Latest ArticlesSulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62662699(Operation and Technical Support)
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
