Latest ArticlesHere an enantioselective total synthesis of bioactive 3-deoxy-epothilone B is reported. Key features of this synthesis include Nelson’s alkaloid-catalyzed asymmetric ketene-aldehyde [2 + 2] cycloaddition to expeditiously construct the froward cis/trans configuration of C6−C8 position in a stereospecific manner and the subsequent allylic transposition nucleophilic addition to forge the C2−C4 unit. Other key steps involve an iridium-catalyzed asymmetric hydrogenation (AH) to introduce the C15 stereogenic center and a rhodium-catalyzed linear selective hydroformylation to install the C1 unit with our catalytic systems. In addition, the highly electrophilic enantioenriched β-lactone is regarded as a potential synthon for modular syntheses of a series of C1−C4 modified epothilones. Further biological activity evaluation indicated significant cytotoxicity of 3-deoxy-epothilone B against a panel of human tumor cell lines.
Transition-metal-catalyzed substitution of propargylic electrophiles with secondary phosphine oxides (SPOs) has emerged as a powerful strategy to phosphorus-containing frameworks. However, precise regiocontrol remains elusive due to competing pathways in allenyl-metal intermediates and SPO tautomerism. Herein, we report a dynamic coordination strategy that leverages the tunable binding modes of SPOs to achieve regiodivergent dienylation of propargylic esters, thereby accessing a diverse range of 1,3-dienyl phosphines. Through fine-tuning of ligands and the strategic use of Brønsted or Lewis acid-assisted catalytic systems, we demonstrate switchable C2- versus C3-selective dienylation, governed by dynamic control over the coordination modes and reactivities of SPOs. Mechanistic studies reveal that the dynamic inner- or outer-sphere coordination dictates the regiochemical outcome, which proceeds via relay catalysis or bimetallic cooperative catalysis pathways, thus offering a rationale for the observed regiodivergence. This method provides a robust and modular platform for synthesizing multisubstituted 1,3-dienyl phosphines with broad substrate scope and excellent regio- and stereoselectivity, underscoring the potential of coordination-controlled reactivity in complex bond-forming processes.
Aging of Pt in diesel oxidation catalyst (DOC) leads to diminished catalytic activity, presenting a considerable challenge for catalyst regeneration and enhancement. This work investigates on the regeneration of Pt/Al2O3-SiO2 (Pt/AS) catalysts in DOC utilizing the synergistic effect of the indirect non-thermal plasma (INTP) and direct non-thermal plasma (DNTP) to optimize catalytic performance for efficient and stable conversion of gaseous pollutants. The distinctive properties of DNTP-INTP promote the removal of surface particulate matter (PM) and increase the availability of adsorbed oxygen (Oads) on the catalyst surface. Moreover, DNTP effectively reduces the particle size of sintered catalysts by applying a high-energy electric field. This process facilitates the conversion of PtOx to metallic Pt0. Additionally, agglomerated Pt structures can be reverted into regular hexahedral nanoparticles through the synergistic process. The regenerated catalyst demonstrates exceptional catalytic performance and stability, which can rival the performance of newly prepared catalysts. Notably, compared to the aged catalyst, the low-temperature performance improves significantly, with a reduction of 90 ℃ in the temperature at the onset of catalytic activity. These results highlight the considerable potential of plasma-assisted synergistic catalysts regeneration for revitalizing aged DOC within the context of advancing clean energy technologies.
Solar-driven hydrogen peroxide (H2O2) production presents a sustainable alternative to energy-intensive industrial methods, yet its efficiency using covalent organic frameworks (COFs) suffer from energy loss caused by strong exciton interactions. Herein, we designed COFs with donor-π-acceptor (D-π-A) architectures, using 2,5-dimethoxy-1,4-benzenedicarboxaldehyde as the D unit and optimizing the N-containing π-bridge units. The resulting TAPT–OCH3 COF, incorporating 4,4′,4′'-(1,3,5-triazine-2,4,6-triyl)trianiline as the A unit, demonstrated the extended electron pathways and the reduced exciton recombination, markedly boosting photocatalytic performance. Experimental results revealed that TAPT–OCH3 achieved a solar-to-chemical efficiency of 0.23% and a quantum yield of 2.21% at 420 nm, outperforming most reported COFs and metal-free catalysts. In situ characterization and theoretical calculations revealed that the TAPT–OCH3 enhances charge separation to drive H2O2 production via a 2e- oxygen reduction pathway, while its tailored electronic structure simultaneously improves the 1e- water oxidation process. Crucially, TAPT–OCH3 maintained high efficacy across diverse water sources and continuous-flow reactors under natural sunlight, enabling scalable H2O2 synthesis for water purification. Life cycle assessment confirmed the application stability of this material, underscoring its potential for sustainable environmental remediation. This work establishes a design paradigm for optimizing exciton dynamics in COF, highlighting the critical role of structural design for artificial H2O2 photosynthesis.
Achieving biomimetic leaves with high reflectance and polarization spectral similarity to vegetation is highly desirable. However, the polarization, often masked by the complex compositions of coatings, has long been overlooked. Herein, the reflectance and polarization spectral properties are simultaneously realized via electrostatic adsorption between hypoxanthine (HX) and sodium copper chlorophyllin (SCC). The SCC-doped HX coating exhibits high reflectance spectral similarity to vegetation, with a correlation coefficient of 0.9440 and a spectral angle cosine of 0.9685. Additionally, the degree of linear polarization is reduced by 39.3%. This study provides a reference for obtaining high-performance pigments for biomimetic leaves.
Overcoming the penetration barrier of nanomedicines remains a paramount challenge in antitumor therapy. Apoptotic bodies (ApoBDs), which are naturally generated from apoptotic cells, can mediate a potent neighboring effect by transferring drug to neighboring tumor cells via macropinocytosis. To amplify this process, we developed a tumor microenvironment-responsive nanoplatform (named as AD-NVs@CPP) to selectively enhance chemokine (C-X-C motif) receptor 4 (CXCR4) receptor-stimulated macropinocytosis. This platform was constructed by co-encapsulating doxorubicin (DOX) and the hypoxia-activated prodrug AQ4N into homologous tumor cell membrane-derived nanovesicles (AD-NVs), followed by biomineralization of a calcium phosphate (CaP) shell that incorporated a CXCR4-targeting peptide (RFFE-SHAPAKPVSLSYR). The resultant AD-NVs@CPP exhibited a core-shell structure with a hydrodynamic diameter of ~180 nm and achieved a high peptide encapsulation efficiency of 81.6% ± 8.2%. The CaP shell demonstrated excellent pH-responsive dissolution, releasing ~50% of the peptide within 24 h at pH 6.5 (vs. negligible release at pH 7.4), which consequently promoted cellular uptake and enhanced cytotoxicity under acidic conditions in vitro. Additionally, AD-NVs@CPP-induced ApoBDs served as efficient drug reservoirs, delivering drugs to adjacent cells with an IC50 value of 0.98 µg/mL (in terms of protein concentration). In vivo, AD-NVs@CPP significantly prolonged the blood circulation time (increasing the half-life of DOX compared to the free drug solution) and improved tumor accumulation. Crucially, it enabled programmed drug penetration: AQ4N was selectively delivered into deep hypoxic tumor regions, mediating comprehensive tumor growth inhibition while maintaining a favorable safety profile. This work provides a robust strategy for achieving deep tumor penetration through the synergistic enhancement of macropinocytosis and the ApoBD-mediated neighboring effect.
In this study, a simple N2 plasma strategy was employed to modify the surface of Co3O4, significantly enhancing its efficiency in activating peroxymonosulfate (PMS) for the degradation of tetracycline hydrochloride (TC). Co3O4 treated with plasma for 30 min (Co3O4–30) achieved a TC degradation efficiency of 93.2% within 30 min (k = 0.078 min−1), which was significantly higher than that of the pristine Co3O4 (k = 0.023 min−1). Studies demonstrated that plasma treatment induced the generation of oxygen vacancies (Ov) on the surface of Co3O4, which serve as key active sites during the catalytic process and facilitate the adsorption of PMS to generate singlet oxygen (1O2). As the dominant reactive oxygen species, the steady-state concentration of 1O2 was positively correlated with the TC degradation rate. Additionally, dominated by the non-radical pathway, the PMS/Co3O4–30 system exhibited high selectivity toward electron-rich pollutants as well as strong anti-interference capability against anions and complex water matrices. This study demonstrates that plasma technology serves as a viable approach for defect engineering in catalysts, enabling the selective generation of 1O2 from PMS.
Selenium (Se) speciation analysis is typically performed using complex and costly hyphenated analytical systems. In this study, we developed a novel strategy for Se speciation using gas chromatography combined with a 3D-printed point discharge micro atomic emission detector (GC-PD-μAED), coupled with chemical vapor generation (CVG) and headspace-solid phase microextraction (HS-SPME), for the simultaneous determination of selenite (Se(Ⅳ)), dimethylselenide (DMSe) and dimethyldiselenide (DMDSe) in aqueous matrices. The method involves derivatization of Se(Ⅳ) to volatile diethylselenide (DEtSe) using NaBEt4, followed by HS-SPME preconcentration of all three Se species prior to GC separation and PD-μAED detection at the Se emission line of 196.03 nm. The optimized method achieved limits of detection (LODs) of 2.34, 0.28 and 0.13 μg/L (as Se) for DMSe, DMDSe and Se(Ⅳ), respectively, with precision (RSD) ranging from 4.6% to 4.9%. The accuracy and practicability of the developed method were demonstrated through speciation analysis of Se in seven water samples with excellent recoveries (90.4%−107.9%). Moreover, this novel approach offers simplified instrumentation, significantly lower costs, and minimal use of consumables while maintaining robust analytical performance comparable to conventional methods, making it particularly valuable for resource-limited settings.
Widespread arsenic contamination in aquatic environments poses a major threat to human health and ecosystems, underscoring the urgent need for effective and selective remediation strategies. However, conventional technologies often suffer from reduced efficiency due to strong competition from coexisting anions such as phosphate, limiting their real-world applicability. In this study, we present a pH-regulated strategy for selective arsenate removal using ferric oxide (α-Fe2O3), a low-cost, non-toxic, and naturally abundant material. By integrating batch adsorption experiments, in-situ ATR-FTIR spectroscopy, two-dimensional correlation spectroscopy, and density functional theory simulations, we demonstrate that acidic conditions significantly enhance arsenate selectivity by promoting protonation-induced surface complexation. Protonation strengthens hydrogen bonding and facilitates a transition from monodentate to bidentate coordination, improving arsenate binding. We further identify the Fe-Fe interatomic distance as a key structural parameter governing complexation geometry and selectivity: Shorter distances (< 3.27 Å) enable dual coordination, while longer distances (~5.10 Å) restrict it. These mechanistic insights highlight the pivotal role of surface structure and protonation in dictating competitive adsorption outcomes. Overall, these findings provide a mechanistic framework for understanding and optimizing arsenate selectivity in multi-anion systems. By leveraging naturally occurring ferric oxide and simple pH adjustment, this work offers a scalable and practical approach to arsenic remediation in phosphate-rich waters.
Metal-organic frameworks (MOFs) hold promise as electrochemiluminescence (ECL) emitters but are limited by high operating potentials and low efficiencies, leading to substantial electrochemical interference and reduced sensitivity. Here, we report a defect-rich Fe(Ⅲ)-based MOF (De-Fe(Ⅲ)-MOF) that exhibits highly efficient ECL triggered at an ultralow potential (-0.3 V vs. Ag/AgCl). Prepared using electron-deficient 3,4,9,10-perylenetetracarboxylic acid (PTCA) as ligands and H3PO4 as the acid modulator, De-Fe(Ⅲ)-MOF features abundant open-metal catalytic sites, which achieves an exceptional cathodic ECL efficiency of 553.06%, even using classical Ru(bpy)3Cl2/S2O82− system triggered at -1.2 V as a standard. This outstanding performance is attributed to three key factors: (1) The abundant Fe(Ⅲ) active sites that efficiently catalyze S2O82− to produce SO4•- radicals at ultralow potentials; (2) the electron-deficient PTCA ligand that enables simultaneous reduction at similarly low potentials; and (3) the unified porous frame that facilitates efficient electron transfer through an ultrashort pathway, enhancing ECL efficiency. These features collectively minimize electrochemical side reactions and significantly enhance the sensitivity of the sensing platform. To demonstrate its practical application, we constructed an ECL sensor for carboxylesterase activity, achieving a limit of detection of 6.6 × 10–7 U/L with minimal interference.
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