Data_Sheet_1_Optimization of the extraction process and metabonomics analysis of uric acid-reducing active substances from Gymnadenia R.Br. and its protective effect on hyperuricemia zebrafish.docx

BackgroundAs Gymnadenia R.Br. (Gym) has an obvious uric acid-lowering effect, but its specific bioactive substances and mechanism are still unclear. The key metabolites and pathways used by Gym to reduce uric acid (UA) were identify.MethodsAn optimized extraction process for urate-lowering active substances from Gym was firstly been carried out based on the xanthine oxidase (XOD) inhibition model in vitro; then, the Ultra-high-performance liquid chromatography and Q-Exactive mass spectrometry (UHPLC-QE-MS) based on non-targeted metabolomics analysis of Traditional Chinese Medicine were performed for comparison of Gym with ethanol concentration of 95% (low extraction rate but high XOD inhibition rate) and 75% (high extraction rate but low XOD inhibition rate), respectively; finally, the protective effect of ethanolic extract of Gym on zebrafish with Hyperuricemia (referred to as HUA zebrafish) was explored.ResultsWe found that the inhibition rate of Gym extract with 95% ethanol concentration on XOD was 84.02%, and the extraction rate was 4.32%. Interestingly, when the other conditions were the same, the XOD inhibition rate of the Gym extract with 75% ethanol concentration was 76.84%, and the extraction rate was 14.68%. A total of 539 metabolites were identified, among them, 162 different metabolites were screened, of which 123 were up-regulated and 39 were down-regulated. Besides significantly reducing the contents of UA, BUN, CRE, ROS, MDA, and XOD activity in HUA zebrafish by Gym and acutely reduce the activity of SOD.ConclusionAlong with the flavonoids, polyphenols, alkaloids, terpenoids, and phenylpropanoids, the ethanolic extract of Gym may be related to reduce the UA level of Gym.</p

Ruthenium-Catalyzed C–F Bond Arylation of Polyfluoroarenes: Polyfluorinated Biaryls by Integrated C–F/C–H Functionalization

Fluorine-containing molecules are central motifs in pharmaceuticals, agrochemicals, and functional materials owing to the unique properties engendered by carbon–fluorine bonds. However, the chemoselective synthesis of multifluorinated biaryls, a motif extensively exploited in drug discovery, is challenging because of the difficulty in controlling selective fluorination. Herein, we report a site-selective arylation of C–F bonds in polyfluoroarenes enabled by a ruthenium catalyst system. The present C–F bond arylation proceeds exclusively at the ortho-position of polyfluorinated arenes through ruthenium(0) chelation to a readily modifiable directing group. A variety of broadly available polyfluoroarenes and organoboranes are applicable to this C–F bond functionalization, furnishing polyfluorinated biaryls featuring a readily removable aldehyde functional handle. Notably, the present conditions enable a programmed synthesis of multifluorinated biaryls by integrated C–F/C–H functionalization by the same ruthenium catalyst. This approach is characterized by broad scope and functional group tolerance to build complex multifluorinated biaryls. The synthetic utility of this approach is highlighted by the synthesis of polyfluorinated ligands, heterocycles, pharmaceuticals, and porphyrin analogues. DFT studies provide insight into the key selectivity of C–F bond activation. We fully expect that this approach will facilitate the implementation of C–F defluorination in the synthesis of polyfluorinated molecules utilizing molecules with high fluorine content

Photoinduced Conversion of Cu Nanoclusters Self-Assembly Architectures from Ribbons to Spheres

Two-dimensional (2D) nanomaterials have attracted much attention because of the unique layered structures and charming properties in many applications. However, with respect to stimulus-responsive 2D nanomaterials, the rigidity of most 2D nanostructures sheds doubt on achieving morphology response. In this paper, a photoresponsive 2D nanostructure is fabricated on the basis of the self-assembly of ultrasmall Cu nanoclusters (NCs) in colloidal solution. The Cu NCs are foremost decorated by the capping ligands with photoresponsive azobenzene (Azo) groups and by virtue of the flexibility of self-assembly techniques to produce nanoribbons. Because the ribbons are composed of individual NCs rather than a rigid whole, the ultraviolet (UV)-induced Cu NCs disassembly permits achieving morphology transformation. The disassembly of Cu ribbons is controlled by the Cu NCs rather than the surface ligands. However, the disassembled Cu NCs will reassemble into spheres if they are coated with Azo groups. The electrocatalytic performance of Cu self-assembly ribbons and spheres in oxygen reduction reaction is further compared. The ribbons show better catalytic activity than the spheres

Engineering the Self-Assembly Induced Emission of Cu Nanoclusters by Au(I) Doping

Aggregation-induced emission (AIE) and self-assembly induced emission (SAIE) effects have been employed to tune the emission properties of metal nanoclusters (NCs). However, it is still not possible to further enhance the photoluminescence quantum yields (PLQYs) and control the emission colors of the NCs using AIE and SAIE. On the basis of our recent work studying the contribution of Cu­(I) defects in the SAIE of Cu NCs, in this article, Au­(I) was doped into Cu NC self-assembled nanosheets (NSASs) to construct a more stable Au­(I)-centered state. As a result, the PLQYs, emission stability, and tunability of emission colors of the Cu NSASs were significantly improved. Detailed studies reveal that the doped Au­(I) induces a Au­(I)–Cu­(I) metallophilic interaction, which leads to a ligand-to-Cu–Au charge transfer, which facilitates the relaxation of excited electrons via a radiative pathway, thereby enhancing the emission intensity. The charge transfer from Cu to Au lowers the energy, thus leading to the red-shift of PL emission. Au­(I) is likely doped into the Cu NSASs rather than in individual NCs, because 0.3% Au doping is enough to alter the emission properties. By mixing Au­(I)-doped Cu NSASs with different emission colors (due to different Au doping percentages) as color conversion materials on commercially available 365 nm GaN chips, a white light-emitting diode prototype is fabricated

Assembly-Induced Enhancement of Cu Nanoclusters Luminescence with Mechanochromic Property

Metal nanoclusters (NCs) as a new class of phosphors have attracted a great deal of interest owing to their unique electronic structure and subsequently molecule-like optical properties. However, limited successes have been achieved in producing the NCs with excellent luminescent performance. In this paper, we demonstrate the significant luminescence intensity enhancement of 1-dodecanethiol (DT)-capped Cu NCs via self-assembly strategy. By forming compact and ordered assemblies, the original nonluminescent Cu NCs exhibit strong emission. The flexibility of self-assembly allows to further control the polymorphism of Cu NCs assemblies, and hence the emission properties. Comparative structural and optical analysis of the polymorphic NCs assemblies permits to establish a relationship between the compactness of assemblies and the emission. First, high compactness reinforces the cuprophilic Cu­(I)···Cu­(I) interaction of inter- and intra-NCs, and meanwhile, suppresses intramolecular vibration and rotation of the capping ligand of DT, thus enhancing the emission intensity of Cu NCs. Second, as to the emission energy that depends on the distance of Cu­(I)···Cu­(I), the improved compactness increases average Cu­(I)···Cu­(I) distance by inducing additional inter-NCs cuprophilic interaction, and therewith leads to the blue shift of NCs emission. Attributing to the assembly mediated structural polymorphism, the NCs assemblies exhibit distinct mechanochromic and thermochromic luminescent properties. Metal NCs-based white light-emitting diodes are further fabricated by employing the NCs assemblies with blue-green, yellow, and red emissions as phosphors