Morphology Engineering of Co₃O₄ Nanoarrays as Free-Standing Catalysts for Lithium–Oxygen Batteries

The effective shape-controlled synthesis of Co₃O₄ nanoarrays on nickel foam substrates has been achieved through a simple hydrothermal strategy. When they served as the binder- and conductive-agent-free porous cathodes for nonaqueous Li–O₂ batteries, they sufficiently reflect the favorable catalytic characteristic of Co₃O₄ and alleviate the problems of serious pore blocking and surface passivation caused by insoluble and insulating discharge products. In particular, Co₃O₄ rectangular nanosheets exhibit superior electrocatalytic performance comparing with Co₃O₄ nanowires and hexagonal nanosheets, leading to higher specific capacity and better cycling stability over 54 cycles at 100 mA g^–1, which relate to their good pore structure, large specific surface area, and highly active {112} exposed plane, effectively promoting the mass transport and reversible formation and decomposition of discharge products in the cathode. These comparisons further indicate the morphology effect of nanostructured Co₃O₄ on their performances as free-standing catalysts for Li–O₂ batteries, which also have been proved through the further analysis of discharge products on different shapes of Co₃O₄ nanoarrays electrodes

Enantioselective Regiodivergent Synthesis of Chiral Pyrrolidines with Two Quaternary Stereocenters via Ligand-Controlled Copper(I)-Catalyzed Asymmetric 1,3-Dipolar Cycloadditions

An unprecedented ligand-controlled regiodivergent Cu­(I)-catalyzed asymmetric intermolecular (3 + 2) cycloaddition reaction of α-substituted iminoesters with β-fluoromethyl β,β-disubstituted enones was developed. This novel strategy provides an efficient method for the enantioselective regiodivergent synthesis of pyrrolidines bearing two adjacent quaternary stereocenters or two discrete quaternary stereocenters, opening up a new era for medicinal chemistry and diversity-oriented synthesis. DFT calculations showed that the P,N-ligand <b>L2</b> acts as a pseudobidentate ligand. The formation of a O–Cu bond with the carbonyl oxygen atom of the enone and dissociation of the amine nitrogen of <b>L2</b> from the Cu­(I) center occurs during the catalytic cycle; this is the main reason for the tuning the regioselectivity of the cycloaddition reaction caused by switching of the ligand. The salient features of this work include high yields (up to >99%), a general substrate scope, the use of commercially available ligands, and high regio-(up to >20:1 rr), diastereo- (up to >20:1 dr), and enantioselectivity (up to >99% ee)

Enantioselective Regiodivergent Synthesis of Chiral Pyrrolidines with Two Quaternary Stereocenters via Ligand-Controlled Copper(I)-Catalyzed Asymmetric 1,3-Dipolar Cycloadditions

An unprecedented ligand-controlled regiodivergent Cu­(I)-catalyzed asymmetric intermolecular (3 + 2) cycloaddition reaction of α-substituted iminoesters with β-fluoromethyl β,β-disubstituted enones was developed. This novel strategy provides an efficient method for the enantioselective regiodivergent synthesis of pyrrolidines bearing two adjacent quaternary stereocenters or two discrete quaternary stereocenters, opening up a new era for medicinal chemistry and diversity-oriented synthesis. DFT calculations showed that the P,N-ligand <b>L2</b> acts as a pseudobidentate ligand. The formation of a O–Cu bond with the carbonyl oxygen atom of the enone and dissociation of the amine nitrogen of <b>L2</b> from the Cu­(I) center occurs during the catalytic cycle; this is the main reason for the tuning the regioselectivity of the cycloaddition reaction caused by switching of the ligand. The salient features of this work include high yields (up to >99%), a general substrate scope, the use of commercially available ligands, and high regio-(up to >20:1 rr), diastereo- (up to >20:1 dr), and enantioselectivity (up to >99% ee)

Enantioselective Regiodivergent Synthesis of Chiral Pyrrolidines with Two Quaternary Stereocenters via Ligand-Controlled Copper(I)-Catalyzed Asymmetric 1,3-Dipolar Cycloadditions

An unprecedented ligand-controlled regiodivergent Cu­(I)-catalyzed asymmetric intermolecular (3 + 2) cycloaddition reaction of α-substituted iminoesters with β-fluoromethyl β,β-disubstituted enones was developed. This novel strategy provides an efficient method for the enantioselective regiodivergent synthesis of pyrrolidines bearing two adjacent quaternary stereocenters or two discrete quaternary stereocenters, opening up a new era for medicinal chemistry and diversity-oriented synthesis. DFT calculations showed that the P,N-ligand <b>L2</b> acts as a pseudobidentate ligand. The formation of a O–Cu bond with the carbonyl oxygen atom of the enone and dissociation of the amine nitrogen of <b>L2</b> from the Cu­(I) center occurs during the catalytic cycle; this is the main reason for the tuning the regioselectivity of the cycloaddition reaction caused by switching of the ligand. The salient features of this work include high yields (up to >99%), a general substrate scope, the use of commercially available ligands, and high regio-(up to >20:1 rr), diastereo- (up to >20:1 dr), and enantioselectivity (up to >99% ee)

TGP treatment reduced the inhibitory neurotransmitter.

<p>The levels of NO (A), NOS (B) and VIP (C) in the MC group increased compared with that in the NC group, while they decreased after TGP treatment. The level of SP (D) decreased in the MC group, but it did not obviously increase in the MC+TGP group. Each bar represents the mean±SEM, n = 10 (each of the three groups). * <i>p</i><0.05, **<i>p</i><0.01 as conducted.</p

TGP ameliorated the function of ICC.

<p>The protein expression (A) and mRNA levels (B, C) of c-kit in the MC group decreased compared with that in the NC group, while they increased after TGP treatment. The protein expression of SCF (D) decreased in the MC group, while it increased in the MC+TGP group. Each bar represents the mean±SEM, (A) n = 10 (each of the three groups), (B, D) n = 6 (each of the three groups). * <i>p</i><0.05, **<i>p</i><0.01 as conducted.</p

Geomorphology and sedimentology of Porto Pino, SW Sardinia, western Mediterranean

This paper presents a detailed (1:4000) geomorphological, sedimentological and ecological map of a Mediterranean microtidal wave-dominated beach system and adjacent inner shelf. This map is an innovative cartographic product that integrates a range of processes of present and past timeframes. It is part of a larger cartography on the coastal geomorphology of Sardinia (Italy) aiming to facilitate coastal management practices and future scientific research. The study area is located in SW Sardinia (Italy), and focuses on Porto Pino beach, an important tourist destination of semi-pristine nature, facing environmental pressures common to many coastal Mediterranean settings. In this context, the main human impact on coastal dune habitats is described and a full environmental characterization of the beach system is presented

DataSheet_1_Selective vulnerability of ARID1A deficient colon cancer cells to combined radiation and ATR-inhibitor therapy.docx

ARID1A is frequently mutated in colorectal cancer (CRC) cells. Loss of ARID1A function compromises DNA damage repair and increases the reliance of tumor cells on ATR-dependent DNA repair pathways. Here, we investigated the effect of ionizing radiation (IR), in combination with ATR inhibitors (ATRi) in CRC cell lines with proficient and deficient ARID1A. The concept of selective vulnerability of ARID1A deficient CRC cells to ATRi was further tested in an ex vivo system by using the ATP-tumor chemosensitivity assay (ATP-TCA) in cells from untreated CRC patients, with and without ARID1A expression. We found selective sensitization upon ATRi treatment as well as after combined treatment with IR (P<0.001), especially in ARID1A deficient CRC cells (P <0.01). Knock-down of ARID1B further increased the selective radiosensitivity effect of ATRi in ARID1A negative cells (P<0.01). Mechanistically, ATRi abrogates the G2 checkpoint (P<0.01) and homologous recombination repair (P<0.01) in ARID1A deficient cells. Most importantly, ex-vivo experiments showed that ATRi had the highest radiosensitizing effect in ARID1A negative cells from CRC patients. Collectively, our results generate pre-clinical and clinical mechanistic rationale for assessing ARID1A defects as a biomarker for ATR inhibitor response as a single agent, or in a synthetic lethal approach in combination with IR.</p

Confocal fluorescence images of histopathological slices in heart region at excitation of 405 laser beams and heart rate of zebrafish:

<p>a) control, b) larvae treated with 100 μg/mL, c) larvae treated with 200 μg/mL. d) heart rate of zebrafish embryos exposed to QGDs at 48, 72, 96 and 120 hpf. * denotes P < 0.05 compared with control. Values represent the mean ± SE.</p