Flavonoids from Camellia oleifera flower ameliorate type 2 diabetes mellitus by regulating the p53 pathway.

BACKGROUND: Camellia oleifera flower (COF) is rich in flavonoids and polyphenols, strongly preventing postprandial hyperglycemia and improving diabetes. However, research on the effective ingredients in COF extracts that have hypoglycemic effects is limited, and the mechanism by which COF extracts improve liver insulin resistance and glucose and lipid metabolism still needs to be clarified, requiring further investigation. AIM: To systematically clarify the role of COF extracts in improving insulin resistance in diabetes mice and to explore their key targets and mechanisms in anti-type 2 diabetes (T2DM). MATERIALS AND METHODS: Ultrafiltration combined with liquid chromatography-mass spectrometry (UPLC-Q-MS) was used to analyze α-glucosidase inhibitors in COF extracts qualitatively. Blood glucose, lipid, oxidative stress, and liver function indicators were detected in the db/db type 2 diabetes mouse model. Then, RNA-seq was used to identify differentially expressed mRNAs (DEGs) in the liver, screen for key genes and metabolic pathways, and validate the results' accuracy through qPCR experiments. RESULTS: 17 α-glucosidase inhibitors were identified as flavonoids from COF. Through db/db type 2 diabetes mouse model, it was indicated that COF could significantly improve symptoms of hyperglycemia and hyperlipidemia, alleviate oxidative stress, and protect liver and pancreatic tissues by regulating key differential genes expressed, including Nek2, Cdk1, Ccnb1, and Ccnb2 via the p53 signaling pathway and ameliorate the insulin resistance effect. CONCLUSION: This study demonstrated the anti-diabetic effect of COF, explored its potential hypoglycemic target, and provided data support for future T2DM prevention and drug treatment.

Crystal structures and properties of derivatives of the alkaloid matrine: salts and hydrate forms.

We report the crystal structures of three matrine derivatives, namely, the salts (1R,2R,9S,17S)-6-oxo-7,13-diazatetracyclo[7.7.1.02,7.013,17]heptadecan-13-ium (2E)-3-(3,4-dihydroxyphenyl)prop-2-enoate (matrine caffeinate) sesquihydrate, C15H25N2O+·C9H7O4-·1.5H2O (Matrine-CA), and the 2-hydroxybenzoate (salicylate) monohydrate, C15H25N2O+·C7H5O3-·H2O (Matrine-SA), as well as the 1.75-hydrate form, (1R,2R,9S,17S)-7,13-diazatetracyclo[7.7.1.02,7.013,17]heptadecan-6-one 1.75-hydrate, C15H24N2O·1.75H2O (Matrine-H). Each derivative exhibited a consistent molecular conformation for the matrine core, which is notably distinct from that of the anhydrous form. Notably, both salts crystallized in the orthorhombic space group P212121, with an asymmetric unit featuring one cation and one anion. Within the two salt structures, intermolecular proton transfer between matrine and the acid is observed, culminating in the formation of a matrine cation protonated at the tertiary amine N site. The Matrine-CA crystal packing is manifested as a three-dimensional (3D) network arising from one-dimensional (1D) supramolecular helical chains, stabilized by N-H...O and O-H...O hydrogen bonds. In the case of Matrine-SA, the matrine cation is interconnected via hydrogen bonds with salicylate anions and water molecules, also forming a 1D helical motif. The structure of the hydrate form, Matrine-H, is reported again with the disordered solvent molecules accurately located. To further elucidate the structural attributes, Hirshfeld surface analysis and fingerprint plots are employed, offering a nuanced perspective on the intermolecular contacts and interactions within these crystalline forms.

Broad-high operating temperature range and enhanced energy storage performances in lead-free ferroelectrics.

The immense potential of lead-free dielectric capacitors in advanced electronic components and cutting-edge pulsed power systems has driven enormous investigations and evolutions heretofore. One of the significant challenges in lead-free dielectric ceramics for energy-storage applications is to optimize their comprehensive characteristics synergistically. Herein, guided by phase-field simulations along with rational composition-structure design, we conceive and fabricate lead-free Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3-Sr(Sc0.5Nb0.5)O3 ternary solid-solution ceramics to establish an equitable system considering energy-storage performance, working temperature performance, and structural evolution. A giant Wrec of 9.22 J cm-3 and an ultra-high ƞ ~ 96.3% are realized in the BNKT-20SSN ceramic by the adopted repeated rolling processing method. The state-of-the-art temperature (Wrec ≈ 8.46 ± 0.35 J cm-3, ƞ ≈ 96.4 ± 1.4%, 25-160 °C) and frequency stability performances at 500 kV cm-1 are simultaneously achieved. This work demonstrates remarkable advances in the overall energy storage performance of lead-free bulk ceramics and inspires further attempts to achieve high-temperature energy storage properties.

Under-Coordinated CoFe Layered Double Hydroxide Nanocages Derived from Nanoconfined Hydrolysis of Bimetal Organic Compounds for Efficient Electrocatalytic Water Oxidation.

Hierarchically structured bimetal hydroxides are promising for electrocatalytic oxygen evolution reaction (OER), yet synthetically challenging. Here, the nanoconfined hydrolysis of a hitherto unknown CoFe-bimetal-organic compound (b-MOC) is reported for the controllable synthesis of highly OER active nanostructures of CoFe layered double hydroxide (LDH). The nanoporous structures trigger the nanoconfined hydrolysis in the sacrificial b-MOC template, producing CoFe LDH core-shell octahedrons, nanoporous octahedrons, and hollow nanocages with abundant under-coordinated metal sites. The hollow nanocages of CoFe LDH demonstrate a remarkable turnover frequency (TOF) of 0.0505 s-1 for OER catalysis at an overpotential of 300 mV. It is durable in up to 50 h of electrolysis at step current densities of 10-100 mA cm-2 . Ex situ and in situ X-ray absorption spectroscopic analysis combined with theoretical calculations suggests that under-coordinated Co cations can bind with deprotonated Fe-OH motifs to form OER active Fe-O-Co dimmers in the electrochemical oxidation process, thereby contributing to the good catalytic activity. This work presents an efficient strategy for the synthesis of highly under-coordinated bimetal hydroxide nanostructures. The mechanistic understanding underscores the power of maximizing the amount of bimetal-dimer sites for efficient OER catalysis.

Redox Homeostasis Disruptors Based on Metal-Phenolic Network Nanoparticles for Chemo/Chemodynamic Synergistic Tumor Therapy through Activating Apoptosis and Cuproptosis.

The combination of chemo/chemodynamic therapy is a promising strategy for improving antitumor efficacy. Herein, metal-phenolic network nanoparticles (NPs) self-assembled from copper ions and gallic acid (Cu-GA) are developed to evoke apoptosis and cuproptosis for synergistic chemo/chemodynamic therapy. The Cu-GA NPs are biodegraded in response to the highly expressed glutathione (GSH) in tumor cells, resulting in the simultaneous release of Cu+ and GA. The intracellular GSH content is dramatically reduced by the released GA, rendering the tumor cells incapable of scavenging reactive oxygen species (ROS) and more susceptible to cuproptosis. Meanwhile, ROS levels within the tumor cells are significantly increased by the Fenton-like reaction of released Cu+ , which disrupts redox homeostasis and achieves apoptosis-related chemodynamic therapy. Moreover, massive accumulation of Cu+ in the tumor cells further induces aggregation of lipoylated dihydrolipoamide S-acetyltransferase and downregulation of iron-sulfur cluster protein, activating cuproptosis to enhance the antitumor efficacy of Cu-GA NPs. The experiments in vivo further demonstrate that Cu-GA NPs exhibited the excellent biosafety and superior antitumor capacity, which can efficiently inhibit the growth of tumors due to the activation by the tumor specific GSH and hydrogen peroxide. These Cu-based metal-phenolic network NPs provide a potential strategy to build up efficient and safe cancer therapy.

Dietary exposure of copper and zinc oxides nanoparticles affect the fitness, enzyme activity, and microbial community of the model insect, silkworm Bombyx mori.

Copper and Zinc oxides nanoparticles (CuO and ZnO NPs, respectively) are among the most produced and commonly used engineered nanomaterials. They can be released into the environment, thereby causing health concerns and risks to biodiversity that indicate a need to evaluate their toxicological effects in a complex situation. Here, we used the insect model organism silkworm Bombyx mori to address the concerns about the biological effects associated with dietary exposure of CuO and ZnO NPs. ICP-MS analysis revealed significant accumulation of Cu and Zn (the latter being more accumulated) in silkworms' tissues (gut, fat body, silk gland, and malpighian tubule), and some elimination through feces in the respective NPs-exposed groups. NPs-exposures led to a decrease in larval body mass, survivorship, and cocoon production, where the effects of ZnO NPs were more pronounced. We also found that NPs-exposure induced gene expression changes (Attacin, lysozyme, SOD, and Dronc) and altered the activities of antioxidant enzymes (SOD, GST, and CAT), as well as impaired nutrient metabolism (alpha-amylase). Given their antibacterial property, CuO and ZnO NPs decreased species richness and diversity of the gut bacterial community and shifted their configuration to overt microbiome i.e., decreased abundance of probiotics (e.g., Acetobacter) and increased pathobionts (e.g., Pseudomonas, Bacillus, Escherichia, Enterococcus, Ralstonia, etc.) proportions. Overall, this integrated study revealed the unintended negative effects of CuO and ZnO NPs on silkworms and highlighted the potential to inevitably affect all living things due to intensive and possible mishandling of nanomaterials.

Hydroxyl free radical route to the stable siliceous Ti-UTL with extra-large pores for oxidative desulfurization.

A facile and mild method was successfully developed to prepare the stable, highly siliceous Ti-UTL zeolite with extra-large pores. The hydroxyl free radical (˙OH) was introduced for the first time to effectively promote the isomorphous substitution of Si for framework Ge under room temperature and neutral conditions, resulting in a stable titanosilicate with an outstanding catalytic activity for oxidative desulfurization.

Elucidation of correlated disorder in zeolite IM-18.

Classical crystallography is based on the translational periodicity of crystals and the analysis of discrete Bragg reflections. However, it is inadequate for determining disordered structures, of which the diffuse scattering is vital to evaluate the disorder level. The correlated disorder of IM-18 presents as zigzag chains arranged in translational periodicity and the double four-ring units randomly distributed along two dimensions. Supercell models regulated by multiple probabilities were systematically built to simulate the single-crystal and powder X-ray diffraction patterns in order to ascertain the specific disorder configuration in the single-crystal or polycrystalline samples of IM-18. The presence of defects in the polycrystalline sample was proved by combining 29Si magic angle spinning (MAS) NMR and 1H-1H double quantum MAS NMR spectra, and was quantitatively explored by the simulation method. The method could also elucidate other disordered structures in polycrystalline or single-crystal samples, despite the presence of defects or multidimensional disorder.

Observation of Interpenetration Isomerism in Covalent Organic Frameworks.

We report herein the first example of interpenetration isomerism in covalent organic frameworks (COFs). As a well-known three-dimensional (3D) COF, COF-300 was synthesized and characterized by the Yaghi group in 2009 as a 5-fold interpenetrated diamond structure ( dia-c5 topology). We found that adding an aging process prior to the reported synthetic procedure afforded the formation of an interpenetration isomer, dia-c7 COF-300. The 7-fold interpenetrated diamond structure of this new isomer was identified by powder X-ray diffraction and rotation electron diffraction analyses. Furthermore, we proposed a universal formula to accurately determine the number of interpenetration degrees of dia-based COFs from only the unit cell parameters and the length of the organic linker. This work not only provides a novel example to the category of interpenetration isomerism but also provides new insights for the further development of 3D COFs.

Synthesis and crystal structure of Sr3Bi2O6 and structural change in the strontium-bismuth-oxide system.

The crystal structures and their changing trend in the strontium-bismuth-oxide system are critical for the studies of the related systems and their applications. The crystal structure of Sr3Bi2O6 was obtained for the first time in the space group of R3[combining macron] with a huge unit cell of a = b = 25.1146(19) Å and c = 18.3685(16) Å and all bismuth ions are Bi3+ forming [BiO3] trigonal pyramids. Sr3Bi2O6 is a key compound for the structural change trend in the SrO-Bi2O3 binary oxide system at 1000 °C. With a decrease in the bismuth content, its valence state changes from +3 to +5 and Bi-O polyhedra changes from connected to isolated before Bi(v) appearance. In the system, the boundary of the solid solution ß-phase (Sr1-xBixO1+0.5x) at 900 °C was also determined accurately as 0.770 ≤ x ≤ 0.862, experimentally.

Endohedral Metallofullerene as Molecular High Spin Qubit: Diverse Rabi Cycles in Gd2@C79N.

An anisotropic high-spin qubit with long coherence time could scale the quantum system up. It has been proposed that Grover's algorithm can be implemented in such systems. Dimetallic aza[80]fullerenes M2@C79N (M = Y or Gd) possess an unpaired electron located between two metal ions, offering an opportunity to manipulate spin(s) protected in the cage for quantum information processing. Herein, we report the crystallographic determination of Gd2@C79N for the first time. This molecular magnet with a collective high-spin ground state (S = 15/2) generated by strong magnetic coupling (JGd-Rad = 350 ± 20 cm-1) has been unambiguously validated by magnetic susceptibility experiments. Gd2@C79N has quantum coherence and diverse Rabi cycles, allowing arbitrary superposition state manipulation between each adjacent level. The phase memory time reaches 5 µs at 5 K by dynamic decoupling. This molecule fulfills the requirements of Grover's searching algorithm proposed by Leuenberger and Loss.