Synthesis of <i>a</i>‑Alkylated Ketones via Tandem Acceptorless Dehydrogenation/<i>a</i>‑Alkylation from Secondary and Primary Alcohols Catalyzed by Metal–Ligand Bifunctional Iridium Complex [Cp*Ir(2,2′-bpyO)(H₂O)]

A new strategy for the synthesis of α-alkylated ketones via tandem acceptorless dehydrogenation/α-alkylation from secondary and primary alcohols was proposed and accomplished. In the presence of metal–ligand bifunctional iridium complex [Cp*Ir­(2,2′-bpyO)­(H₂O)], various desirable products were obtained in high yields. Compared with previous methods for the direct dehydrogenative coupling of secondary alcohols with primary alcohols to α-alkylated ketones, this protocol has obvious advantages including complete selectivity for α-alkylated ketones and more environmentally benign conditions. Notably, the study also exhibited the potential to develop tandem reactions catalyzed using a metal–ligand bifunctional iridium complex

α‑Alkylation of Ketones with Primary Alcohols Catalyzed by a Cp*Ir Complex Bearing a Functional Bipyridonate Ligand

A Cp*Ir complex bearing a functional bipyridonate ligand was found to be a highly effective and versatile catalyst for the α-alkylation of ketones with primary alcohols under extremely environmentally benign and mild conditions (0.1 equiv of Cs₂CO₃ per substrate, reflux in <i>tert</i>-amyl alcohol under an air atmosphere for 6 h). Furthermore, this complex also exhibited a high level of catalytic activity for the α-methylation of ketones with methanol. The mechanistic investigation revealed that the carbonyl group on the ligand is of critical importance for catalytic hydrogen transfer. Notably, the results of this study revealed the unique potential of Cp*Ir complexes bearing a functional bipyridonate ligand for the development of C–C bond-forming reactions with the activation of primary alcohols as electrophiles

Effective Recognition of Different Types of Amino Groups: From Amino­benzene­sulfonamides to Amino‑(<i>N</i>‑alkyl)­benzene­sulfonamides via Iridium-Catalyzed <i>N</i>‑Alkylation with Alcohols

A simple, highly efficient, and general strategy for the direct synthesis of amino-(<i>N</i>-alkyl)­benzene­sulfonamides has been accomplished via direct <i>N</i>-alkylation of amino­benzene­sulfonamides bearing both different types of amino groups with alcohols as alkylating agents. Notably, this research exhibited the potential for the recognition of different types of amino groups in the <i>N</i>-alkylation of complex molecules with alcohols, facilitating the progress of the transition-metal-catalyzed “hydrogen autotransfer (or hydrogen-borrowing) process.

Rhodium(III)-Catalyzed Triple Aryl/Alkenyl C–H Bond Activation of Aryl Enaminones to Access Naphtho[1,8-<i>bc</i>]pyrans

Rhodium(III)-catalyzed triple C–H bond activation of aryl enaminones was achieved to access naphtho[1,8-bc]pyrans by oxidative annulation to internal alkynes. 1-Naphthols might be formed as the only products, depending on the steric and/or electronic environment around the aroyl moiety of the aryl enaminones or the electronic impact from the alkynes. With propargyl alcohols as the masked terminal alkynes, aryl enaminones underwent rhodium(III)- or rhodium(I)-catalyzed internal alkenyl C–H bond activation to afford functionalized but-2-ene-1,4-diones. The resultant naphtho[1,8-bc]pyrans are highly fluorescent and can be further transformed by chlorination, bromination, and difluoromethylation, demonstrating potential practicability of the synthetic protocol

Comparative Study on the Transcriptome of Maize Mature Embryos from Two China Elite Hybrids Zhengdan958 and Anyu5

<div><p>Zhengdan958 and Anyu5 are two elite maize hybrids of China, which manifest similar paternal lines (Chang7-2) but different maternal lines (Zheng58 and Ye478). Zhengdan958 has a 10–15% yield advantage over Anyu5. In this study, we applied digital gene expression technology to analyze transcriptomes of mature embryos from the two hybrids and their parents, aimed to investigate molecular mechanism of heterosis and genetic effects of maternal lines. Results showed that 71.66% and 49.70% of differentially expressed genes exhibited non-additive expression in Zhengdan958 and Anyu5, respectively. The number of non-additive genes involved in abiotic and biotic stress responses in Zhengdan958 was higher than that in Anyu5, which was in agreement with their phenotypic performance. Furthermore, common over-dominance and under-dominance genes (137 and 162, respectively) between the two hybrids focused on plant development and abiotic stress response. Zhengdan958 contained 97 maternal expression-level dominance (maternal-ELD) genes, and the number was higher than that of Anyu5 (45). Common up-regulated maternal-ELD genes were significantly enriched in meristem and shoot development while common down-regulated maternal-ELD genes were involved in pyruvate metabolic process, negative regulation of catalytic activity and response to stress. Therefore, non-additive genes mainly contribute to heterosis in Zhengdan958, including many genes for plant development, abiotic and biotic stress responses. Maternal effects may play important roles in maize heterosis.</p></div

GO enrichment analysis of specific maternal expression-level dominance genes of Ye478.

<p>GO enrichment analysis of specific maternal expression-level dominance genes of Ye478.</p

Reagent-Controlled Tandem Reactions of Vinyl Epoxides: Access to Functionalized γ‑Butenolides

A new approach to functionalized γ-butenolides based on reagent-controlled tandem reaction sequences of Morita–Baylis–Hillman-type vinyl epoxides is described. The nucleophilic addition of a tertiary phosphine to the electron-deficient alkene led to ring-opening of the epoxide followed by lactonization to produce phosphonium ylides, which could undergo Wittig olefination with aryl trifluoromethyl ketones and aryl aldehydes to give 3-alkenyl γ-butenolides in moderate to good yields and high <i>E</i>/<i>Z</i> selectivity. Tertiary amine promoted the Michael-type addition of carbon- and nitrogen-based nucleophiles to the vinyl epoxides followed by lactonization to provide diverse 3-substituted γ-butenolides

Stirring-Time Control Approach to Manage Colloid Nucleation Size for the Fabrication of High-Performance Sn-Based Perovskite Solar Cells

Colloidal nucleation is first observed to exist in a Sn-based perovskite solution, and its components and size are discovered to alter in real time with stirring time. Then, a simple stirring-time control approach is developed to manage the size of the colloids, and with continuous stirring for 3 days an optimal colloid with size <10 nm is confirmed to successfully form a continuous, dense, high-quality perovskite film. Herein, the colloids exist in the form of [SnI6]4– complete coordination compounds, with which a compact FA0.75MA0.25SnI3 perovskite film with reduced defects and enhanced crystallinity concentration is obtained as nucleation sites, and a planar inverted perovskite solar cell with a champion power conversion efficiency of 10.74% is eventually realized. This work provides a novel perspective to enhance perovskite film quality and thus device performance via controlling high-quality nucleation in precursor solution

Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

The complete detoxification of hazardous organic pollutants is crucial for water treatment. However, this often requires the cooperation of multiple treatment processes catalyzed by different catalysts, leading to a complex water treatment infrastructure design and high operational costs. To address this challenge, we developed fully exposed palladium (Pd) ensemble (Pdn)-loaded ultrathin Co3O4 nanosheets (NSs) (Pdn/Co3O4 NSs) as a reductive–oxidative dual-active catalyst for the efficient detoxification of halogenated organic pollutants. During the treatment of simulated water contaminated by 4-chlorophenol (4-CP), a representative persistent organic pollutant, Pdn reactive centers rapidly hydrodechlorinate 4-CP into low-toxicity phenol with activity ≥10 times that of benchmark catalysts. The synergy between the Pd ensembles and oxygen vacancies further promotes the rapid and selective hydrogenation of phenol into cyclohexanone on Co3O4 NSs. Subsequently, cyclohexanone is oxidized by peroxymonosulfate (PMS) under Co3O4 activation. A cell assay-based toxicity study confirmed that stimulated polluted environmental water is fully detoxified after treatment with the designed Pdn/Co3O4 NSs catalyst. This study provides new insights into the rational design of Pd catalysts for the catalytic removal of persistent organic pollutants, particularly halogenated aromatics, paving the way for facile, low-cost, and highly efficient water treatment processes

Data_Sheet_1_Anxiety, depression, and somatic symptom disorders in health care workers at high altitude during the rapid spread of the SARS-CoV-2 Omicron variant: A prospective cohort study.docx

ObjectiveThe ongoing spread of the Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) Omicron variant and hypoxia exposure to high altitude are the susceptible factors of people’s psychological abnormalities, especially the health care workers (HCWs) in the front line of the epidemic. There is no dynamic observation data on the prevalence of mental health disorders among HCWs at high altitude. The study is to assess the prevalence of mental health outcomes and its influencing factors among HCWs at high altitude exposed to the SARS-CoV-2 Omicron variant.MethodsThis prospective cohort study collected sociodemographic data and mental health measurements from 647 HCWs in 3 hospitals in Xining, Qinghai province from 13 April to 4 May 2022. After the mental health intervention for the above-mentioned people in the Chengdong district, we collected mental health indicators on days 7 and 14, respectively. We used the generalized linear model and the generalized estimation equation and for further analysis.ResultsThe baseline cross-sectional survey of 647 HCWs in the Chengdong and Chengbei districts of Xining, Qinghai province shows that the prevalence of depression, anxiety, and somatic disorders were 45.75, 46.52, and 52.55%, respectively. The multivariable model showed that chronic diseases and nucleic acid collection were associated with increased scores of GAD-7, PHQ-9, and PHQ-15. And the GAD-7 score of HCWs with elderly people at home increased by 0.92 points. Subsequent repeated measurements of the mental health of HCWs in Chengdong district in Xining, Qinghai province, showed that anxiety, depression, and somatic disorders were significantly relieved, and physical exercise showed a significant protective effect, while loans and nucleic acid collection showed an adverse effect after 2 weeks of intervention. Additionally, engaged in nucleic acid collection was the risk factor of anxiety and depression.ConclusionIn this survey of HCWs on frontline at high altitude during the rapid spread of the SARS-CoV-2 Omicron variant, participants reported experiencing mental health disorders, especially in those with chronic disease, loans, and those who worked with longer hours and engaged in nucleic acid collection in Xining, Qinghai province, China. Exercise may help to improve anxiety and physical disorders.</p