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Particle-attached bacterial (PAB) communities play pivotal roles in water organic matter decomposition, nutrient cycling, and the natural self-purification processes. However, we know little about their responses to seasonal environmental fluctuations, under eutrophication in reservoir ecosystems. In this study, we studied the shifts of PAB communities to seasonal environmental fluctuations in tropical China. Trophic state index (TSI) indicated that the studied reservoirs ranged from mesotrophic to eutrophic state with a gradual increase in TSI from 31 to 58. In eutrophic reservoirs, Cyanobacteria, especially Raphidiopsis raciborskii, significantly increased in its relative abundance from wet to dry season, but Synechococcales and Microcystaceae decreased. In contrast, the relative abundance of Clostridia, Bacilli, Coriobacteriia, Enterobacteriales, and Vibrionales were more susceptible to seasonal environmental fluctuations in mesotrophic than eutrophic reservoirs. PAB co-occurrence relationships in mesotrophic reservoirs varied more greatly in response to seasonal environmental fluctuations, compared with eutrophic reservoirs, in terms of topological properties of connectedness, average degree, robustness and vulnerability. Our results further demonstrated that the seasonal stability of PAB co-occurrence relationships was strongly correlative with TSI through mediating key bacterial taxa and community biodiversity. We proposed that eutrophication dramatically reduced the seasonal variation of PAB community compositions and co-occurring relationships in reservoir ecosystems., (© The Author(s) 2024. Published by Oxford University Press on behalf of FEMS.)

The role of circadian rhythm genes (CRGs) in gastric cancer (GC) is poorly understood. This study aimed to develop a CRG signature to improve understanding of prognosis and immunotherapy responses in GC patients. We integrated the The Cancer Genome Atlas-Stomach adenocarcinoma (TCGA-STAD) dataset with CRGs to develop a prognostic signature for GC. The signature's predictive ability was validated using Kaplan-Meier and ROC curves. The CIBERSORT algorithm evaluated immune cell proportions, and tumor immune dysfunction and exclusion score, as well as immune phenotype score, determined the response to immunotherapy for STAD patients. Finally, we assessed signature genes expression using real-time quantitative polymerase chain reaction. We developed a 4-CRG signature for STAD, demonstrating accurate prognostic ability. The low-risk group showed increased B cell memory and CD8 + T cells, and decreased M2 Macrophages compared to the high-risk group. Patients in the low-risk group had a higher likelihood of benefiting from immunotherapy. Additionally, gastric cancer tissues exhibited elevated expression of OPN3 and decreased expression of TP53 compared to adjacent tissue. This study successfully established a prognostic signature for CRGs, accurately predicting prognosis and immunotherapeutic response among STAD patients, providing insights for the development of personalized therapeutic strategies for these patients., (© 2024. The Author(s).)

Stereoconvergent reactions enable the transformation of mixed stereoisomers into well-defined, chiral products─a crucial strategy for handling Z / E -mixed olefins, which are common but challenging substrates in organic synthesis. Herein, we report a stereoconvergent and highly enantioselective method for synthesizing Z -homoallylic alcohols via the nickel-catalyzed reductive coupling of Z / E -mixed 1,3-dienes with aldehydes. This process is enabled by an N -heterocyclic carbene ligand characterized by C 2 -symmetric backbone chirality and bulky 2,6-diisopropyl N -aryl substituents. Our method achieves excellent stereocontrol over both enantioselectivity and Z -selectivity in a single step, producing chiral Z -homoallylic alcohols that are valuable in natural products and pharmaceuticals.

Objective: To investigate the differences in resting-state functional connectivity (FC) between patients with vestibular migraine (VM) and migraine without aura (MwoA) in order to infer the possible neuroimaging mechanisms of VM. Methods: Thirty VM patients admitted to the Department of Neurology of the Second Affiliated Hospital of Xuzhou Medical University from December 2019 to December 2022 were selected as the experimental group (EG) (6 males and 24 females, with mean age of 38.3 years) and 26 MwoA patients as the control group (7 males and 19 females, mean age 35.5 years). General demographic and clinical data such as gender, age, year of education, course of disease and frequency of attacks were collected for all the patients, as well as data of Hamilton Anxiety Scale (HAMA), Hamilton Depression Scale (HAMD), Montreal Cognitive Assessment (MoCA), headache Visual Arialogue Scale (VAS), Headache Impact Test 6 (HIT-6) and Migraine Disability Assessment Questionnaire (MIDAS). VM patients were also assessed by Dizziness Handicap Inventory (DHI), dizziness VAS and Vestibular Disorders Activities of Daily Living (VADL) scales. All patients underwent resting-sate functional Magnetic Resonance Imaging (fMRI) scans. Bilateral parietal opercular cortex 2 (OP2) and primary visual cortex (V1) were used as regions of interests (ROIs). Differences in FC between ROIs and other brain regions were calculated between the two groups. In view of the brain regions with significant differences, z-values of FC were extracted for each subject in the EG, and Pearson partial correlation analysis was conducted between z-values of FC and clinical characteristics of patients, P <0.05 was considered to have significant correlation. SPSS 22.0 was used for statistical analysis. Results: There was no significant difference in gender, age, years of education, course of disease, frequency of attack and scores of MoCA, HAMA and HAMD between the two groups ( P >0.05). Headache VAS, HIT-6 and MIDAS scores in VM patients were significantly lower than those in MwoA patients ( P <0.05). Compared with MwoA patients, the FC between left OP2 and bilateral precuneus and left thalamus was significantly increased in VM patients, and the FC between right OP2 and left thalamus and right anterior cingulate gyrus were significantly increased ( P <0.05, False Discovery Rate correction). Correlation analysis showed that the FC between left OP2 and left precuneus was positively correlated with DHI score in VM patients ( P =0.007, r =0.480), and the FC between right OP2 and left thalamus was positively correlated with the disease course in VM patients ( P =0.015, r =0.439). Conclusions: The pathogenesis of VM may be related to the altered FC of vestibular, pain and visual-motor networks, abnormalities of these neural pathways may be important imaging biomarkers of VM pathogenesis.

The method of ultra-high performance liquid chromatography-quadrupole-electrostatic field orbitrap high-resolution mass spectrometry(UHPLC-Q/Orbitrap HRMS)combined with molecular network was developed in this study for rapidly analyzing the chemical components of the Qinggu San reference sample of classical prescription. Firstly, an ACQUITY UPLC BEH Shield RP&#95;(18) column(2.1 mm×100 mm, 1.7 μm)was used, and acetonitrile and 0.1% formic acid were taken as the mobile phases for gradient elution. The flow rate was 0.4 mL·min~(-1), and the column temperature was 30 ℃. Under these conditions, the mass spectrum data were collected in both positive and negative ion modes of the heated electrospray ionization source. Subsequently, the mass spectrum data of the Qinggu San reference sample were uploaded to the Global Natural Products Social Molecular Network(GNPS)platform for calculation and analysis, and a visual molecular network was built with Cytoscape 3.8.2 software. On this basis, the chemical components of the Qinggu San reference sample were identified by fragmentation regularity of standard compounds, retention time, accurate relative molecular weight of HR-MS, characteristic fragment ions information, literature, and databases. Finally, a total of 105 chemical components were identified and speculated in the Qinggu San reference sample, including 19 iridoid glycosides, 23 flavonoids, 15 phenylpropanoids, 11 triterpene saponins, and 37 other components. Meanwhile, two of these components are potential new compounds. The method used in this study not only achieved rapid and accurate identification of chemical components in the Qinggu San reference sample and provided a scie-ntific basis for the study of pharmacological substances and quality control of Qinggu San compound preparations but also provided a refe-rence for the rapid identification of chemical components in traditional Chinese medicine compound preparations.

Unactivated aliphatic alkenes are particularly desirable as starting materials because they are readily accessible in large quantities, but the enantioselective intermolecular reductive coupling of unactivated alkenes with imines is challenging. In this paper, we report a method for nickel-catalyzed intermolecular reductive coupling reactions between aliphatic alkenes and imines to yield chiral amines with excellent enantioselectivities and good linear selectivities. The reaction conditions are compatible with a broad range of aliphatic alkenes, including those derived from bioactive molecules. The success of this method can be attributed to the use of newly developed monodentate chiral spiro phosphine ligands.

Highly substituted aminotetrahydropyrans were synthesized via sequential C-H functionalizations. The process was initiated with a Pd(II)-catalyzed stereoselective γ-methylene C-H arylation of aminotetrahydropyran, followed by α-alkylation or arylation of the corresponding primary amine. The initial γ-C-H (hetero)arylation was compatible with a range of aryl iodides containing various substituents and provided the corresponding products in moderate to good yields. The subsequent α-alkylation or arylation of the isolated arylated products proceeded with high diastereoselectivity to afford value-added disubstituted aminotetrahydropyrans.

We developed a method for the enantioselective synthesis of germanium-stereogenic compounds by the desymmetric carbene insertion of dihydrogermanes. A chiral rhodium phosphate catalyst decomposes diaryldiazo-methanes to generate rhodium carbenes that insert enantioselectively into one of the two Ge-H bonds of dihydrogermanes to form germanium-stereogenic compounds under mild reaction conditions. By this method, a variety of chiral germanes with germanium-stereogenic centers were synthesized in high yields and excellent enantioselectivities. Kinetic studies of the reaction showed that the diazo decomposition process was the rate-determining step. The remaining Ge-H bond of the chiral germane products provides a possibility for preparing chiral tetra-substituted germanium-stereogenic compounds.

Ligand modulation of transition-metal catalysts to achieve optimal reactivity and selectivity in alkene hydrofunctionalization is a fundamental challenge in synthetic organic chemistry. Hydroaminoalkylation, an atom-economical approach for alkylating amines using alkenes, is particularly significant for amine synthesis in the pharmaceutical, agrochemical, and fine chemical industries. However, the existing methods usually require specific substrate combinations to achieve precise regio- and stereoselectivity, which limits their practical utility. Protocols allowing for regiodivergent hydroaminoalkylation from the same starting materials, controlling both regiochemical and stereochemical outcomes, are currently absent. Herein, we report a ligand-controlled, regiodivergent nickel-catalyzed hydroaminoalkylation of unactivated alkenes with N -sulfonyl amines. The reaction initiates with amine dehydrogenation and involves aza-nickelacycle intermediates. Tri tert -butylphosphine promotes branched regioselectivity and syn diastereoselectivity, whereas ethyldiphenylphosphine enables linear selectivity, yielding regioisomers with inverse orientation. Systematic evaluation of diverse monodentate phosphine ligands reveals distinct regioselectivity cliffs, and % V bur ( min ), a ligand steric descriptor, was established as a predictive parameter correlating ligand structure to regioselectivity. Computational investigations supported experimental findings, offering mechanistic insights into the origins of regioselectivity. Our method provides an efficient and predictable route for amine synthesis, demonstrating broad substrate scope, excellent tolerance toward various functional groups, and practical advantages. These include the use of readily available starting materials and cost-effective nickel(II) salts as precatalysts.

Inflammatory bowel disease (IBD), mainly comprising ulcerative colitis and Crohn's disease, is a group of gradually progressive diseases bringing significant mental anguish and imposes serious economic burdens. Interplay of genetic, environmental, and immunological factors have been implicated in its pathogenesis. Nutrients, as crucial environmental determinants, mainly encompassing carbohydrates, fats, proteins, and micronutrients, are closely related to the pathogenesis and development of IBD. Nutrition is essential for maintaining the dynamic balance of intestinal eco-environments to ensure intestinal barrier and immune homeostasis, while this balance can be disrupted easily by maladjusted nutrition. Research has firmly established that nutrition has the potential to shape the composition and function of gut microbiota to affect the disease course. Unhealthy diet and eating disorders lead to gut microbiota dysbiosis and further destroy the function of intestinal barrier such as the disruption of membrane integrity and increased permeability, thereby triggering intestinal inflammation. Notably, appropriate nutritional interventions, such as the Mediterranean diet, can positively modulate intestinal microecology, which may provide a promising strategy for future IBD prevention. In this review, we provide insights into the interplay between nutrition and gut microbiota and its effects on IBD and present some previously overlooked lines of evidence regarding the role of derived metabolites in IBD processes, such as trimethylamine N-oxide and imidazole propionate. Furthermore, we provide some insights into reducing the risk of onset and exacerbation of IBD by modifying nutrition and discuss several outstanding challenges and opportunities for future study., (© 2024 Chinese Medical Association Shanghai Branch, Chinese Society of Gastroenterology, Renji Hospital Affiliated to Shanghai Jiaotong University School of Medicine and John Wiley & Sons Australia, Ltd.)

Keratin 80 (KRT80) is a filament protein that participates in cell differentiation and the integrity of the epithelial barrier. Here, KRT80 expression was higher in gastric cancer compared with normal mucosa at both mRNA and protein levels by bioinformatic analysis, qRT-PCR and Western blot (p<0.05), however, the methylation of KRT80 was lower than in normal mucosa (p<0.05). There was a negative relationship between promoter methylation and expression level of KRT80 gene in gastric cancer (p<0.05). KRT80 mRNA and protein expression was positively correlated with the differentiation of gastric cancer (p<0.05), while KRT80 methylation was negatively associated with gastric cancer differentiation and p53 mutation (p<0.05). The expression of KRT80 mRNA was positively linked to the short survival time of gastric cancers (p<0.05). The differential genes of KRT80 mRNA were involved in ligand-receptor interaction, estrogen signal pathway, peptidase, filament and cytoskeleton, keratinocyte differentiation, vitamin D receptor, muscle contraction, and B cell-mediated immunity (p<0.05). KRT80-related genes were classified into cell adhesion and junction, cadherin binding, skin and epidermis development, and so forth (p<0.05). KRT80 knockdown suppressed proliferation, anti-apoptosis, anti-pyroptosis, migration, invasion and epithelial-mesenchymal transition in gastric cancer cells (p<0.05). These findings indicated that up-regulated expression of KRT80 played a crucial part in gastric carcinogenesis, and might be considered as a biological marker for aggressive behaviors and poor prognosis. Its silencing might be used as an approach of target therapy for gastric cancer patients., (©The Author(s) 2024. Open Access. This article is licensed under a Creative Commons CC-BY International License.)

Background: Belonging to the G-protein coupled receptor 1 family, G protein-coupled receptor 176 (GPR176) is associated with the Gz/Gx G-protein subclass and is capable of decreasing cAMP production., Methods: GPR176 expression was detected by qRT-PCR, bioinformatics analysis, Western blot and immunohistochemistry, and compared with clinicopathological characteristics of breast cancer. GPR176-related genes and pathways were subjected to bioinformatic analysis. We also explored the effects of GPR176 on the phenotypes of breast cancer cells., Results: Lower expression of GPR176 mRNA was seen in breast cancer than in normal tissues, but the opposite pattern was found for its protein (p < 0.05). GPR176 mRNA was associated with female sex, low T staging, non-Her-2 + subtypes, non-mutant p53 status in breast cancer (p < 0.05). GPR176 methylation was negatively correlated with its mRNA level and T staging in breast cancer, and was higher in breast cancer than normal tissues (p < 0.05). GPR176 protein expression was positively correlated with older age, small tumor size, and non-luminal-B subtype of breast cancers (p < 0.05). The differential genes of GPR176 were involved in receptor-ligand interaction, RNA maturation, and so forth (p < 0.05). GPR176-related genes were categorized into cell mobility, membrane structure, and so on (p < 0.05). GPR176 knockdown weakened the proliferation, glucose catabolism, anti-apoptosis, anti-pyroptosis, migration, invasion, and epithelial-mesenchymal transition of breast cancer cells., Conclusion: These results indicate that GPR176 might be involved in the tumorigenesis and subsequent progression of breast cancer by deteriorating aggressive phenotypes. It might be utilized as a potential biomarker to indicate the aggressive behaviors and poor prognosis of breast cancer and a potential target of genetic therapy., (© 2023. The Author(s).)

We present the first enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes, providing an efficient route to highly valuable homoallylic alcohols in a single step. The reaction involves the 1,4-carboboration of dienes, leading to the formation of C-C and C-B bonds accompanied by the construction of two continuous stereogenic centers. Enabled by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields products with exceptional diastereoselectivity, E -selectivity, and enantioselectivity. The diastereoselectivity of the reaction can be controlled by employing either ( Z )-1,3-dienes or ( E )-1,3-dienes.

Molecules with an allylic amine motif provide access to important building blocks and versatile applications of biologically relevant chemical space. The need for diverse allylic amines requires the development of increasingly general and modular multicomponent reactions for allylic amine synthesis. Herein, we report an efficient catalytic multicomponent coupling reaction of simple alkenes, aldehydes, and amides by combining nickel catalysis and Lewis acid catalysis, thus providing a practical, environmentally friendly, and modular protocol to build architecturally complex and functionally diverse allylic amines in a single step. The method is remarkably simple, shows broad functional-group tolerance, and facilitates the synthesis of drug-like allylic amines that are not readily accessible by other methods. The utilization of accessible starting materials and inexpensive Ni(ii) salt as the alternative precatalyst offers a significant practical advantage. In addition, the practicality of the process was also demonstrated in an efficient, gram-scale preparation of the prostaglandin agonist., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Chiral benzylic amines are privileged motifs in pharmacologically active molecules. Intramolecular enantioselective radical C(sp 3 )-H functionalization by hydrogen-atom transfer has emerged as a straightforward, powerful tool for the synthesis of chiral amines, but methods for intermolecular enantioselective C(sp 3 )-H amination remain elusive. Herein, we report a cationic copper catalytic system for intermolecular enantioselective benzylic C(sp 3 )-H amination with peroxide as an oxidant. This mild, straightforward method can be used to transform an array of feedstock alkylarenes and amides into chiral amines with high enantioselectivities, and it has good functional group tolerance and broad substrate scope. More importantly, it can be used to synthesize bioactive molecules, including chiral drugs. Preliminary mechanistic studies indicate that the amination reaction involves benzylic radicals generated by hydrogen-atom transfer., (© 2023 Wiley-VCH GmbH.)

Control of the regioselectivity of α-alkylation of carbonyl compounds is a longstanding topic of research in organic chemistry. By using stoichiometric bulky strong bases and carefully adjusting the reaction conditions, selective alkylation of unsymmetrical ketones at less-hindered α-sites has been achieved. In contrast, selective alkylation of such ketones at more-hindered α-sites remains a persistent challenge. Here we report a nickel-catalysed alkylation of unsymmetrical ketones at the more-hindered α-sites with allylic alcohols. Our results indicate that the space-constrained nickel catalyst bearing a bulky biphenyl diphosphine ligand enables the preferential alkylation of the more-substituted enolate over the less-substituted enolate and reverses the conventional regioselectivity of ketone α-alkylation. The reactions proceed under neutral conditions in the absence of additives, and water is the only byproduct. The method has a broad substrate scope and permits late-stage modification of ketone-containing natural products and bioactive compounds., (© 2023. The Author(s).)

Although ovarian cancer usually responds well to platinum- and taxane-based first-line chemotherapy, most patients develop recurrence and chemoresistance. Regenerating gene 4 (REG4) is a secretory protein involved in cell differentiation and proliferation. We found higher REG4 expression in ovarian cancer than in normal tissues ( p  < .05). Regenerating gene 4 expression was negatively associated with overall, progression-free or post-progression survival rates of patients with ovarian cancer receiving platinum or paclitaxel treatment ( p  < .05) according to a Kaplan-Meier plotter. Regenerating gene 4 overexpression resulted in either cisplatin or paclitaxel resistance, and apoptosis resistance in CAOV3 ovarian cancer cells ( p  < .05). REG4-transfected ovarian cancer cells showed stronger migration and invasion treated with cisplatin or paclitaxel ( p  < .05). Additionally, cisplatin or paclitaxel exposure led to the overexpression of phosphorylated phosphoinositide 3-kinase (p-PI3K), p-Akt, phosphorylated mammalian target of rapamycin (p-mTOR), glutathione S-transferase-π, survivin, and B-cell lymphoma 2 in REG4 transfectants compared with control cells ( p  < .05). These findings suggested that REG4 expression was up-regulated in ovarian cancer, and associated with poor survival and chemotherapy resistance. REG4 promoted the occurrence, development, and chemotherapy resistance of ovarian cancer by regulating cell proliferation, apoptosis, migration, and invasion, and PI3K/Akt/m-TOR signalling pathways. IMPACT STATEMENT What is already known on this subject? REG4 mRNA expression is up-regulated in many digestive cancers. High REG4 expression was associated with an adverse prognosis, high tumour and nodal stages, poor differentiation, and hepatic and peritoneal metastases of digestive cancers. REG4 expression conferred cancer cells with increased resistance to chemoradiotherapy, especially 5-FU-based treatment, by activating the MAPK/Erk/Bim signalling pathway. What do the results of this study add? REG4 was highly expressed in ovarian cancer. The expression of p-PI3K, p-AKT, p-mTOR, GST-π, survivin, and Bcl-2 was increased in REG4-overexpressing cells. High REG4 expression was significantly associated with inferior OS, PFS, and PPS rates in patients with ovarian cancer receiving platinum chemotherapy. REG4 mediated cisplatin and paclitaxel resistance in CAOV3 ovarian cancer cells. The percentage of apoptotic cells was markedly lower in REG4-transfected compared to mock-transfected cells after cisplatin or paclitaxel treatment. What are the implications of these findings for clinical practice and/or further research? This study aimed to evaluate the prognostic significance of REG4 expression in ovarian cancer treated with platinum and paclitaxel, to explore REG4 chemoresistance mechanisms to platinum and paclitaxel, and to provide a scientific experimental basis for the clinical treatment and outcome evaluation of ovarian cancer. In order to provide comprehensive clinical treatment of ovarian cancer, it is helpful to improve our understanding of multi-drug resistance and identify new cancer diagnostic biomarkers.

Objective: To observe the effect of electroacupuncture (EA) at "Zusanli" (ST 36) on duodenal mast cells, nerve growth factor (NGF) and neurotrophic tyrosine kinase receptor type 1 (NTRK1), and to explore the mechanism of electroacupuncture at Zusanli (ST 36) on functional dyspepsia (FD)., Methods: Sixty SPF-grade 10-day-old SD rats were randomly divided into a normal group, a model group, a ketotifen group and an EA group, 15 rats in each group. The FD model was prepared by iodoacetamide combined with rat tail clamping method in the model group, the ketotifen group and the EA group. The rats in the ketotifen group were injected intraperitoneally with ketotifen (1 mg • kg -1 • d -1 ) for 7 days; the rats in the EA group were treated with EA at bilateral "Zusanli" (ST 36), with disperse-dense wave, frequency of 2 Hz/50 Hz and intensity of 0.5 mA, 20 min each time, once a day for 14 days. The gastric emptying rate and small intestinal propulsion rate in each group were observed; the morphology of duodenal mucosa was observed by HE staining; the toluidine blue staining was used to observe the number and degranulation of mast cells in duodenal mucosa; the protein and mRNA expressions of NGF, NTRK1 in duodenum were detected by Western blot and real-time PCR; the level of interleukin-1β (IL-1β) in duodenum was measured by ELISA., Results: Compared with the normal group, the gastric emptying rate and small intestinal propulsion rate in the model group were decreased ( P <0.01); compared with the model group, the gastric emptying rate and small intestinal propulsion rate in the ketotifen group and the EA group were increased ( P <0.01); the small intestinal propulsion rate in the EA group was higher than that in the ketotifen group ( P <0.01). In the model group, local defects in duodenal mucosa were observed with a small amount of inflammatory cell infiltration; no obvious abnormality was found in duodenal mucosa of the other groups. Compared with the normal group, the mast cells of duodenal mucosa in the model group were increased significantly with significant degranulation; compared with the model group, the mast cells of duodenal mucosa in the ketotifen group and the EA group were decreased significantly, and the degranulation was not obvious. Compared with the normal group, the protein and mRNA expressions of NGF, NTRK1 as well as the level of IL-1β in duodenum in the model group were increased ( P <0.01); compared with the model group, the protein and mRNA expressions of NGF, NTRK1 as well as the levels of IL-1β in duodenum in the ketotifen group and the EA group were decreased ( P <0.01, P <0.05); compared with the ketotifen group, the mRNA expression of NGF, as well as the protein and mRNA expressions of NTRK1 in duodenum in the EA group were decreased ( P <0.05, P <0.01)., Conclusion: EA at "Zusanli" (ST 36) could inhibit the activation of duodenal mast cells and regulate the expressions of NGF and its receptor to improve the low-grade inflammatory response of duodenum, resulting in treatment effect on FD.

Occurring worldwide, blooms of Raphidiopsis raciborskii threaten the use of water resources especially in tropical and subtropical waterbodies. Its high flexibility in the uses of light and macronutrients (C, N, P) frustrates any bloom prediction and control based on macronutrients regulation. To identify the critical factors promoting periodic blooms of R. raciborskii, the trends of meteorological, hydrodynamic, physical, and chemical variables (including macro- and micronutrients: N, P, Fe) were analyzed in a Chinese tropical large reservoir (Dashahe reservoir) over five years. It was hypothesized that Fe availability, mediated by the mixing pattern of the reservoir, played a crucial role in the periodic blooms of the cyanobacterium. To have a more complete understanding, the effects of Fe on growth of a local R. raciborskii strain were tested in a monoculture experiment. The biomass and relative abundance of R. raciborskii in the reservoir showed a clear seasonal trend, with relative abundance > 50% in summer/autumn (July to October). Three habitat types along a dominance gradient were identified in the reservoir and 17 variables were used to compare them. Statistical analysis and habitat comparison showed that temperature and stratification, dissolved Fe and N concentrations in the epilimnion, and dissolved Fe and oxygen concentrations in the hypolimnion were the critical factors driving the dynamics of R. raciborskii in the study reservoir. The habitat dominated by R. raciborskii was characterized by a relatively low availability of macro resources (Z eu /Z m < 1, SRP < 0.01 mg/L, DIN < 0.3 mg/L) and by a high Fe availability supplemented from hypoxic hypolimnion. The dependence of growth on Fe concentration increase was confirmed in culture where the maximum was reached at 0.689 mg Fe /L. Our results suggest that a high Fe bioavailability, also originating from the hypoxic hypolimnion, influences the dynamics R. raciborskii and favors the blooms of the species. As a consequence, Fe concentrations in the water column as well as oxygen measurements along the water column should be routinely included in the monitoring programs aimed at predicting and controlling R. raciborskii blooms., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

We report the first example of selective Pd II -catalyzed tertiary C-H activation of cyclobutylmethyl ketones using a transient directing group. An electron-deficient 2-pyridone ligand was identified as the optimal external ligand to enable tertiary C-H activation. A variety of cyclobutylmethyl ketones bearing quaternary carbon centers was readily accessed without preinstalling internal directing groups in up to 81 % yield and >95 : 5 regioisomeric ratios of tertiary C-H arylation to β-methylene (β-methyl) or γ-C-H arylation., (© 2022 Wiley-VCH GmbH.)

Objective: To better understand the clinical characteristics of pulmonary nocardiosis associated with bronchiectasis. Methods: Patients diagnosed as bronchiectasis complicated with pulmonary nocardiosis in 9 tertiary general hospitals in China were enrolled from March 2016 to March 2020, with the record of general data, imaging performance and pathogen. The literature was reviewed. Results: Totally 17 patients were included. There were 12 females and 5 males. The ages ranged from 45 to 79 years, with an average of (63±9) years. There were 15 nonsmokers and 2 smokers, all of whom with chronic course. The clinical manifestations were mostly cough, expectoration, hemoptysis, fever, and dyspnea. The imaging manifestation was bronchiectasis in both lungs, with the most common involvement in the left lower lung, right middle lobe and left lingual lobe. Sputum cultures were positive in 10 cases, bronchoalveolar lavage fluid (BALF) cultures were positive in 6 cases, and next generation gene sequencings were positive in 4 cases, including 2 cases of Nocardia gelsenkii , 2 cases of Nocardia abscess , 2 cases of Nocardia stellate , 1 case of Nocardia mexicana , 1 case of Nocardia otitis caviae , and 9 cases of undetermined Nocardia. There were 3 cases of Klebsiella pneumoniae, 2 cases of Pseudomonas aeruginosa and 2 cases of Aspergillus . The symptoms and imaging of all patients were improved after anti Nocardia therapy. Conclusions: Bronchiectasis combined with nocardiosis is more common in middle-aged and elderly women without smoking, which is similar to the clinical manifestations of Lady Windermere syndrome. Bronchiectasis often involves the left lower lobe, right middle lobe and left lingual lobe. Nocardia infection might further precipitate the initiation and progression of bronchiectasis.

We have developed a nickel-catalyzed desymmetric reductive cyclization/coupling of 1,6-dienes. The reaction provides an efficient method for constructing a chiral tertiary alcohol and a quaternary stereocenter by a single operation. The method has excellent diastereoselectivity and high enantioselectivity, a broad substrate scope, as well as good tolerance of functional groups. Preliminary mechanism studies show that alkyl nickel(I) species are involved in the reaction., (© 2022 Wiley-VCH GmbH.)

Bromodomain and extra-terminal proteins (BETs) are potential targets for the therapeutic treatment of prostate cancer (PC). Herein, we report the design, the synthesis, and a structure-activity relationship study of 6-(3,5-dimethylisoxazol-4-yl)benzo[cd]indol-2(1H)-one derivative as novel selective BET inhibitors. One representative compound, 19 (Y06014), bound to BRD4(1) in the low micromolar range and demonstrated high selectivity for BRD4(1) over other non-BET bromodomain-containing proteins. This molecule also potently inhibited cell growth, colony formation, and mRNA expression of AR-regulated genes in PC cell lines. Y06014 also shows stronger activity than the second-generation antiandrogen enzalutamide. Y06014 may serve as a new small molecule probe for further validation of BET as a molecular target for PC drug development., (© 2021. The Author(s), under exclusive licence to CPS and SIMM.)

A ligand-enabled nickel-catalyzed intramolecular hydroalkenylation of imines with unactivated alkenes has been developed. A variety of five- and six-membered cyclic allylic amines were synthesized in high yields. The use of both wide-bite-angle diphosphine ligand and Brønsted acid is crucial for realizing the reaction. Preliminary investigation of the asymmetric intramolecular hydroalkenylation of imines shows promising potential for the application of the method in the synthesis of enantio-enriched cyclic allylic amines.

A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity-determining step., (© 2020 Wiley-VCH GmbH.)

Background: Cricopharyngeal muscle dysfunction (CPD) management has been challenging in clinical practice., Objective: To compare the efficacy and safety of ultrasound-guided botulinum toxin injection and balloon catheter dilatation in treating CPD., Methods: Forty patients with CPD were randomly divided into two groups, namely the botulinum toxin injection group (BTX group) and balloon dilatation group (BD group). Patients in the BTX group received a single ultrasound-guided injection of 50 units of botulinum toxin type A, while the BD group received dilatation therapy five times per week, consecutively for two weeks. Relative opening percentage of the upper esophageal sphincter (UES), the penetration-aspiration scale (PAS), and the Dysphagia Outcome Severity Scale (DOSS) were evaluated by a videofluoroscopic swallowing study (VFSS) at baseline, 1-month, and 3-months posttreatment. The Functional Oral Intake Scale (FOIS) and Standardized Swallowing Assessment (SSA) were also used to evaluate participants' swallowing function at baseline and the 1-week, 2-week, 1-month, and 3-month follow-ups., Results: A generalized estimating equation (GEE) model revealed the significant main effect for time in UES, PAS, DOSS, FOIS, and SSA compared to baseline (P <0.05), while no group-by-time interactions (except for the PAS assessment) or main effect for treatment was detected among the above multiple variances. No systematic complications or severe adverse effects were noted., Conclusion: Both ultrasound-guided botulinum toxin type A injections and balloon dilatation therapy have been proven as safe and effective treatments for CPD patients. Future clinical trials with longer follow-up periods and more participants are warranted.

Background and Objectives: The worldwide exclusive breastfeeding rate is suboptimal and this study aims to evaluate effects on infant immune development of formula feeding., Methods and Study Design: A prospective study including 221 infants fed with breast milk or formula was conducted. At 3-month and 9-month, the concentrations of total immunoglobulin (Ig)G, IgM, IgA, IgG1, IgG2, interleukin (IL)-4, interferon-gamma (IFN-γ) and tumor necrosis factor-alpha (TNF-α) were measured by using enzyme-linked immunosorbent assay (ELISA). Natural killer (NK) cell activity and lymphocyte transformation testing were conducted. Furthermore, the occurrence of infantile diarrhea, respiratory infections and allergic diseases were questioned., Results: The levels of total IgG (Z=-3.21, p=0.001), IgG1 (Z=-2.12, p=0.034), IFN-γ (t=-2.09, p=0.039) and NK cell activity (t=-2.14, p=0.034) were significant higher in formula-fed infants compared to breast-fed after 3 months. At 9-month, the levels of total IgG (Z=-4.34, p<0.001), IgA (Z=-2.05, p=0.041) and TNF-α (t=-2.10, p=0.037) of formula-fed infants were higher, but the lymphocyte stimulation index (t=2.76, p=0.007) was lower than breast-fed infants. While, no significant differences were found in the incidences of diarrhea and respiratory tract infection (p>0.05)., Conclusions: This investigation suggested that formula- and breast-feeding have different contributions to infant immune development, but the formula feeding would not cause significantly increase of diarrhea and respiratory infections.

Phytoplankton communities are sensitive to environmental changes and are used to assess water quality and ecosystem states. However, their responses to environment are affected by the classifications. To understand the impact of different classifications, the response relationship between phytoplankton communities and environment were compared with five phytoplankton classifications (species, genus, phyla, morphology-based functional groups, and functional groups) by investigating eight reservoirs in summer in the southern subtropical region. The eight reservoirs were mesotrophic and their environment was characterized by a high temperature (32.6±1.1)℃ and low light bioavailability ( Z eu / Z m was 0.48±0.28). The variance of dissolved nutrients contributed to the main environmental differences between the eight reservoirs. The environmental gradient, in terms of dissolved nutrients concentration, was significantly higher than in terms of total nutritional status, temperature, and light bioavailability ( P <0.05). The number of species and genus was higher but their biomass was lower than those of other classifications. This contributed to the higher Bray-Curtis distance and lower species gradient (SCBD) and location gradient (LCBD) of phytoplankton communities with species and genus classifications than other classifications. A statistical analysis showed that only the phytoplankton community gradient with MBFG and phylum classifications was significantly correlated with environmental gradient, in particular the gradient of pH value and PO 4 3- -P concentration. A significant regress was detected between the TSI gradient and the phytoplankton community gradient with MBFG and phylum classifications. In conclusion, as the variance of environment stemmed from the supply of nutrients, the response of the phytoplankton community classified with MBFG and phylum was more sensitive than other classifications.

Background: High red cell distribution width (RDW) is correlated with poor prognosis in acute coronary syndromes (ACS), including ST-segment elevation myocardial infarction (STEMI). However, the association of red cell distribution width to erythrocyte count ratio (RER) with STEMI undergoing percutaneous coronary intervention (PCI) during hospitalization has not been investigated. Therefore, we performed a retrospective study to investigate whether RER is associated with STEMI patients after PCI during hospitalization., Methods: A total of 331 patients, who were hospitalized for STEMI and underwent PCI, were enrolled. Receiver operating characteristic curve (ROC) analyses were used to find the cutoff value of RER and classify the patients into two groups including higher RER group and lower RER group by cutoff value. Differences between measured parameters in higher RER and lower RER groups were analyzed by the Mann-Whitney U test. The evaluation correlation of RDW, red blood cell, and RER with major adverse cardiovascular events was determined by bivariate regression analysis. Univariate logistic regression analysis was used to determine the factors associated with adverse cardiovascular events during the hospitalization of STEMI patients. Multivariate logistic regression analysis was performed to evaluate the potential independent predictors of STEMI., Results: According to ROC analysis, the cutoff value of RER and RDW is 3.10 and 13.9, the sensitivity is 51% and 35%, the specificity is 76% and 80%, respectively. RER showed improved diagnostic capacity compared to RDW in correlation with adverse cardiovascular events during hospitalization in STEMI patients (p < 0.001). Compared with the lower RER group, the incidence of adverse cardiovascular events in STEMI patients is elevated in the higher RER group (75% vs. 64.5%, p < 0.05). Bivariate regression analysis indicated that RER and RDW showed a good correlation with adverse cardiovascular events, and the difference was statistically significant (R = 0.10 p < 0.05 vs. R = 0.05 p < 0.05). Univariate logistic regression analysis showed that age, heart rate, left ventricular ejection fraction, hyperlipidemia, RDW, mean platelet volume, total cholesterol, and RER were correlated with the occurrence of adverse cardiovascular events during the hospitalization of STEMI patients (p < 0.05). Multivariate logistic regression analysis demonstrated that RER could be an independent predictor of adverse cardiovascular events in STEMI patients (B: 0.574, OR: 1.776, 95% CI: 1.043 ~ 3.023, p < 0.05)., Conclusions: RER and RDW demonstrated good correlation with adverse cardiovascular events during hospitalization in STEMI patients. RER is a potential independent predictor of adverse cardiovascular events during hospitalization in STEMI patients.

The use of chiral transient directing groups (TDGs) is a promising approach for developing Pd II -catalyzed enantioselective C(sp 3 )-H activation reactions. However, this strategy is challenging because the stereogenic center on the TDG is often far from the C-H bond, and both TDG covalently attached to the substrate and free TDG are capable of coordinating to Pd II centers, which can result in a mixture of reactive complexes. We report a Pd II -catalyzed enantioselective β-C(sp 3 )-H arylation reaction of aliphatic ketones using a chiral TDG. A chiral trisubstituted cyclobutane was efficiently synthesized from a mono-substituted cyclobutane through sequential C-H arylation reactions, thus demonstrating the utility of this method for accessing structurally complex products from simple starting materials. The use of an electron-deficient pyridone ligand is crucial for the observed enantioselectivity. Interestingly, employing different silver salts can reverse the enantioselectivity., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: To observe and compare the stress distribution of implant, crown, abutment and surrounding bone tissues in the aesthetic zone after restoration of resin-ceramic composite single crown, and provide theoretical basis for clinical restoration., Methods: Three-dimensional finite element models of alveolar bone, implant, crown, and the thickness of different adhesives between crown and abutment (0.05 mm and 0.1 mm) were established by using Mimics 17.0 software.Force was applied at the angle of 130° with the long axis of the implant, the loading position was 2 mm from the incisal cingulum, and other force on the incisal margin was loaded in parallel to the long axis of the implant. The size was 100 N. Linear static stress analysis was carried out to compare the Von Mises stress after single crown restoration with different materials., Results: When the thickness of adhesive was 0.05 mm, and resin cement was selected, after restoration of Enamic, Ultimate resin ceramic composite crown, the peak stress of alveolar bone, implant, crown and abutment was more uniform and decreased slightly, but the difference was not significant compared with that of IPS Empress, blocs Mark Ⅱ ceramic crown. When the thickness of adhesive was 0.05 mm, the peak stress was significantly lower than that of 0.1 mm. There was no significant difference in the stress between glass ionomer cement and resin cement.Under the same conditions, restoration with Ultimate crown had smaller stress value of peak Von Mises., Conclusions: The stress of resin composite ceramics single crown when applied to implantation in aesthetic area is slightly less and more uniform. The proportion of resin in composites and the thickness of adhesive can affect the stress distribution and peak value.

Background: The treatment options of systemic lupus erythematosus (SLE) patients in active and inactive phases are very different clinically, and the prognosis of patients with active SLE is much worse than inactive patients. However, the present indicators for diagnosis of SLE in activity are limited and inefficient., Methods: Three hundred thirty patients with SLE were included. All patients are classified as SLEDAI (systemic lupus erythematosus disease activity index) > 4 as active and SLEDAI ≤ 4 as inactive. The linear correlation between variables was assessed by Pearson's correlation analysis. The difference between parameters in active and inactive patients was evaluated by the Mann-Whitney U test. The evaluation capacity of erythrocyte sedimenta-tion/red blood cell (ERR) and red blood cell/albumin ratio (RAR) on SLE activity was determined by bivariate regression analysis. Sensitivity and specificity are assessed by receiver operating characteristic curve (ROC)., Results: Compared with the inactive SLE, ESR (52.97 ± 35.66 vs. 32.38 ± 29.16 p < 0.001), ERR (15.40 ± 12.41 vs. 8.19 ± 8.10 p < 0.001) and RAR (0.13 ± 0.10 vs. 0.11 ± 0.20 p = 0.038) are all elevated in active SLE (52.97 ± 35.66 vs. 32.38 ±2 9.16 p < 0.001). ERR shows better correlation than RAR with ESR (p < 0.001 vs. p = 0.911). Patients with active SLE exhibited higher SLEDAI than those with inactive SLE (8.67 ± 2.67 vs. 3.27 ± 1.36, p < 0.001). According to ROC analysis, when ESR levels > 58.5 and ERR levels > 13.18, the sensitivity is 37.6% and 45.2%, the specificity is 83.0% and 83.2%., Conclusions: ESR and ERR are potential indicators for diagnosis of active and inactive SLE.

Objective: To observe the difference of pulmonary function among patients with dysphagia after stroke, patients without dysphagia and normal people, and to explore the correlation between swallowing function and pulmonary function. Methods: From September 2018 to April 2019, 310 stroke patients were enrolled from the rehabilitation department and neurology department of sun yat-sen memorial hospital, sun yat-sen university, of which 60 were selected as standard stroke patients. Pulmonary function of the three groups was assessed by pulmonary function detector and further compared. The swallowing function of the dysphagia group after stroke was examined by using videofluroscopic swallowing study (VFSS). The swallowing function was quantitatively assessed by Rosenbek penetration-aspiration scale (PAS), dysphagia outcome and severity scale (DOSS) and videofluoroscopy dysphagia scale (VDS), and the correlation between swallowing function and respiratory function was analyzed. Results: There were significant differences in pulmonary function among three groups ( P< 0.05). Besides the FEF25,FVC, FIVC between patients with dysphagia after stroke and patients without dysphagia, the FEF75 between patients without dysphagia and normal people (all P> 0.05), there were significant differences in the pairwise comparison of other indicators (all P< 0.05). There were correlations between PAS and MIP ( r= -0.618, P= 0.001),PAS and MEP ( r= -0.410, P= 0.038), PAS and PEF ( r= -0.443, P= 0.024), DOSS and MIP ( r= 0.602, P= 0.000),DOSS and MEP ( r= 0.496, P= 0.005), DOSS and PEF ( r= 0.553, P= 0.002), VDS and MEP ( r= -0.483, P= 0.012),VDS and PEF ( r= -0.494, P= 0.010), respectively. Conclusion: The pulmonary function of dysphagia patients after stroke decrease significantly, and the severity of dysphagia is correlated with the decrease of pulmonary function.

An analytical approach was developed to simultaneously determine 13 antibiotics in sulfonamides, quinolones, and macrolides in leafy vegetables by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-MS/MS). After optimizing extracted solutions, purification methods, and eluents of antibiotics in vegetable substrates, and taking into account the influence of environmental changes and experimental conditions on the results, the optimal experimental scheme was determined. This involved ①weighing 500 mg of vegetable samples and adding 20 mL of methanol-Mcllvaine-Na 2 EDTA solution; ② conducting ultrasonic and centrifugal extraction three times; ③ Allowing rotary evaporation to 20 mL to pass a HLB solid phase extraction column; ④ Eluting the extraction column using 6 mL of methanol, upon which the eluent was dried almost completely; ⑤ Re-dissolving the eluent with a mixed solution of acetonitrile:water (volume ratio of 2:8); ⑥ Detecting by UPLC-MS/MS after centrifugation and filtering. Phase A and B of UPLC-MS/MS used an aqueous solution of 1‰ formic acid and acetonitrile, respectively to conduct gradient elution. Results showed that when the pakchoi spiked at 300 ng·g -1 , the spiked recoveries of 13 antibiotics were 38.05%-96.97%. At 150 ng·g -1 , the spiked recoveries were 34.52%-111.10%. At 50 ng·g -1 , the recoveries of standard addition were 41.75%-107.13%, and the relative deviation (RSD) values were all below 8.68%. The detection limit was 0.4-1 ng·g -1 , and the limit of quantification was 1.5-3 ng·g -1 . This demonstrated good extraction and recovery efficiency on different types of leafy vegetables, and presented a good analytical application effect. The antibiotic residues were detected in four kinds of leafy vegetables in found in markets. The total content ranged from 1.59 ng·g -1 to 32.01 ng·g -1 , and the antibiotic content in samples was calculated by dry weight. The content of antibiotics in pakchoi was the highest, followed by Chinese cabbage, lettuce, and coriander. Among the antibiotics detected, sulfadimidine was the most abundant from the selected leafy vegetables. The content of antibiotics was very low, however the potential health risks caused by long-term consumption could not be ignored.

Background: Juglans sigillata, or iron walnut, belonging to the order Juglandales, is an economically important tree species in Asia, especially in the Yunnan province of China. However, little research has been conducted on J. sigillata at the molecular level, which hinders understanding of its evolution, speciation, and synthesis of secondary metabolites, as well as its wide adaptability to its plateau environment. To address these issues, a high-quality reference genome of J. sigillata would be useful., Findings: To construct a high-quality reference genome for J. sigillata, we first generated 38.0 Gb short reads and 66.31 Gb long reads using Illumina and Nanopore sequencing platforms, respectively. The sequencing data were assembled into a 536.50-Mb genome assembly with a contig N50 length of 4.31 Mb. Additionally, we applied BioNano technology to identify contacts among contigs, which were then used to assemble contigs into scaffolds, resulting in a genome assembly with scaffold N50 length of 16.43 Mb and contig N50 length of 4.34 Mb. To obtain a chromosome-level genome assembly, we constructed 1 Hi-C library and sequenced 79.97 Gb raw reads using the Illumina HiSeq platform. We anchored ∼93% of the scaffold sequences into 16 chromosomes and evaluated the quality of our assembly using the high contact frequency heat map. Repetitive elements account for 50.06% of the genome, and 30,387 protein-coding genes were predicted from the genome, of which 99.8% have been functionally annotated. The genome-wide phylogenetic tree indicated an estimated divergence time between J. sigillata and Juglans regia of 49 million years ago on the basis of single-copy orthologous genes., Conclusions: We provide the first chromosome-level genome for J. sigillata. It will lay a valuable foundation for future research on the genetic improvement of J. sigillata., (© The Author(s) 2020. Published by Oxford University Press.)

Transition-metal-catalyzed hydrofunctionalization of 1,3-dienes is a useful and atom-economical method for constructing allylic compounds. Although substantial progress on hydroalkylation of dienes with stabilized carbon nucleophiles has been made, hydroalkylation of dienes with unstabilized carbon nucleophiles has remained a challenge. In this article, we report a protocol for nickel-catalyzed hydroalkylation of dienes with hydrazones, which serve as equivalents of alkyl carbon nucleophiles. In addition, we developed a protocol for hydroalkenylation of dienes with α,β-unsaturated hydrazones, providing a new method for the synthesis of 1,4-dienes. These hydroalkylation and hydroalkenylation reactions feature mild conditions and a wide substrate scope, and the utility of the reaction products is demonstrated by the preparation of an activator of soluble guanylate cyclase., (This journal is © The Royal Society of Chemistry 2019.)

Phytoplankton is the most important biological component in the reservoir ecosystem, which could indicate the status of aquatic ecosystem due to its sensitive to environmental variation. To understand the application and difference between two methods of phytoplankton functional group classification, functional groups (FG) and morphology-based functional groups (MBFG), in indicating the changes of reservoir environment, we investigated water quality and phytoplankton in Qingshitan Reservoir monthly from March 2016 to February 2017. Two phytoplankton functional groups classifications (FG and MBFG) were used to analyze phytoplankton community composition, seasonal succession, and its driving factors. We compared the application and differences of two methods of functional group classifications in indicating environmental changes. The results showed that there were 109 species belonged to seven phylum, which could be classified into 17 FG or 5 MBFG functional groups. Results from both methods indicated that the reservoir was meso-eutrophic. The phytoplankton seasonal succession under 8 or 9 steps with FG or 8 steps with MBFG. Results from the redundancy analysis showed that the response of phytoplankton community reflected with FG to environmental variation was more sensitive than that with MBFG, especially in the response to the changes of pH and nitrate concentration. In conclusion, FG was more appropriate in describing community succession and exploring the relationship between phytoplankton and environment.

A functional group exchange reaction between allylamines and alkenes via nickel-catalyzed C-C bond cleavage and formation was developed. This reaction provides a novel protocol, which does not require the use of unstable imine substrates, for the synthesis of allylamines, which are widely used in the production of fine chemicals, pharmaceuticals, and agrochemicals.

A novel and efficient direct oxidative phosphonylation of α-amino ketones and α-amino acid derivatives with dialkyl phosphites by the catalysis of a cobalt salt under air is disclosed. A variety of α-amino ketones and α-amino acid derivatives underwent the reaction well with dialkyl phosphites to produce the desired α-aminophosphonates. This protocol not only provides an alternative synthetic route for the preparation of diverse α-aminophosphonates but also avoids the use of potentially explosive peroxide agents.

A practical sulfa-Michael/aldol cascade reaction of 1,4-dithiane-2,5-diol and α-aryl-β-nitroacrylates has been developed, which allows efficient access to functionalized 2,5-dihydrothiophenes bearing a quaternary carbon stereocenter in moderate to good yields with high enantioselectivities., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We developed a highly regioselective addition of 1,3-dienes with simple ketones by nickel-hydride catalyst bearing DTBM-SegPhos ligand. A wide range of aromatic and aliphatic ketones directly coupled with 1,3-dienes, providing synthetically useful γ,δ-unsaturated ketones in high yield and regioselectivity. The asymmetric version of the reaction was also realized in high enantioselectivity by using novel chiral ligand DTBM-HO-BIPHEP. The utility of this hydroalkylation was demonstrated by facile product modification and enantioselective synthesis of ( R)-flobufen.

Infrasound, a kind of ambient noise, can cause severe disorders to various human organs, specially to central nervous system (CNS). Our previous studies have shown that infrasound-induced CNS injury was closely related with astrocytes activation and astrocytes-mediated neuroinflammation, but the underlying molecular mechanisms are still largely unclear. FGF2/FGFR1 (Fibroblast growth factor 2/Fibroblast growth factor receptor 1) pathway was reported to play an important role in anti-inflammation in CNS disorders. To further study the possible roles of FGF2/FGFR1 pathway in infrasound-induced CNS injury, here we exposed Sprague-Dawley rats or cultured astrocytes to 16 Hz, 150 dB infrasound, and explored the effects of FGF2 on infrasound-induced astrocytes activation and neuroinflammation. Western blotting, immunofluorescence and liquid chip method were used in this experiment. Our results showed that after 3- or 7-day exposure (2 h/day) of rats as well as 2 h exposure of cultured astrocytes to 16 Hz, 150 dB infrasound, astrocyte-expressed FGFR1 was downregulated in vivo and in vitro . FGF2 pretreatment not only inhibited infrasound-induced astrocyte activation in rat hippocampal CA1 region, but also reduced the levels of pro-inflammatory cytokines, such as TNF-α, IL-1β, IL-18, IL-6, and IFN-γ in vitro and in vivo . However, FGF2 significantly upregulated the expression of FGFR1. Furthermore, we showed that FGF2 could attenuate IκBα phosphorylation, NF-κB p65 translocation, pro-inflammatory cytokines levels, and neuronal loss in the CA1 region induced by infrasound. On the contrary, PD173074, a special antagonist of FGFR1, could reverse the effects above in vitro and in vivo . Taken together, our findings showed that FGF2/FGFR1 pathway may exert inhibitive effects on astrocyte-mediated neuroinflammation in vitro and in vivo after infrasound exposure.

Herein, we describe the first linear-selective hydroarylation reaction of unactivated alkenes and styrenes with aryl boronic acids, which was achieved by introducing a directing group on the alkenes. This efficient, scalable reaction serves as a method for modular assembly of structurally diverse alkyl arenes, including γ-aryl butyric acid derivatives, which are widely utilized as chemical building blocks for the synthesis of various drugs and other biologically active compounds.

A nickel(0)-catalyzed hydroalkenylation of imines with styrene and its derivatives is described. A wide range of aromatic and aliphatic imines directly coupled with styrene and its derivatives, thus providing various synthetically useful allylic amines with up to 95 % yield. The reaction offers a new atom- and step-economical approach to allylic amines by using alkenes instead of alkenyl-metallic reagents. Experiments and DFT calculations showed that TsNH 2 promotes the proton transfer from the coordinated olefin to the imine, accompanied by a new C-C bond formation., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Highly efficient red-emitting phosphors, CaAlSiN 3 :Eu 2+ , were successfully prepared by the solid-state method using calcium cyanide (CaCN 2 ) as the single calcium source. The influences of crystallization temperature, crystallization time, calcination mode and compounds ratio on the photoluminescent properties were investigated. The CaAlSiN 3 :Eu 2+ phosphors were obtained with 1 mol% CaCN 2 by a two-step calcination procedure at 900°C for 2 h and subsequently at 1600°C for 8 h. The CaAlSiN 3 :Eu 2+ phosphors showed the strongest luminescent intensity at 660 nm when excited by 468 nm. With an increase in crystallization time, the maximum wavelength of the emission was shifted from 644 nm to 660 nm., (Copyright © 2018 John Wiley & Sons, Ltd.)

A Ni-catalyzed hydroarylation of styrenes and 1,3-dienes with organoboron compounds has been developed. The reaction offers a highly selective approach to diarylalkanes and allylarenes under redox-neutral conditions. In this hydroarylation reaction, a new strategy that uses the proton of methanol to generate the active catalyst species Ni-H was developed. The Ni-catalyzed hydroarylation, combined with a Ir-catalyzed C-H borylation, affords a very efficient and straightforward access to a retinoic acid receptor agonist., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Iron (Fe) and manganese (Mn) are redox-sensitive elements that are both important chemical indicators of water quality. To study their vertical distribution characteristics in south-subtropical reservoirs during summer, Fe and Mn concentrations in the water column, as well as the physical and chemical conditions of the water, were investigated in the lacustrine zones of nine reservoirs in the eastern of Guangdong Province, in July 2016. These results showed that Fe and Mn exhibited a strong concentration gradient in deep reservoirs due to thermal stratification. The total Fe (TFe), total Mn (TMn), dissolved Fe (DFe), and dissolved Mn (DMn) concentrations in the surface water are significantly lower than in these in bottom zones (TFe, F =6.708, P =0.032; TMn, F =9.720, P =0.014; DFe, F =8.129, P =0.029; DMn, F =11.125, P =0.016). The average concentrations of TFe and TMn are 0.399 mg·L -1 and 0.422 mg·L -1 , respectively at the bottom five of the deep reservoirs, and the dissolved ions accounted for more than 70% of this concentration. In shallow reservoirs without thermal stratification, TFe, TMn, DFe and DMn concentrations in surface water are lower than those measured at bottom of the reservoir, no significant difference was detected (TFe, F =0.135, P =0.726; TMn, F =0, P =1; DFe, F =0.006, P =0.943; DMn, F =0.007, P =0.936). The average concentrations of TFe and TMn are 0.110 mg·L -1 and 0.089 mg·L -1 , respectively at the bottom of the four shallow reservoirs, and they were present predominantly in particulate form. The concentrations of TFe and DFe correlated significantly ( P <0.05) with the dissolved oxygen (DO) concentration, pH and depth, but did not significantly correlate with TN or TP concentration in the deep reservoirs. The gradient distributions of DO and pH levels is critical to the gradient distribution of Fe and Mn in deep reservoirs because of water stratification. Low DO concentrations and acidic conditions in these areas contributed to the release of Fe and Mn from sediment and result in high dissociation of these elements in the bottom of deep reservoirs. Simultaneously, high concentrations of Fe and Mn at the bottom of reservoirs may also attribute to the characteristic red soil of this region. The results from this study imply that the high concentrations of Fe and Mn common in the bottom of deep reservoirs is associated with the stable stratification of these reservoirs in the summer. The concentrations of Fe and Mn may be exceed water standards when deep water is taken for public water provision. The problem may be avoided with surface water supplying.

The aberrant alterations of calmodulin (CaM) and its downstream substrates have been reported in some neurodegenerative diseases, but rarely described in prion disease. In this study, the potential changes of Ca 2+ /CaM and its associated agents in the brains of scrapie agent 263K-infected hamsters and the prion infected cell line SMB-S15 were evaluated by various methodologies. We found that the level of CaM in the brains of 263K-infected hamsters started to increase at early stage and maintained at high level till terminal stage. The increased CaM mainly accumulated in the regions of cortex, thalamus and cerebellum of 263K-infected hamsters and well localization of CaM with NeuN positive cells. However, the related kinases such as total and phosphorylated forms of CaMKII and CaMKIV, as well as the downstream proteins such as CREB and BDNF in the brain of 263K-infected hamsters were decreased. Further analysis showed a remarkable increase of S-nitrosylated (SNO) form of CaM in the brains of 263K-infected hamsters. Dynamic analysis of S-nitrosylated CaM showed the SNO form of CaM abnormally increases in a time-dependent manner during prion infection. Compared with that of the normal partner cell line SMB-PS, the CaM level in SMB-S15 cells was increased, meanwhile, the downstream proteins, such as CaMKII, p-CaMKII, CREB, as well as BDNF, were also increased, especially in the nucleic fraction. No SNO-CaM was detected in the cell lines SMB-S15 and SMB-PS. Our data indicate an aberrant increase of CaM during prion infection in vivo and in vitro.