Theaflavins (TFs) are good for health because of their bioactivities. Enzymatic synthesis of TFs has garnered much attention; however, the source and activity of the enzymes needed limit their wide application. In this study, a microbial polyphenol oxidase from was screened for the synthesis of theaflavin-3,3'-digallate (TFDG). Based on structural and mechanistic analyses of the enzyme, the O-O bond dissociation was identified as the rate-determining step. To address this issue, a transition state (TS) conformation optimization strategy was adopted to stabilize the spatial conformation of the O-O bond dissociation, which improved the catalytic efficiency of tyrosinase. Under the optimum transformation conditions of pH 4.0, temperature 25 °C, (-)-epigallocatechin gallate/epicatechin gallate molar ratio of 2:1, and time of 30 min, Mu (Tyr) produced 960.36 mg/L TFDG with a 44.22% conversion rate, which was 6.35-fold higher than that of the wild type. Thus, the method established has great potential in the synthesis of TFDG and other TFs.
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http://dx.doi.org/10.3390/molecules28093831 | DOI Listing |
Adv Biotechnol (Singap)
July 2024
MOE Key Laboratory of Gene Function and Regulation, State Key Laboratory of Biocontrol, School of Life Sciences, Sun Yat-sen University, Guangzhou, 510275, Guangdong, China.
Cellular plasticity, the remarkable adaptability of cancer cells to survive under various stress conditions, is a fundamental hallmark that significantly contributes to treatment resistance, tumor metastasis, and disease recurrence. Oncogenes, the driver genes that promote uncontrolled cell proliferation, have long been recognized as key drivers of cellular transformation and tumorigenesis. Paradoxically, accumulating evidence demonstrates that targeting certain oncogenes to inhibit tumor cell proliferation can unexpectedly induce processes like epithelial-to-mesenchymal transition (EMT), conferring enhanced invasive and metastatic capabilities.
View Article and Find Full Text PDFAdv Biotechnol (Singap)
July 2024
State Key Laboratory of Plant Genomics, Institute of Microbiology, Chinese Academy of Sciences, Beijing, China.
RNA silencing (or RNA interference, RNAi) initiated by double-stranded RNAs is a conserved mechanism for regulating gene expression in eukaryotes. RNAi-based crop protection strategies, including host-induced gene silencing (HIGS), spray-induced gene silencing (SIGS) and microbe-induced gene silencing (MIGS), have been successfully used against various pests and pathogens. Here, we highlight the challenges surrounding dsRNA design, large-scale production of dsRNA and dsRNA delivery systems.
View Article and Find Full Text PDFJ Mol Model
January 2025
School of Chemistry and Chemical Engineering, Xian Yang Normal University, Xian Yang, China.
Context: This study investigates the reaction mechanism of luteolin with selenium dioxide in ethanol. Through a detailed search for transition states and thermodynamic energy calculations, it was found that the reaction proceeds via two possible pathways, leading to the formation of products P1 and P2, respectively. A common feature of both pathways is that the first elementary step results in the formation of the intermediate INT1.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of California-Davis, Davis, California 95616, United States.
A post-transition state surface intersection (PTSSI) between radical and zwitterionic states that causes a bifurcation in the reaction pathway was discovered through density functional theory calculations on potential energy surfaces and ab initio molecular dynamics simulations of cycloadditions between a bicyclobutane and a triazolinedione (BCB-TAD). It was predicted that changes to the solvent polarity would enable control over the dynamic selectivity in this system; indeed, experimental evidence supported this prediction. This work not only provides new insights into an unusual type of post-transition state bifurcation, but also demonstrates how the nonstatistical dynamic effects that control selectivity for such reactions can be manipulated rationally to increase the yields of synthetically useful reactions.
View Article and Find Full Text PDFJ Org Chem
January 2025
Key Laboratory of Tropical Biological Resources of Ministry of Education, School of Pharmaceutical Sciences, Hainan University, Haikou 570228, P.R. China.
The complicated mechanism makes the regiodivergent rearrangement of ammonium ylide seem to be out of reach. Herein, we reported a regiodivergent rearrangement of gramine ammonium ylide well controlled by the substituents. Density functional theory studies reveal that the ammonium ylide with a more steric hindrance substituent 2-diazo-2-arylacetate goes through a stepwise mechanism to yield both a kinetically and thermodynamically preferred [1,2]-rearrangement product.
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