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The first catalytic asymmetric synthesis of highly functionalized difluoromethylated cyclopropanes is described. The method, based on a rhodium-catalyzed cyclopropanation of difluoromethylated olefins, gives access to a broad range of cyclopropanes bearing ester, ketone, or nitro functional groups. By using Rh ((S)-BTPCP) as a catalyst, the corresponding products were obtained in high yields and high diastereo- and enantioselectivities (up 20:1 d.r. and 99 % ee). This methodology allowed preparation of enantioenriched difluoromethylcyclopropanes for the first time.
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http://dx.doi.org/10.1002/anie.201707375 | DOI Listing |
J Am Chem Soc
September 2025
National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Zeolite-confined Rh-based catalysts have emerged as promising heterogeneous candidates for olefin hydroformylation. However, they face challenges of reactant- and product-induced Rh leaching and aggregation. Herein, zeolite framework-anchored Rh-(O-Zn) sites were designed and are shown to have remarkable activity and stability for gas-phase ethylene hydroformylation.
View Article and Find Full Text PDFPLoS One
September 2025
Department of Anatomy and Physiology, The University of Melbourne, Parkville, Victoria, Australia.
Food intake is a key regulator of the digestive system function; however, little is known about organ- and sex-specific differences in food-driven regulation. We placed male and female C57Bl/6 mice on time-restricted feeding (TRF), limiting access to food to an 8-hour window. Food was added either at dark (ZT12) or light (ZT0) onset for 14 days.
View Article and Find Full Text PDFPLoS One
September 2025
Department of Computer Science, Emory University, Atlanta, Georgia, United States of America.
Background: Erythema, an early visual indicator of tissue damage preceding pressure injuries (PrIs), presents as redness in light skin tones but is harder to detect in dark skin tones. While thermography shows promise for early PrI detection, validation across different skin tones remains limited. Furthermore, most protocols and models have been developed under highly controlled conditions.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
September 2025
State Key Laboratory of Green Biomanufacturing, College of Life Science and Technology, Beijing University of Chemical Technology, Beijing 100029, China.
High-mobility group box protein 1 (HMGB1) is a chromatin-associated nonhistone protein widely distributed in the nucleus of eukaryotic cells. It is transported extracellularly as a proinflammatory mediator or late warning protein to induce immune and inflammatory reactions upon stimuli such as microbial infection. Here, we have found that HMGB1 directly interacts with bacterial DNA analogue CpG-A in the extracellular environment to undergo liquid-liquid phase separation (LLPS) via its positively charged DNA-binding domain.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
September 2025
Key Laboratory of Pathogen Microbiology and Immunology, Institute of Microbiology, Chinese Academy of Sciences, Beijing 100101, China.
In eukaryotic systems, three major types of cell junctions have been well characterized. While bacterial adhesion mechanisms also exhibit remarkable diversity, the molecular processes that regulate the dynamic modulation of binding strength between elongated bacterial cells and host cells remain poorly understood. () utilizes the surface adhesin CbpF to interact with the highly expressed host receptors CEACAM1 and CEACAM5 on cancer cells to facilitate tumor colonization.
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