X-ray Crystal Structures and the Facile Oxidative (Au−C) Cleavage of the Dimethylaurate(I) and Tetramethylaurate(III) Homologues

Dimethylaurate(I) has been prepared as the crystalline tetrabutylammonium salt for comparison with the known tetramethylaurate(III) analogue. The linear structure of dimethylaurate(I) and the square-planar structure of tetramethylaurate(III) have both been confirmed by X-ray crystallography. One-electron oxidation of dimethylaurate(I) by either ferrocenium or arenediazonium cations produces the metastable dimethylgold(II) intermediate, which can be trapped as the paramagnetic 9,10-phenanthrenequinone (PQ) adduct. Otherwise, dimethylgold(II) is subject to rapid reductive elimination of ethane and affords metallic gold (mirror). The analogous oxidation of tetramethylaurate(III) by ferrocenium, arenediazonium, or nitrosonium cations also proceeds via electron transfer to generate the putative tetramethylgold(IV) intermediate. The highly unstable (CH3)4AuIV spontaneously undergoes homolytic cleavage to produce methyl radical and the coordinately unsaturated trimethylgold(III), which can be intercepted by added triphenylphosphine to afford Me3AuIIIPPh3

How the α-substititionof substrate affects the specific activity and stereoselectivity of carbonyl reductase

In asymmetric catalysis, the enantioselectivity of the reaction product is generally controlled by steric repulsion between asymmetric catalyst and substrate. This is also happened when enzyme as the asymmetric catalyst. But steric repulsion wasn’t the sole factor effected on the enzyme activity. The electronic effect of amino acids in or near the enzymatic activity center which interact with substrate can play an important role in this phenomenon. Stereoselective reduction of aromatic ketones with α-halo groups are of particular interest, since the corresponding chiral halohydrins (β-halo alcohols) are key-intermediates in the synthesis of a number of biologically active compounds. For the mono- or multi- halomethyl ketones as the substrates, the increased electrophilicity of the carbonyl carbon compensates for the lower Lewis basicity and greater steric shielding of the carbonyl oxygen[1]. Please click Additional Files below to see the full abstract

Engineering a carbonyl reductase to simultaneously increase activity toward bulky ketone and isopropanol for dynamic kinetic asymmetric reaction

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Altered Expression of Signaling Genes in Jurkat Cells upon FTY720 Induced Apoptosis

FTY720, a novel immunosuppressant, has a marked activity in decreasing peripheral blood T lymphocytes upon oral administration. Recent investigations suggest that the action of FTY720 on lymphocytes may result from its ability to induce cell apoptosis. However, the cell signaling mechanism involved in the FTY720-induced cell apoptosis remains unclear. Here we examined the apoptotic signal pathways mediated by FTY720 in Jurkat cells using microarray analysis. The results showed that FTY720 can induce Jurkat cell apoptosis in a dose and time dependent manner as assessed by cell viability, Hoechst 33258 staining, Annexin V binding and DNA fragmentation tests. cDNA microarray analysis showed that 10 µM of FTY720 up-regulated 54 and down-regulated 10 genes in Jurkat cells among the 458 apoptotic genes examined following the 6 h incubation period. At least five-fold increased expression of modulator of apoptosis-1 (MOAP-1), vascular endothelial growth factor (VEGF), tumor necrosis factor receptor-associated factors (TRAF 6), Caspase 2 (CASP 2), E2F transcription factor 1 (E2F 1) and Casapse 5 (CASP 5) genes was observed in microarray analyses; these results were confirmed with reverse transcription polymerase chain reaction (RT-PCR) examination. Our findings suggest that the mitochondria related signaling pathways are the key pathways involved in the FTY720-induced apoptosis in Jurkat cells. And our results provide a new insight into the mechanism of FTY720, which allows us to draw the first simple diagram showing the potential pathways mediated by FTY720

Synthesis of α,β-unsaturated esters via a chemo-enzymatic chain elongation approach by combining carboxylic acid reduction and Wittig reaction

α,β-Unsaturated esters are versatile building blocks for organic synthesis and of significant importance for industrial applications. A great variety of synthetic methods have been developed, and quite a number of them use aldehydes as precursors. Herein we report a chemo-enzymatic chain elongation approach to access α,β-unsaturated esters by combining an enzymatic carboxylic acid reduction and Wittig reaction. Recently, we have found that Mycobacterium sp. was able to reduce phenylacetic acid (1a) to 2-phenyl-1-ethanol (1c) and two sequences in the Mycobacterium sp. genome had high identity with the carboxylic acid reductase (CAR) gene from Nocardia iowensis. These two putative CAR genes were cloned, overexpressed in E. coli and one of two proteins could reduce 1a. The recombinant CAR was purified and characterized. The enzyme exhibited high activity toward a variety of aromatic and aliphatic carboxylic acids, including ibuprofen. The Mycobacterium CAR catalyzed carboxylic acid reduction to give aldehydes, followed by a Wittig reaction to afford the products α,β-unsaturated esters with extension of two carbon atoms, demonstrating a new chemo-enzymatic method for the synthesis of these important compounds

A New 3-Ketosteroid-Δ¹–Dehydrogenase with High Activity and Broad Substrate Scope for Efficient Transformation of Hydrocortisone at High Substrate Concentration

3-Ketosteroid-Δ1-dehydrogenases (KstDs [EC 1.3.99.4]) catalyze the Δ1-dehydrogenation of steroids and are a class of important enzymes for steroid biotransformations. In this study, nine putative kstD genes from different origins were selected and overexpressed in Escherichia coli BL21(DE3). These recombinant enzymes catalyzed the Δ1-desaturation of a variety of steroidal compounds. Among them, the KstD from Propionibacterium sp. (PrKstD) displayed the highest specific activity and broad substrate spectrum. The detailed catalytic characterization of PrKstD showed that it can convert a wide range of 3-ketosteroid compounds with diverse substituents, ranging from substituents at the C9, C10, C11 and C17 position through substrates without C4-C5 double bond, to previously inactive C6-substituted ones such as 11β,17-dihydroxy-6α-methyl-pregn-4-ene-3,20-dione. Reaction conditions were optimized for the biotransformation of hydrocortisone in terms of pH, temperature, co-solvent and electron acceptor. By using 50 g/L wet resting E. coli cells harboring PrKstD enzyme, the conversion of hydrocortisone was about 92.5% within 6 h at the substrate concentration of 80 g/L, much higher than the previously reported results, demonstrating the application potential of this new KstD

Effect of pore water pressure on mechanical performance of recycled aggregate concrete under triaxial compression

The pore water pressure in concrete can significantly increase due to volume compression. Recycled aggregate concrete (RAC) possesses a more complex microstructure compared to natural aggregate concrete (NAC). Understanding the porosity and micromechanical properties of RAC is crucial for analysing its failure mechanism under the influence of coupled confining pressure and pore water pressure. This study compares the constituent proportions and micromechanical properties of interfacial transition zones (ITZs) and the adjacent paste matrix in NAC and RAC. Compressive stress-strain curves were obtained for concrete under coupled confining pressure and pore water pressure. The results indicate that the newly formed ITZ, which bonds to old mortar, outperformed the one bonded to natural aggregate when considering the same water-cement ratio. Compressive strength, ductility, and maximum volumetric strain gradually increased with increasing confining pressure. However, when pore water pressure was removed, compressive strength decreased while elastic modulus improved. Due to the inferior microstructures of RAC compared to NAC, the supportive effect of pore water becomes more pronounced. This is evident in the gradual increase in peak strain with increased pore water pressure for the stress-strain curves of RAC (100 % replacement ratio). Finally, a failure criterion and stress-strain theoretical model considering pore water pressure are proposed, and satisfactory fitting results are obtained.This article is published as Li, Yunan, Hanbing Zhao, Yong Hu, Fulin Qu, Dunming Zhu, Kejin Wang, and Wengui Li. "Effect of pore water pressure on mechanical performance of recycled aggregate concrete under triaxial compression." Cement and Concrete Composites (2023): 105402. doi: https://doi.org/10.1016/j.cemconcomp.2023.105402. © 2023 The Authors. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)