Latest ArticlesFluorine locates a pivotal position in modern medicinal chemistry due to its distinctive impact on the properties of organic molecules. This work described an efficient divergent palladium/XPhos-catalyzed ring-opening defluorinative cross-coupling of gem-difluorocyclopropanes with less nucleophilic fluorinated malonates or fluorobis(phenylsulfonyl)methane. The corresponding difluoro malonates and 2,4-difluorobutadienyl sulfones were obtained in good yields, respectively. Besides, this protocol also enabled the modification of structurally diverse complex molecules.
As an essential micronutrient, selenium (Se) plays crucial roles in maintaining cutaneous homeostasis through multifaceted mechanisms including redox regulation, immunomodulation, and anti-tumorigenic activity. While epidemiological and preclinical studies substantiate the therapeutic promise of Se in managing dermatological pathologies such as psoriasis, atopic dermatitis, and cutaneous malignancies, conventional Se formulations face translational challenges due to suboptimal bioavailability and dose-limiting hepatotoxicity. Recent advancements in nanobiotechnology have catalyzed the emergence of Se nanoparticles (SeNPs) as next-generation therapeutic platforms. These engineered nanostructures exhibit superior pharmacokinetic profiles characterized by enhanced epithelial permeability, stimuli-responsive drug release kinetics, and targeted biodistribution. This comprehensive review systematically examines: (1) pathophysiological barriers in dermatologic therapy; (2) Se-mediated molecular circuitry; (3) nano-enabled theranostic breakthroughs; (4) preclinical validation of SeNPs-based combinatorial regimens. By critically evaluating structure-activity relationships of various nanoformulations, we delineate a translational roadmap bridging nanomaterial design principles with clinical needs in precision dermatology. This synthesis aims to accelerate the clinical deployment of Se nanotechnology while addressing key regulatory and manufacturing challenges.
Immunosuppressive tumor microenvironment (TME) is a key regulator in the high recurrence and metastasis rate of breast cancer after microwave (MW) thermal therapy. Pyroptosis, a form of programmed cell death initiated by inflammasomes, which can activate tumor immunogenicity and reprogram immune TME. Here, we report an extremely simple Al-based metal-organic frameworks nano-immunoadjuvants (AM NIAs) that programmatically activate nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 (NLRP3)-mediated pyroptosis to enhance MW-immunotherapy (MW-ICB). After entering the TME, AM NIAs programmed activation of NLRP3-mediated pyroptosis by inducing mitochondrial dysfunction, upregulating HSP90 and promoting lysosomal stress. Consequently, substantial amounts of lactate dehydrogenase, interleukin-18 (IL-18), and calreticulin are released, which improves immunosuppressive TME and hinders tumor cell proliferation by facilitating T-cell infiltration. The integration of immune checkpoint inhibitors with MW elicits potent immune responses, demonstrating high inhibition of both primary and distant tumors. Thus, a simple yet effective nano-immunoadjuvant is developed to enhance MW-ICB in breast cancer simply by NLRP3-mediated pyroptosis and immunosuppression reversal.
Four novel Daphniphyllum alkaloids with highly rearranged skeletons involving a 6/5/7/7/5 pentacyclic scaffold (1), a 6/5/7/5/6/5/6 heptacyclic scaffold (2 and 4), and a 6/5/7/5/6/5 hexacyclic scaffold (3), were isolated from Daphniphyllum calycinum. Particularly, compound 1 contains a unique 13-oxa-17-aza-pentacyclo[7.6.4.112,15.04,8.09,15] eicosane core. Their structures were elucidated by comprehensive spectroscopic analyses, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Putative biosynthetic pathways for compounds 1–4 were discussed with caldaphnidine C (5) as their biosynthetic precursor. Compound 2 markedly enhanced the survival of H9c2 cardiomyocytes under oxygen glucose deprivation and reoxygenation conditions. Mechanistic study revealed that 2 exerted its cardioprotective effects by activating the nuclear factor erythroid 2-related factor 2/heme oxygenase-1 (Nrf2/HO-1) antioxidant pathway, thereby enhancing cellular antioxidant capacity and alleviating oxidative stress induced by hypoxia.
Chemodynamic therapy (CDT) represents a novel strategy for the safe treatment of malignant melanoma. It capitalizes on transition metal-catalyzed Fenton-like reactions to generate hydroxyl radicals (•OH) that directly eradicate tumor cells. However, its efficacy is hindered in the tumor microenvironment (TME) by low endogenous hydrogen peroxide (H2O2) levels and high glutathione (GSH) content. To overcome these limitations, an injectable self-healing adipic dihydrazide (ADH)-modified hyaluronic acid (HA) (HA-ADH)/aldehyde terminated polyethylene glycol (PEG-CHO)/PVP-cupric peroxide (CuO2) nanoparticles (HPC) hydrogel was developed. This hydrogel system is injectable, pH-responsive, self-healing, and enables sustained GSH depletion through dual Cu2+/•OH-mediated mechanisms. The HPC hydrogel system not only compensates for the TME's endogenous H2O2 deficiency through self-generated H2O2 but also disrupts redox homeostasis via GSH oxidation, thereby inactivating glutathione peroxidase 4 (GPX4) and promoting lipid peroxide accumulation to trigger ferroptosis in melanoma cells. Such a strategy represents a promising approach to achieve enhanced CDT and potent ferroptosis induction by synergizing dual GSH-depleting cycling and self-sufficient H2O2 generation.
Photocatalytic H2O2 production has emerged as a promising strategy for solar-to-H2O2 energy conversion. However, the inevitable requirement for aeration or sacrificial agents poses great challenges for its further application, particularly in environmental remediation process. Previous works often struggles to simultaneously balance the antibiotics degradation and H2O2 production. Herein, bifunctional TiO2 mesocrystal with oxygen vacancy (meso–TiO2-x) was prepared through a facile pyromellitic diimide assisted hydrothermal process. The well-aligned meso–TiO2-x superstructures with unique oxygen vacancies on the surface collectively facilitated the direct h+ oxidation and oxygen reduction reaction (ORR). The ciprofloxacin degradation through direct h+ oxidation boosted the separation of photogenerated carriers, which enhances the e- participation in ORR, resulting H2O2 production rate up to 904.2 µmol g−1 h−1. This work provides an ingenious strategy of constructing bifunctional catalyst to achieve synergistic antibiotics degradation and H2O2 production without the addition of exogenous reagents.
Probes that can undergo photoconversion in situ within cells are advantageous tools for live cell imaging in terms of precise spatial and temporal control. We herein present a new concept to construct photoconvertible probes based on intramolecular oxygen direct arylation within cells. Xanthones bearing aryls (XO-Ars) were designed and prepared. XO-Ars undergo oxygen direct arylation under visible light irradiation in cells to afford xanthene derivatives (XE-Ars). XO-Ars initially accumulate in the endoplasmic reticulum (ER) with green emission and then migrate to the mitochondria with bright red emission. Sequential single-cell lighting up experiments show high spatiotemporal control ability and utility in single or multi-cell tracking. In addition, the photoproducts irradiated with optimized wavelength light source show excellent photodynamic therapy effects. As the duration of light exposure increases, the cells begin to undergo apoptosis. These innovative photoconvertible probes capable of migrating from ER to mitochondria driven by light provide a feasible approach for the in-situ monitoring of subcellular physiological events and cell apoptosis.
To enhance the suitability of noble metal-based electrocatalysts for acidic overall water splitting, a Pt/Ir-based electrocatalyst incorporating Co and Pd anchored on Ti3C2Tx MXene (Ir/Co Pt Pd@MX) has been successfully synthesized. The incorporation of Co during the synthesis process increases the valence states of Ir and Pt, resulting in improved electrocatalytic performance. The Ir/Co Pt Pd@MX exhibits a low HER overpotential of 38 mV and an OER overpotential of 230 mV, outperforming commercial catalysts. The low noble metal containing electrocatalyst shows nearly 10 times the mass activity of Pt/C for HER and 35 times that of Ir/C for OER. The water splitting cell voltage is 1.46 V, with no observable decay after a 24-h stability test at 10 mA/cm2, establishing it as a top-tier noble metal-based electrocatalyst in acidic environments. Density functional theory (DFT) calculations indicate that Co facilitates the deposition of Ir, enhancing OER performance, while Pd restrict H+absorption of Ir, ensuring the stability. The energy barrier of the rate-determining steps for both the HER and OER decreases.
Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(Ⅱ) metallamacrocycles [Ru(η6-p-cymene)(µ2-m-bitmb)Cl]2·2X, m-bitmb = 1,3,5-trimethyl-2,4-di(imidazole-1-ylmethyl)benzene, X = Cl- (1·2Cl), NO3- (1·2NO3), CF3SO3- (1·2CF3SO3), PF6- (1·2PF6), or BF4- (1·2BF4). X-ray crystal structures reveal 1·2Cl in boat and chair conformations, 1·2NO3 in twist-boat and chair conformations, and 1·2CF3SO3 in a chair conformation. Chair/boat isomers of mono- and bis-DMSO adducts from 1·2Cl, 1·2CF3SO3 or 1·2NO3 in DMSO/H2O were separated and characterized. Slow anion-dependent interconversion of configurational isomers was observed in solution. Ligand field molecular mechanics and density functional theory calculations suggest an unusual macrochelate ring-opening isomerization mechanism. Such dynamic stimuli-responsive configurational changes offer scope for design of metallocycles for induced-fit recognition of biological targets.
Polycyclic pyrrole fused indolo[2,1-a]isoquinolins were efficiently generated from alkene-tethered indole derivatives and di–tert-butyldiaziridinone in up to 99% yield in the presence of Pd catalyst. The reaction likely proceeded via sequential Heck, CH activation, and amination process. Varying N-substituents of indole substrates led to indolo[3,2-b]indoles in up to 98% yields.
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