A Multimode Optical Sensor for Selective and Sensitive Detection of Harmful Heavy Metal Cr(VI) in Fresh Water and Sea Water.

Water pollution originating from heavy metals has shown great impacts on the ecological environment and human health due to their extremely low biodegradability. Hexavalent chromium Cr(VI), as one harmful heavy metal with strong oxidation, high biological permeability, and high carcinogenicity, is becoming an increasingly serious threat to human health. Therefore, conveniently but accurately, monitoring the Cr(VI) level in water to maintain its normal level and ensuring the stability of the ecosystem and human health become very valuable. However, most of these heavy metal sensors reported are turn-off type single-emission sensors. In this work, a ratiometric fluorescence/colorimetry/smartphone triple-mode turn-on optical sensor for Cr(VI) was developed based on a multifunctional metal-organic framework platform. The detection limits for these three mutual verification modes were only 1.28, 4.89, and 68.4 nM, respectively. Additionally, the color changes of the detection system under sunlight can also be observed directly by the naked eye. The accuracy and practicability of this multimode sensor were further proved by the detection of Cr(VI) in actual water and seawater samples, and the recovery rate ranged from 97.308 to 104.041%.

High-rate and selective conversion of CO2 from aqueous solutions to hydrocarbons.

Electrochemical carbon dioxide (CO2) conversion to hydrocarbon fuels, such as methane (CH4), offers a promising solution for the long-term and large-scale storage of renewable electricity. To enable this technology, CO2-to-CH4 conversion must achieve high selectivity and energy efficiency at high currents. Here, we report an electrochemical conversion system that features proton-bicarbonate-CO2 mass transport management coupled with an in-situ copper (Cu) activation strategy to achieve high CH4 selectivity at high currents. We find that open matrix Cu electrodes sustain sufficient local CO2 concentration by combining both dissolved CO2 and in-situ generated CO2 from the bicarbonate. In-situ Cu activation through alternating current operation renders and maintains the catalyst highly selective towards CH4. The combination of these strategies leads to CH4 Faradaic efficiencies of over 70% in a wide current density range (100 - 750 mA cm-2) that is stable for at least 12 h at a current density of 500 mA cm-2. The system also delivers a CH4 concentration of 23.5% in the gas product stream.

Iridium-catalyzed direct asymmetric reductive amination utilizing primary alkyl amines as the N-sources.

Direct asymmetric reductive amination is one of the most efficient methods for the construction of chiral amines, in which the scope of the applicable amine coupling partners remains a significant challenge. In this study we describe primary alkyl amines effectively serve as the N-sources in direct asymmetric reductive amination catalyzed by the iridium precursor and sterically tunable chiral phosphoramidite ligands. The density functional theory studies of the reaction mechanism imply the alkyl amine substrates serve as a ligand of iridium strengthened by a (N)H-O(P) hydrogen-bonding attraction, and the hydride addition occurs via an outer-sphere transition state, in which the Cl-H H-bonding plays an important role. Through this concise procedure, cinacalcet, tecalcet, fendiline and many other related chiral amines have been synthesized in one single step with high yields and excellent enantioselectivity.

In vitro and in vivo immunologic potentiation of herb extracts on shrimp (Litopenaeus vannamei).

In vitro and in vivo effects of Astragalus polysaccharide (APS), chlorogenic acid (CGA) and berberine (BBR) on shrimp (Litopenaeus vannamei) were studied. In vitro test showed that the combination of APS and BBR and the combination of APS and CGA have strong immune enhancement effects and no lysosomal membrane damage on hemocyte. Then, feeding experiment was proceeded to optimize the concentrations of compound herbal extracts. Four diets containing G1-G4(0.5 g kg -1 APS + 0.5 g kg -1 BBR, 1.0 g kg -1 APS +1.0 g kg -1 BBR, 0.5 g kg -1 APS +0.5 g kg -1 CGA, 1.0 g kg -1 APS + 1.0 g kg -1 CGA) associated with the control group (common diet) were compared and determined their biomolecule damage to hepatopancreas including DNA damage, lipid peroxidation and protein carbonyl. The results indicated that G3 (0.5 g kg -1 APS +0.5 g kg -1 CGA) showed higher total hemocyte counts, phagocytic activities, antibacterial activities and bacteriolytic activities during 6 days feeding, and without biomolecule damages after 6 days post-withdrawal. Therefore, the appropriate immunostimulants formula in this study was the combination of 0.5 g kg -1 APS and 0.5 g kg-1 CGA, which was used for 6 days followed by 6 days post-withdrawal. Additionally, our study provides new support for screening composite immunostimulants formula by using primary shrimp hemocyte culture.

The combination of asymmetric hydrogenation of olefins and direct reductive amination.

Asymmetric hydrogenation (AH) and direct reductive amination (DRA) are both efficient transformations frequently utilized in industry. Here we combine the asymmetric hydrogenation of prochiral olefins and direct reductive amination of aldehydes in one step using hydrogen gas as the common reductant and a rhodium-Segphos complex as the catalyst. With this strategy, the efficiency for the synthesis of the corresponding chiral amino compounds is significantly improved. The practical application of this synthetic approach is demonstrated by the facile synthesis of chiral 3-phenyltetrahydroquinoline and 3-benzylindoline compounds.

Secondary amines as coupling partners in direct catalytic asymmetric reductive amination.

The secondary amine participating asymmetric reductive amination remains an unsolved problem in organic synthesis. Here we show for the first time that secondary amines are capable of effectively serving as N-sources in direct asymmetric reductive amination to afford corresponding tertiary chiral amines with the help of a selected additive set under mild conditions (0-25 °C). The applied chiral phosphoramidite ligands are readily prepared from BINOL and easily modified. Compared with common tertiary chiral amine synthetic methods, this procedure is much more concise and scalable, as exemplified by the facile synthesis of rivastigmine and N-methyl-1-phenylethanamine.

Direct Asymmetric Reductive Amination for the Synthesis of (S)-Rivastigmine.

In this article we demonstrate how asymmetric total synthesis of (S)-rivastigmine has been achieved using direct asymmetric reductive amination as the key transformation in four steps. The route started with readily available and cheap m-hydroxyacetophenone, through esterification, asymmetric reductive amination, N-diphenylmethyl deprotection and reductive amination, to provide the final (S)-rivastigmine in 82% overall yield and 96% enantioselectivity. In the asymmetric reductive amination, catalysed by the iridium⁻phosphoramidite ligand complex and helped by some additives, the readily prepared 3-acetylphenyl ethyl(methyl)carbamate directly reductively coupled with diphenylmethanamine to yield the chiral amine product in 96% ee and 93% yield.

DW09849, a selective phosphatidylinositol 3-kinase (PI3K) inhibitor, prevents PI3K signaling and preferentially inhibits proliferation of cells containing the oncogenic mutation p110α (H1047R).

Phosphatidylinositol 3-kinase, α isoform (PI3Kα) plays essential roles in cell metabolism, growth, and proliferation and has been validated as a promising anticancer target. In an effort to search for new PI3Kα-selective inhibitors, DW series compounds were designed and synthesized aiming to reduce the off-target effects of their parent compound PIK-75 [2-methyl-5-nitro-1-benzenesulfonic acid 2-[(6-bromoimidazo[1,2-a]pyridin-3-yl)methylene]-1-methylhydrazide], which was reported to selectively target PI3Kα. A series of compounds named DW series potently inhibited the kinase activity of PI3Kα with little activity against PI3K-related protein kinases and a panel of 15 tyrosine kinases. Similar to PIK-75, DW series compounds were more potent to inhibit PI3Kα among four class I PI3K isoforms, whereas a representative compound DW09849 [(E)-N'-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-N-ethyl-2-methyl-5-nitrobenzohydrazide] displayed distinct binding mode compared with PIK-75. Although DW series compounds inhibited proliferation of rhabdomyosarcoma RH30 cells at elevated 50% inhibitory concentrations (IC50) in comparison with PIK-75, they were more selective than PIK-75 to inhibit PI3K signaling in the cellular context. In particular, DW09849 significantly and persistently blocked PI3K/protein kinase B signaling in RH30 cells, which consequently arrested RH30 cells in the G1 phase. Moreover, DW09849 selectively suppressed the proliferation and clonogenesis of transformed RK3E/HR cells harboring oncogenic mutation of p110α H1047R, as well as a panel of human breast cancer cells containing mutated PI3Kα, which is consistent with the finding that DW09849 demonstrated preference against H1047R mutated PI3Kα in molecular docking stimulation. These results suggest that DW series compounds, especially DW09849, selectively targeting PI3Kα with less off-target effects than PIK-75, provide new clues for the design and discovery of new specific PI3Kα inhibitors for cancer therapy.

2-Methyl-3-(1H-pyrazol-3-yl)imidazo[1,2-a]pyrimidine.

In the title compound, C(10)H(9)N(5), the fused 2-methyl-imidazo[1,2-a]pyrimidine ring system is approximately planar [dihedral angle of 1.14 (9)° between the two fused rings] and the 1H-pyrazole ring is rotated by 28.16 (11)° out of that plane. In the crystal, the mol-ecules are linked into linear chains along the [100] direction by classical inter-molecular N-H⋯N hydrogen bonds.