As one of the famous traditional Chinese herbal medicines, Fritillariae Cirrhosae Bulbus (FCB) is widely used in the prevention and treatment of respiratory diseases and has the best curative effect among the known fritillarias medicines. Due to the variety, complex sources, similar appearance and shape, it is difficult to distinguish FCB with high curative effect (h-FCB) from other common fritillarias (c-FCB) in the market. In this paper, a very simple chemiresistor is used to identify FCB from three commonly used fritillarias drugs. The sensors are fabricated by anisotropic electrically conductive metal-organic framework (cMOF) thin film Cu ₃(HHTP) ₂ (Cu-HHTP _[001] and Cu-HHTP _[100]) as active materials owing to their ability to detect specific groups of volatile organic compounds (volatolomics) as the functional motifs of chemiresistor. As a result, the sensors show orientation-dependence identification ability to FCB. Cu-HHTP _[001]- based sensor shows the highest response (344.17%) to 0.5 g h-FCB powder volatiles among its three other c-FCB which is much higher than Cu-HHTP _[100] (135.50%). Ultimately, Cu-HHTP _[001] can realize the identification of FCB with an accuracy of 97.2% in a simple and real-time manner.

A catalyst-free and additive-free ring-opening reaction of polyfluoroalkyl peroxides, triethylenediamine (DABCO), and 1, 2-dichloroethane (DCE) has been developed for the defluorinative synthesis of structurally diverse piperazines featuring a fluoroenone framework and a N-chloroethyl-substituent with high Z-stereoselectivity. The success of this three-component reaction is attributed to the in situ generation of an active 1-(2-chloroethyl)-1, 4-diazabicyclo[2.2.2]octan-1-ium (DABCO·DCE) salt, which judiciously acts as a formal N-(2-chloroethyl)piperazine equivalent in the defluorinative coupling with less-studied aliphatic fluorinated substances. Impressively, this reaction accomplishes multi-activation of robust C(sp ³)-F, C(sp ³)-Cl, C(sp ³)-O, and C(sp ³)-N bonds in a one-pot process, offering a practical platform for the late-stage functionalization of complex molecules. Furthermore, the resulting products can not only serve as versatile building blocks for the synthesis of fluorinated heterocycles, but also undergo C—Cl bond displacement transformations with N-, O-, and S-nucleophiles.

Arylidenecyclopropanes (ACPs) are highly strained substrates that can be readily utilized for diverse transformations. This study showcases the outcomes of copper-catalyzed ring-opening hydrosilylation and hydroboration reactions of ACPs, showcasing precise cleavage of C—C bonds. The reaction presents an effective and convenient method for producing homoallylic silanes and boronates.

A variety of 3-nitroindazoles and 3-aminoindazoles were prepared in good to excellent yields with high regioselectivity through TBN-mediated nitration at the C3-position of indazoles under the air conditions and sequential reduction. Mechanistic studies revealed that TBN played crucial roles to produce ·NO ₂ radical source in the presence of air conditions and C3-nitration of indazoles was initiated by N1-nitration and sequential migration of NO ₂ group to C3-position. Moreover, this method could be easily applied in the gram scalable synthesis of ibuprofen and ciprofibrate-derived 3-aminoindazoles. The present method highlights air as mild oxidant, metal-free radical nitration of indazole, N—N bond formation and cleavage, and late-stage modification of drugs.

The pursuit of advanced sodium-ion batteries (SIBs) has been intensified due to the escalating demand for sustainable energy storage solutions. A W-doped P2-type layered cathode material, Na _0.67Ni _0.246W _0.004Mn _0.75O ₂ (NNWMO), has been developed to address the limitations of traditional cathode materials. Compared to the pristine Na _0.67Ni _0.25Mn _0.75O ₂ (NNMO), NNWMO exhibits improved reversible capacity, excellent cycle performance, and remarkable rate performance. It can deliver an increased discharge capacity of 142.20 mAh/g at 0.1 C, with an admirable capacity retention of 80.5% after 100 cycles at high voltage. In situ XRD results demonstrate that the rivet effect related to the strong W—O bonds inhibits irreversible phase transition and enhances structural reversibility during charge/discharge processes. High-resolution scanning transmission electron microscopy and X-ray diffraction results confirm successful lattice doping of W ⁶⁺ and increased layer spacing, contributing to favorable sodium ion diffusion kinetics. Density-functional theory (DFT) calculation results further reveal that the smoother Na ⁺ ion diffusion dynamics is attributed to the reduced migration energy barrier of Na ⁺ with the insertion of W ⁶⁺. This study provides valuable insights into the design of high-performance cathode materials for next-generation SIBs, showcasing the potential for more efficient, stable, and enduring energy storage solutions.

Hydrazine hydrate (DH) is a widely used chemical agent, but it is highly toxic. Thus, the development of low-cost and easy-to-prepare materials for the detection and adsorption of DH is very significant. Herein, a novel and easy-to-prepare supramolecular smart material based on bisquinoline-functionalized naphthalene diimide ( DQ8) has been designed and synthesized. In the DQ8, the synergistic effect between quinoline and naphthalene diimide groups has been employed to improve the selectivity and sensitivity for binding of DH. The DQ8-based crystalline porous material ( DQ8-CPM) can simultaneously detect and adsorb DH and produce noticeable fluorescence color changes after adsorption of DH vapor. More significantly, the DQ8-CPM shows nice recycling performance on DH detection and adsorption. Meanwhile, a smart gel based on DQ8 ( DQ8-G) shows multi-channel response for DH through color, fluorescence, and state changes. The DQ8 shows high selectivity and sensitivity for DH. The detection limit of DQ8 for DH is 8.6 × 10 ^-7 mol/L. According to the investigation of the DH binding and response mechanism, the synergistic effect between quinoline and naphthalene diimide groups plays an important role in the DH response process. It’s a simple and feasible way to develop materials for detection and adsorption of DH through synergistic effects.

We described a Yb(OTf) ₃ combined with Pybox ligand catalyzed asymmetric [3+3] cycloaddition of N-vinyl cinnamaldehyde nitrones with activated cyclopropanes to prepare various functionalized 1, 2-oxazines in 24%—95% yields and 22%—96% ee. Experimental results revealed that the reaction underwent a domino [3+3] cycloaddition, dealkenylation, and aza-1, 4-addition in three steps. The chiral 1, 2-oxazine could be obtained in gram scales and easily converted into various 1, 2-oxazine scaffolds. The present method features broad substrate scope, good functional group compatibility, three-component domino reaction, and asymmetric [3+3] cycloaddition of N-vinyl nitrones with activated cyclopropanes.

Crystalline materials with diastereomerism serve as ideal prototypes for investigating the influence of coordination environments on chemophysical properties. In this study, we synthesized a pair of axial-equatorial isomers [Co(II)(HB(tim ^tBu) ₃)( cis-dppen)](BF ₄)· solv ([HB(tim ^tBu) ₃] ^- = hydrotris(3-tertbutyl-2-thioxoimidazol-1-yl)borate; cis-dppen = cis-1, 2-bis(diphenylphosphino)ethene; solv = 0.5THF·2H ₂O and 2H ₂O for ax-CoHS ₂P ₂ and eq-CoHS ₂P ₂, respectively), by varying the crystallization temperatures. Despite both diastereoisomers adopting distorted square pyramidal geometries, the bidentate cis-dppen ligand chelates to the central Co(II) either in an axial-equatorial or equatorial-equatorial manner, with a boron-hydrogen binding to the metal center. Magnetic studies reveal differences in g-values between these axial-equatorial isomers. X-band electron paramagnetic resonance spectra suggest rapid equilibrium and potential conformational interconversion in response to temperature changes in solution. Magnetic measurements indicate field-induced slow relaxation of magnetization in this low-spin S = 1/2 system, with spin-lattice relaxations dominated by Raman and quantum tunneling of magnetization mechanisms due to the absence of thermally populated excited states.

3, 3-Disubstituted oxindoles, forming the core of extensive bioactive natural products and drugs, attract tremendous efforts to develop efficient methods for their preparation. Here, a photocatalyst-free approach for the synthesis of 3, 3-disubstituted oxindoles via a substrate-photosensitive strategy under visible light was successfully developed. Preliminary mechanistic studies illustrated that isatin-derived imines can be directly excited by visible light to generate strong oxidant states, facilitating subsequent single-electron transfer (SET) processes with Hantzsch esters to afford the corresponding α-amino radical intermediates. Thus, these α-amino radicals promote the subsequent Giese radical addition or radical/radical cross-coupling reactions to furnish diverse functionalized 3-substituted 3-aminooxindoles in high yields.

An efficient transannular cyano migration is reported for gem-dicyano-1, 6-diene, which is triggered by the addition of external arylsulfonyl radicals. The overall transformation proceeds through a sequence of intramolecular 5-exo-trig cyclization, suprafacial 1, 4-cyano migration, and the capture by H or D atom, leading to the production of valuable polysubstituted cyclopentanes under mild photoredox catalytic conditions. The reaction is adapted to a wide range of sodium (hetero)arylsulfinates, demonstrating good functional group compatibility. This method provides a new protocol for radical-mediated functional group migration.

Terpenoids are a large and diverse family of secondary metabolites that have gained more attention from chemists and pharmacologists for their intriguing skeletons and broad biological activities, including anti-inflammatory, antitumoral, antimicrobial, and anti-viral effects. Based on the previous reviews, this review comprehensively summarized recent advances on bioactive terpenoids, focusing on their intriguing structural features and promising biological activities, covering literature from 2020 to 2023. In this review, 532 terpenoids with remarkable chemical architectures and biological properties are classified into sesquiterpenoids (142), diterpenoids (129), sesterterpenoids (24), triterpenoids (52), and meroterpenoids (185), that were isolated from terrestrial and marine resources. This review would provide a reference for researchers to rapidly discover the interesting terpenoids for further study as promising drug leads.