Catalytic Asymmetric Desymmetrization of Cyclic 1,3-Diketones Using Chiral Boro-phosphates.

Herein, we report a chiral boro-phosphate-catalyzed reductive amination for the desymmetrization of 2,2-disubstituted 1,3-cyclopentadiones with pinacolborane as the reducing agent, delivering chiral ß-amino ketones with an all-carbon quaternary stereocenter in good yields (≤94%), high enantioselectivities (≤97% ee), and excellent diastereoselectivities (>20:1 dr). This reaction has a broad substrate scope and high functional group tolerance. The importance of the chiral products was also demonstrated through the preparation of multifunctional building blocks and heterocycles.

Asymmetric Rubottom-Type Oxidation Catalyzed by Chiral Calcium Phosphates.

Invited for the cover of this issue is the group of Jon C. Antilla at Zhejiang Sci-Tech University. The image depicts asymmetric Rubottom-type oxidation catalyzed by chiral calcium phosphates. Read the full text of the article at 10.1002/chem.202203720.

Asymmetric Rubottom-Type Oxidation Catalyzed by Chiral Calcium Phosphates.

A highly efficient catalytic asymmetric Rubottom-type oxidation is described. Using meta-chloroperbenzoic acid (m-CPBA) as the oxidant and chiral calcium phosphate as the catalyst, the facile transformation enables direct hydroxylation of N-Boc oxindoles and ß-ketoesters in high yields (up to 99 %) and in a highly enantioenriched fashion (up to >99 % ee). The application of the established method was demonstrated by the synthesis of a pharmaceutically important 3-hydroxyoxindole with excellent enantiocontrol.

Effects of childhood trauma on aggressive behaviors and hippocampal function: the modulation of COMT haplotypes.

Background: Aggression is a commonly hostile behavior linked to the hippocampal activity. Childhood trauma (CT) exposure has been associated with altered sensitization of the hypothalamic-pituitary-adrenal (HPA) axis and hippocampal volume，which could increase violent aggressive behaviors. Additionally, Catechol-O-methyltransferase (COMT), the major dopamine metabolism enzyme, is implicated in stress responsivity, including aggression. Hence, CT exposure may affect aggression through the effect on the hippocampal function, which might also be modulated by the COMT variations. Objectives: This study examined whether both CT and haplotypes of COMT moderate hippocampal function and thus affect human aggressive behavior. Methods: We obtained bilateral hippocampal functional connectivity maps using resting state functional magnetic resonance imaging (MRI) data. COMT haplotype estimation was performed using Haploview 4.2 and PHASE 2.1. Then we constructed a moderated mediation model to study the effect of the CTQ × COMT on aggressive behavior. Results: Three major haplotypes were generated from thirteen single nucleotide polymorphisms (SNPs) within the COMT gene and formed three haplotypes corresponding to high, medium, and low enzymatic activity of COMT. The results showed interactive relationships between the Childhood Trauma Questionnaire (CTQ) and COMT with respect to the functional connectivity (FC) of the bilateral hippocampus (HIP)-orbital frontal cortex (OFC). Specifically, CT experience predicted lower negative HIP-OFC coupling in the APS and HPS haplotypes corresponding to the medium and high enzymatic activity of COMT, but greater FC in the LPS haplotypes corresponding to the low enzymatic activity. We also observed a conditional mediation effect of the right HIP-OFC coupling in the link between COMT and aggressive behavior that was moderated by CT experience. Conclusions: These results suggest that CT and COMT have a combined effect on aggressive behavior through hippocampal function. This mediation analysis sheds light on the influence of childhood experience on aggressive behavior in different genetic backgrounds.

Asymmetric Reductive Amination with Pinacolborane Catalyzed by Chiral SPINOL Borophosphates.

The catalytic asymmetric reductive amination of ketones with pinacolborane employing chiral SPINOL-derived borophosphates as catalysts has been realized. A series of chiral amine derivatives bearing multiple functional groups were obtained in good to excellent yields and enantioselectivities (up to 97% yield, 98% ee) under mild reaction conditions. Moreover, the synthetic applicability of the established method has been demonstrated by the asymmetric synthesis of (R)-Fendiline.

Immunostimulatory and antioxidant activities of the selenized polysaccharide from edible Grifola frondosa.

Grifola frondosa polysaccharide (GFP2) was extracted and purified by anion-exchange chromatography. A selenized G. frondosa polysaccharide, SeGFP2, was modified in selenylation by nitric acid-sodium selenite (HNO3-Na2SeO3) method. Structural features were investigated, and the lymphocyte proliferation and antioxidant activities were compared taking GFP2 as control. SeGFP2 with a molecular weight of 2.12 × 104 Da was composed of mannose, glucose, and galactose with a ratio of 3.5:11.8:1.0. A typical absorption of selenium ester was observed in SeGFP2 molecule. SeGFP2 was proposed as a branched polysaccharide, which consisted of 1,3-D-Glcp, 1,6-D-Glcp, 1,4,6-D-Galp, and 1,3,6-D-Manp. SeGFP2 showed a linear filamentous structure with some branches. SeGFP2 could significantly promote T- or B-lymphocyte proliferation and the enhancement was higher than GFP2. The in vitro antioxidant activities of SeGFP2 were more potent than GFP2. These present data suggested that selenylation could significantly improve the lymphocyte proliferation and in vitro antioxidant activities of GFP2.

The clinical significance and biological function of lncRNA SOCAR in serous ovarian carcinoma.

BACKGROUND: Ovarian cancer (OvCa) is one of the most lethal gynecologic malignancies worldwide. Pelvic and abdominal metastasis is a leading cause for the poor prognosis of OvCa patients. The relationship between long non-coding RNAs (lncRNAs) and OvCa remains unclear. Identifying key lncRNAs related with OvCa metastasis is crucial for research on the mechanism of OvCa metastasis. This study was designed to investigate the role of a novel lncRNA, which we named SOCAR, in serous OvCa. METHODS: LncRNA microarray and Real-time PCR were used to examine SOCAR expression in high grade serous ovarian cancer (HGSOC) and normal ovary tissues. The proliferation, migration and invasion of OvCa cell lines SKOV-3 and OVCAR-3 were analyzed by CCK-8, Transwell and Scratch wound healing assays. Western blotting was used to detect the expression of Wnt/ß-catenin pathway-related proteins. RESULTS: A novel serous OvCa-related lncRNA, SOCAR, was identified via microarray. SOCAR was overexpressed in primary HGSOC tumors compared with normal ovary tissues, and the expression of SOCAR correlated with progression in HGSOC patients. SOCAR also had higher expression in metastatic HGSOC tissues compared with primary cancer tissues. Moreover, upregulation of SOCAR promoted proliferation, migration and invasion in OvCa cells. Expression of Wnt1, ß-catenin and MMP-9 were all increased by SOCAR overexpression. CONCLUSION: SOCAR is related with HGSOC oncogenesis and progression. It may promote proliferation, migration and invasion in OvCa cells partially by upregulating MMP-9 through the Wnt/ß-catenin pathway.

CTD-2020K17.1, a Novel Long Non-Coding RNA, Promotes Migration, Invasion, and Proliferation of Serous Ovarian Cancer Cells In Vitro.

BACKGROUND Ovarian cancer is the most lethal malignant tumor of the female reproductive system, and the metastasis is one of the major factors that contribute to the poor outcome of patients with OC. Accumulating evidence indicates that lncRNAs are expressed and play important regulatory roles in ovarian cancer. MATERIAL AND METHODS Aberrant lncRNAs in primary ovarian cancer tissues (POCTs) and paired omental metastasis tissues (OMTs) of patients with HGSOC were studied via lncRNA microarray. Real-time PCR was performed to examine CTD-2020K17.1 expression in HGSOC tissues from 38 patients, a normal ovarian surface epithelium cell line, and 4 ovarian cancer cell lines. Additionally, Transwell assays, wound healing assays, CCK-8 proliferation assays, and flow cytometry were used to explore the biological function of CTD-2020K17.1 in ovarian cancer cells. Finally, Western blot analysis was used to verify the potential target gene of CTD-2020K17.1. RESULTS A novel lncRNA named CTD-2020K17.1 was identified via microarray analysis. Expression of CTD-2020K17.1 was significantly increased in OMTs and in 4 ovarian cancer cell lines compared with POCTs (P<0.05) or normal ovarian surface epithelial cell line (P<0.05). Moreover, CTD-2020K17.1 overexpression promoted migration, invasion, and proliferation of ovarian cancer cells, and CTD-2020K17.1 regulated the expression of CARD11. CONCLUSIONS CTD-2020K17.1 is significantly upregulated in OMTs and ovarian cancer cell lines. It can promote the migration, invasion, and proliferation of ovarian cancer cells, and CARD11 is regulated by CTD-2020K17.1.

Enhanced adsorption and photocatalytic activity of BiOI-MWCNT composites towards organic pollutants in aqueous solution.

BiOI-MWCNT composites, with high absorption and visible-light photocatalytic performance, were synthesized by a solvothermal process, in which ethylene glycol (EG) participated in the reaction. Synthesized BiOI-MWCNT composites were characterized by X-ray diffraction (XRD), diffuse reflectance spectra (DRS), scanning electronic microscopy (SEM), transmission electron microscopy (TEM), and electrochemical impedance spectroscopy (EIS). The results showed that the prepared BiOI-MWCNT composites exhibit strong adsorption ability with the increase of doped MWCNT amount. The efficiency of AOII degradation increased with the increase of MWCNT amount from 0.5 to 1.0% significantly. The photocatalytic degradation of AOII using BiOI-MWCNT composites under visible light (λ>400 nm) was almost completed within 180 min. BiOI-MWCNT composites maintained its degradation efficiency and durability after being reused for 5 batch runs. The high adsorption ability and degradation efficiency of BiOI-MWCNT for AOII was attributed to the sorption of doped MWCNT and the effective charge transfer from excited BiOI to MWCNTs, respectively. Moreover, organic compounds as intermediates of the degradation process were identified by LC/MS.

A novel wet-scrubbing process using Fe(VI) for simultaneous removal of SO2 and NO.

The objective of this work was to develop a novel wet-scrubbing process using Fe(VI) for the simultaneous removal of gaseous NO and SO(2). The oxidation of SO(2) and NO with Fe(VI) was studied in aqueous solution at alkaline pH (9.0-11.0). A stoichiometric molar ratio for NO and SO(2) oxidation with Fe(VI) was determined to be nearly 3.0. Sulfate and nitrate was identified as final products by ion chromatography from the reaction at pH 9.0-11.0. The feasibility of simultaneous removal of multiple gas pollutants with the continuous feeding of ferrate in lab-scale was investigated from the view of industrial application. It was found that the removal efficiency of NO and SO(2) was enhanced with the increase of Fe(VI) concentration, more than 90% NO removal efficiency and 100% SO(2) removal efficiency were achieved by wet-scrubbing process using Fe(VI) at room temperature and ambient atmosphere. The results demonstrate that Fe(VI) could be an effective wet-scrubbing agent for the simultaneous removal of NO and SO(2).