) was synthesized by using tetracarboxyphenyl porphyrin as the ligand and the lanthanide Nd as the coordination metal. Its specific crystal structure information was obtained by single-crystal diffraction with the space group C2/c and the empirical formula C72H45N6Nd2O15.25. This new Nd porphyrin-based MOF with an organic framework formed by a unique coordination method enables the effective separation of photogenerated electrons and holes under photoluminescence, giving it excellent photocatalytic property which could be verified by the characterization data. The photocatalytic performance was examined by taking tert-butyl hydroperoxide as the oxidant and Nd-PMOFs as the catalyst for photocatalytic oxidation of styrene to benzaldehyde with 91.4% conversion and 81.2% benzaldehyde selectivity under optimal reactions, which surpasses most of the results reported in the literature. Several styrenes with other substituents were screened to explore the general applicability of Nd-PMOF for photocatalysis of styrene, among which Nd-PMOFs also exhibited excellent photocatalytic performance. This work offers the possibility to apply lanthanide organometallic frameworks, which are widely used in fluorescent materials, to photocatalysis. In addition, it also provides a new method for the catalytic generation of benzaldehyde from styrene that is consistent with the needs of modern green development.

Visible-Light-Mediated NHC and Tertiary Amine Catalysis Enabling α-H Acylation of Alkenes.

An intermolecular direct α-C-H acylation of alkenes was revealed by the visible-light-mediated N-heterocyclic carbene and quinuclidine catalysis. This convenient protocol provides a facile synthesis toward novel natural products and drug derivatives of α-substituted vinyl ketones. Mechanistic investigations indicated that the transformation proceeded via sequential radical addition, radical coupling, and an elimination process.

Copper-Catalyzed Monofluoroalkylation of Allyl Phosphates with Nucleophilic Ethyl 2-Fluoro-2-(trimethylsilyl)acetate.

An efficient method for C(sp3)-CHF bond formation was successfully developed by copper-catalyzed cross-coupling of allyl phosphate with 2-fluoro-2-(trimethylsilyl)acetate. Under moderate circumstances, the conversion was carried out in a good strategic range to provide a series of monofluoroalkylation products in high yields, which also demonstrates the practicality of gram-scale reactions.

Cooling neutral atoms into maximal entanglement in the Rydberg blockade regime.

We propose a cooling scheme to prepare stationary entanglement of neutral atoms in the Rydberg blockade regime by the combination of periodically collective laser pumping and dissipation. In each cycle, the controlled unitary dynamics process can selectively pump atoms away from the nontarget state while keeping the target state unchanged. The subsequent dissipative process redistributes the populations of ground states through the engineered spontaneous emission. After a number of cycles, the system will eventually be stabilized into the desired steady state, independent of the initial state. This protocol does not rely on coherent addressing of individual neutral atoms or fine control of Rydberg interaction intensity, which can, in principle, greatly improve the feasibility of experiments in related fields.

Cooperative NHC and Photoredox Catalysis for the Synthesis of 1,4-Dicarbonyl Compounds via Diacylation of Alkenes.

An intermolecular 1,2-diacylation of alkenes is disclosed via cooperative N-heterocyclic carbene and photoredox catalysis under the mediation of PPh3 and Cs2CO3. This protocol provides a practical approach for construction of 1,4-dicarbonyl compounds toward novel diketone and pharmaceutical derivatives. Furthermore, the regioselective dicarbonyl compounds can be synthesized by adding acyl azolium salt. Mechanistic investigations suggest that the process was a critical radical/radical cross coupling of ketyl radicals with benzylic C-radicals.

Regioselective Alkylpolyfluoroarylation of Styrenes by Copper-Catalyzed C(sp3)-H and C(sp2)-H Double Activation.

A novel dehydrogenative dicarbofunctionalization of vinyl arenes with polyfluoroarenes and unactivated alkanes enabled by copper catalysis has been accomplished under mild conditions. This transformation provides a regioselective route to highly functionalized polyfluoroaryl compounds that occur as structural scaffolds in a variety of pharmaceuticals and materials. Preliminary mechanistic studies indicate that the carbon-based radical and copper intermediate are involved in the reaction, and the reaction pathway is dominated by the bond dissociation energy (BDE) of C(sp3)-H bonds.

Habitual tea consumption and postoperative delirium after total hip/knee arthroplasty in elderly patients: The PNDABLE study.

PURPOSE: To clarify the effects of habitual tea consumption on postoperative delirium (POD) in elderly patients undergoing total hip/knee arthroplasty. PATIENTS AND METHODS: A prospective cohort study was carried out at Qingdao Municipal Hospital Affiliated to Qingdao University between June 2020 and June 2021. A total of 332 patients aged 65-85 years undergoing total hip/knee arthroplasty under combined spinal and epidural anesthesia were enrolled from the Perioperative Neurocognitive Disorder and Biomarker Lifestyle (PNDABLE) study in the final analysis, consisting of 168 patients with habitual tea consumption and 164 patients with infrequent tea consumption. The primary endpoint was the effects of habitual tea consumption on POD and the incidence of POD, which was assessed by the Confusion Assessment Method (CAM) twice daily during the first 7 postoperative days, and POD severity was measured by the Memorial Delirium Assessment Scale (MDAS). The secondary endpoints were the concentrations of caffeine and tea polyphenols in plasma and cerebrospinal fluid (CSF), which were detected by the enzyme-linked immunosorbent assay. RESULTS: POD occurred in 61 of 332 patients (18.37%), among whom 19 had habitual tea consumption (5.72%) and 42 had infrequent tea consumption (12.65%). Habitual tea consumption (odds ratio [OR] = 0.370, 95% confidence interval [CI]: 0.205-0.670, P = .001) was significantly associated with POD in the logistic analysis, and then after adjusting for age and American Society of Anesthesiologists (ASA) physical status (OR = 0.353, 95% CI: 0.190-0.655, P = .001). Furthermore, caffeine in T0 plasma (OR = 0.834, 95% CI: 0.752-0.924, P = .001), T1 plasma (OR = 0.818, 95% CI: 0.738-0.908, P < .001), and CSF (OR = 0.899, 95% CI: 0.820-0.984, P = .022) and tea polyphenols in T0 plasma (OR = 0.541, 95% CI: 0.416-0.704, P < .001), T1 plasma (OR = 0.477, 95% CI: 0.359-0.633, P < .001), and CSF (OR = 0.526, 95% CI: 0.397-0.696, P < .001) were associated with POD after adjusting for age and ASA physical status. CONCLUSION: Habitual tea consumption may be associated with a lower incidence of POD in elderly patients.

Metal-Free Transformation of Sulfonyl Oxime Ethers with Amines to Oxime Ethers.

Sulfonyl oxime ethers undergo facile radical substitutions with various amines to yield the corresponding oxime ethers. An efficient arylation of sulfonyl oxime ethers was accomplished under ambient temperature and metal-free conditions, with a wide range of functional group tolerance. Mechanistic investigations indicate that a phenyl radical is involved in the catalytic cycle.

Traditional Chinese Medicine Strategy for Patients with Tourette Syndrome Based on Clinical Efficacy and Safety: A Meta-Analysis of 47 Randomized Controlled Trials.

OBJECTIVE: Although increasing evidence reveals the efficacy of traditional Chinese medicine (TCM) and its safety on Tourette Syndrome (TS) patients, whether TCM is indeed improving TS remains unclear. The purpose of the current study is to perform a meta-analysis to evaluate the efficacy and safety of TCM on treating TS patients. METHOD: An elaborate search strategy was conducted based on several databases including Medline, Embase, Cochrane, Web of Science, CINAHL, CBM, VIP, CNKI, and Wanfang Data in order to identify the relevant randomized controlled trials (RCTs) from their inception to as late as May 1st, 2020. General information and data needing analysis were extracted simultaneously for the necessity of various analyses such as descriptive analysis and metaquantitative analysis. RESULTS: Forty-seven trials with 5437 TS patients in total were eventually included according to our criteria. All trials were conducted in China, and the publication years ranged from 2004 to 2017. In terms of clinical efficacy, clinical symptoms of patients with TCM were more likely to be improved compared with the control group (odds ratio, OR = -1.29, 95% confidence interval, CI: -2.54 to -0.06, I 2 = 0.00%). As to the outcome of recurrence rate, the pooled results revealed that the TCM group was more inclined to stabilize the recurrence (OR = 0.44, 95% CI: 0.24 to 0.78, I 2 = 0.00%). Similar results were observed in adverse reaction (OR = 0.32, 95% CI: 0.24 to 0.43, I 2 = 32.90%). CONCLUSION: The results of our study recommend applying TCM to treat TS patients for better efficacy and safety. Results need to be interpreted cautiously due to certain limitations in our study.

Whole transcriptome sequencing and integrated network analysis elucidates the effects of 3,8-Di-O-methylellagic acid 2-O-glucoside derived from Sanguisorba offcinalis L., a novel differentiation inducer on erythroleukemia cells.

Acute erythroid leukemia (AEL) is a rare and aggressive hematologic malignancy with no specific treatment. Sanguisorba officinalis L. (S. officinalis), a well-known traditional Chinese medicine, possesses potent anticancer activity. However, the active components of S. officinalis against AEL and the associated molecular mechanisms remain unknown. In this study, we predicted the anti-AML effect of S. officinalis based on network pharmacology. Through the identification of active components of S. officinalis, we found that 3,8-Di-O-methylellagic acid 2-O-glucoside (DMAG) not only significantly inhibited the proliferation of erythroleukemic cell line HEL, but also induced their differentiation to megakaryocytes. Furthermore, we demonstrated that DMAG could prolong the survival of AEL mice model. Whole-transcriptome sequencing was performed to elucidate the underlying molecular mechanisms associated with anti-AEL effect of DMAG. The results showed that the total of 68 miRNAs, 595 lncRNAs, 4030 mRNAs and 35 circRNAs were significantly differentially expressed during DMAG induced proliferation inhibition and differentiation of HEL cells. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analyses revealed that the differentially expressed miRNAs, lncRNAs, mRNAs and circRNAs were mainly involved in metabolic, HIF-1, MAPK, Notch pathway and apoptosis. The co-expression networks showed that miR-23a-5p, miR-92a-1-5p, miR-146b and miR-760 regulatory networks were crucial for megakaryocyte differentiation induced by DMAG. In conclusion, our results suggest that DMAG, derived from S. officinalis might be a potent differentiation inducer of AEL cells and provide important information on the underlying mechanisms associated with its anti-AEL activity.

One-step implementation of Toffoli gate for neutral atoms based on unconventional Rydberg pumping.

Compared with the idea of universal quantum computation, a direct synthesis of a multiqubit logic gate can greatly improve the efficiency of quantum information processing tasks. Here we propose an efficient scheme to implement a three-qubit controlled-not (Toffoli) gate of neutral atoms based on unconventional Rydberg pumping. By adjusting the strengths of Rabi frequencies of driving fields, the Toffoli gate can be achieved within one step, which is also insensitive to the fluctuation of the Rydberg-Rydberg interaction. Considering different atom alignments, we can obtain a high-fidelity Toffoli gate at the same operation time ∼7 µs. In addition, our scheme can be further extended to the four-qubit case without altering the operating time.

Correction to: miR-205-5p inhibits human endometriosis progression by targeting ANGPT2 in endometrial stromal cells.

An amendment to this paper has been published and can be accessed via the original article.

miR-205-5p inhibits human endometriosis progression by targeting ANGPT2 in endometrial stromal cells.

BACKGROUND: miRNA expression profiles in ectopic endometrium (EC) serving as pathophysiologic genetic fingerprints contribute to determining endometriosis progression; however, the underlying molecular mechanisms remain unknown. METHODS: miRNA microarray analysis was used to determine the expression profiling of EC fresh tissues. qRT-PCR was performed to screen miR-205-5p expression in EC tissues. The roles of miR-205-5p and its candidate target gene, angiopoietin-2 (ANGPT2), in endometriosis progression were confirmed on the basis of both in vitro and in vivo systems. miR-205-5p and ANGPT2 expression were measured by in situ hybridization and immunochemistry, and their clinical significance was statistically analysed. RESULTS: miR-205-5p was screened as a novel suppressor of endometriosis through primary ectopic endometrial stromal cell migration, invasion, and apoptosis assay in vitro, along with endometrial-like xenograft growth and apoptosis in vivo. In addition, ANGPT2 was identified as a direct target of miR-205-5p through bioinformatic target prediction and luciferase reporter assay. Re-expression and knockdown of ANGPT2 could respectively rescue and simulate the effects induced by miR-205-5p. Importantly, the miR-205-5p-ANGPT2 axis was found to activate the ERK/AKT pathway in endometriosis. Finally, miR-205-5p and ANGPT2 expression were closely correlated with the endometriosis severity. CONCLUSION: The newly identified miR-205-5p-ANGPT2-AKT/ERK axis illustrates the molecular mechanism of endometriosis progression and may represent a novel diagnostic biomarker and therapeutic target for disease treatment.

Irradiation-Induced Cobaloxime-Catalyzed C-H Monofluoroalkylation of Styrenes at Room Temperature.

A cobaloxime-catalyzed photochemical synthesis of allyl monofluorides from styrenes is described herein. This method is characterized by mild reaction conditions, low-cost catalyst, and broad substrate scope. Furthermore, this convenient method will provide a facile synthesis toward novel monofluoroalkylated natural product and pharmaceutical derivatives. Mechanistic investigations indicate that a monofluoroalkyl radical is involved in the catalytic cycle.