Continuous-Flow Enantioselective Hydrogenative Enyne Cyclization with Chiral Heterogeneous Rh Catalysts

Continuous-flow hydrogenations provide greatly improved reaction efficiency due to the efficient mass-transfer between heterogeneous catalysts and hydrogen gas. However, reported flow hydrogenations were limited to only simple functional group transformations, and the development of sophisticated catalysis such as enantioselective reductive C–C bond formations remains challenging. Herein, we have developed continuous-flow enantioselective cyclization of 1,6-enynes using chiral heterogeneous catalysts supported on heteropoly acid/amine-functionalized SiO2 composites developed in our group. Investigations under continuous-flow conditions revealed that the tuning of the structure of heteropoly acids and amines could improve the catalyst performance. A variety of substrates could produce products with high yields and enantioselectivities under optimized reaction conditions without leaching of the Rh catalyst. Mechanistic studies revealed the cause of catalyst deactivation of this transformation

Effects of various inhibitors on <i>Txnip</i> suppression in response to LPS.

<p>(A and B) RAW264.7 cells were treated with Vehicle (dimethyl sulfoxide in (A) or diethyl ether in (B)), 10 µM compound C (Comp. C), or 50 nM okadaic acid for 1 h, followed by stimulation with 100 ng/ml LPS for 90 min. (C) RAW264.7 cells were treated with 0.5 mM iodoacetate or sodium acetate for 1 h, followed by treatment with 100 ng/ml LPS, 5 mM sodium azide, or 5 µM rotenone for 90 min. <i>Txnip</i> mRNA copy numbers normalized to that of β-actin are shown. Data shown are mean ± S.E. of triplicate samples of a representative of at least three independent experiments.</p

Suppression of <i>Txnip</i> expression by LPS.

<p>RAW264.7 cells (A and B), BMDM (C and D), or differentiated THP-1 cells (E) were stimulated with 100 ng/ml LPS. Cells were lysed at the indicated time after stimulation. <i>Txnip</i> mRNA copy numbers normalized to that of <i>β-actin</i> are shown (A and C). Data shown are mean ± S.E. of at least 4 independent experiments. Txnip and β-actin proteins were detected by western blotting (B, D, and E). Data shown are a representative of at least three independent experiments.</p

Dissociation of MondoA:Mlx from the <i>Txnip</i> promoter on LPS stimulation.

<p>(A) Chromatin immunoprecipitation assay was performed to examine occupation of Mlx, MondoA, and NF-YA in <i>Txnip</i> promoter region with RAW264.7 cells stimulated with or without 100 ng/ml LPS for 45 min. Enriched DNAs was eluted and <i>Txnip</i> promoter region was quantified by quantitative PCR. Data shown are mean ± S.E. of duplicate samples. (B) RAW264.7 cells stimulated with or without 100 ng/ml LPS for 45 min. Cells were fixed, permeabilized, and stained with anti-MondoA antibody and Alexa488-conjugated polyclonal anti-rabbit IgG antibody. Fluorescence microscopic images were obtained and analyzed by three-dimentional deconvolution. (C) Nuclear and cytoplasmic fractions of RAW264.7 cells stimulated with or without 100 ng/ml LPS for 45 min were analyzed by western blotting with anti-<i>MondoA</i>, histone deacetylase 1 (<i>Hdac1</i>) or ribosomal S6 ribosomal protein (<i>Rps6</i>). Data shown are a representative of at least three independent experiments.</p

Suppression of <i>Txnip</i> expression by proinflammatory stimulation.

<p>BMDM (A), NIH3T3 (B), or RAW264.7 (C) cells were stimulated with 2 µM CpG DNA 100 ng/ml LPS, 10 ng/ml IL-1β, 10 ng/ml TNF-α, or 10 ng/ml IL-10. Cells were lysed at the indicated time after stimulation. Txnip, β-actin, phosphorylated STAT3 (pSTAT3), or STAT3 proteins were detected by western blotting. Data shown are a representative of at least three independent experiments.</p

Intercrystal Self-Assembly for the Design of High-Quality Nickel Molybdate Nanocrystals

Nanowire of nickel molybdate hydrate, being recognized as an emerging supercapacitor material, was synthesized from the intercrystal self-assembly process (commonly referred to as oriented aggregation or attachment). The detailed lattice image of a NiMoO₄·0.75H₂O nanowire and the intermediate nanostructure before reaching the interplanar binding were successfully captured by means of high-resolution transmission and scanning electron microscopies. NiMoO₄·0.75H₂O possessed highly crystalline surface and internal nanostructures

Results of multiple regression analysis in the effect of originality with creative production score as the objective variable.

(DOCX)</p

Moderation effects of creative personality scale on the relationship between creative production score and creative achievement score.

(A) fluency, (B) elaboration. CPS: creative personality scale.</p

Results of multiple regression analysis in the effect of flexibility with creative production score as the objective variable.

(DOCX)</p

Correlations of creativity indices.

Correlations of creativity indices.</p