Background The health problems of the elderly, especially the elderly women, are increasingly concerned. The prevalence of abnormal liver lipid metabolism in women after menopause is increasing, which is highly related to estrogen and follicle stimulating hormone. However, hormone replacement therapy is highly controversial, and will bring risks such as breast cancer and coronary heart disease. Therefore, this study aims to build an effective and convenient in vitro disease model and perform functional verification to analyze the molecular mechanism of candidate lncRNAs participating in FSH-induced liver lipid metabolism. Result The results indicated the successful preliminary establishment of an in vitro model for FSH-induced lipid metabolism abnormalities. High-throughput sequencing and bioinformatics analysis revealed a total of 174 differentially expressed lncRNAs. Utilizing a comprehensive database, we screened five candidate lncRNAs and conducted interference tests specifically on the upregulated lncRNA ENSMUST00000244884. The findings demonstrated that knocking down this lncRNA led to an increase in the expression of the LXR and ACOX1 genes, which are crucial for lipid metabolism. Consequently, the lipid metabolism abnormality phenotype was alleviated. Conclusion Based on the experimental results, we have determined that bile-derived liver organoids are well-suited for constructing an in vitro disease model of hormone-induced lipid metabolism abnormalities, enabling effective observation of lipid phenotypes. Furthermore, we have screened and identified lncRNAs involved in hormone-regulated lipid metabolism abnormalities at the non-coding regulatory level. These findings offer potential diagnostic markers and therapeutic targets for disorders related to lipid metabolism.
In the field of biomedical sensing, traditional sensing materials often suffer from low sensitivity, poor selectivity, and insufficient stability in complex biological samples, making it difficult to achieve precise detection. With their long-range ordered pore structures, ultra-high surface areas, and tunable properties, crystalline porous materials (CPMs) have become ideal candidates for next-generation sensing platforms, offering key advantages such as customizable active sites, efficient signal amplification through intrinsic enzyme-mimicking activities or functional molecule integration, and synergistic effects enabled by modular assembly. This review systematically examines the design strategies, signal transduction mechanisms, and application advances of CPMs—including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and hydrogen-bonded organic frameworks (HOFs), organic cages (OCs), metal–organic cages (MOCs), zeolites and various other porous materials —in biomedical sensing, covering detection targets ranging from clinical biomarkers to highly complex pathogens. It also provides an in-depth analysis of the stability and anti-interference performance of these materials in complex biological environments and identifies the key technical bottlenecks currently hindering their clinical translation. By elucidating the inherent relationship between material structure and sensing function, this review aims to offer forward-looking theoretical guidance and practical technical pathways for the development of next-generation, high-performance, and intelligent biomedical sensors.
Efficient and selective SO2 capture from flue gas, particularly under humid conditions, remains a significant challenge. Herein, we report the successful molecular design and construction of Pillar‐Layered Co6 Cluster MOF (PLC‐Co), an ultramicroporous columnar layered MOF featuring a unique tfz‐d topology. Comprehensive studies revealed remarkable performance: single‐component isotherms showed a record SO2/CO2 selectivity ratio exceeding 22 (5.71 mmol/g SO2 vs. 0.36 mmol/g CO2 at 0.1 bar), the highest reported among crystalline porous materials. Its high performance was validated in multicomponent breakthrough simulations and experiments, demonstrating sustained high‐efficiency SO2 removal even under challenging 50% RH conditions. A combined experimental and computational study on the interaction between SO2 and PLC‐Co single crystals has revealed the true adsorption sites of SO2 within the material. This research elucidates the molecular adsorption mechanism and identifies specific interaction sites responsible for the observed unique selectivity. Furthermore, PLC‐CO exhibits excellent thermal and chemical stability, along with outstanding repeatability and regenerability. These findings highlight PLC‐CO as a highly promising material for practical flue gas desulfurization and showcase the effectiveness of topological design strategies for developing high‐performance porous materials for demanding gas separations.
Benzimidazolone-metal complex pigments are widely used in various industrial fields owing to their comprehensive chromatograms, good color performance, excellent durability, and moderate cost. To expand their applications to flexible conductive materials, the conductivities of these pigments must be increased to make them compatible with the electrospinning technique. In this study, benzimidazolone-metal complex pigments with various chelating metals were prepared and combined with reduced graphene oxide (rGO) to form rGO composite pigments. The performance of various metal chelated pigments was compared, and the results showed that the pigment with Ni as the chelated metal had the highest crystallinity and thermal stability. The molecular geometries of the complexes were optimized at the DSD-PBEP86 level of the density functional theory. Nylon fiber membranes with or without rGO composite pigments were prepared via electrospinning, and the conductivity, surface morphology and mechanical properties of the fiber membranes were analyzed. The fiber membrane with rGO composite pigments demonstrated a maximum electrical conductivity of 21.7 S cm-1. The average fiber diameter of the membranes decreased from 779 to 150 nm after the addition of rGO composite pigments, and the corresponding Young's modulus increased from 21.1 to 91.7 MPa. The experimental results indicated that adding rGO composite pigments to electrospun nylon could produce flexible composite fiber membranes with high conductivity and excellent mechanical properties.
The poor electrical conductivity of metal-organic frameworks (MOFs) limits their electrocatalytic performance in the oxygen evolution reaction (OER). In this study, a Py@Co-MOF composite material based on pyrene (Py) molecules and {[Co-2(BINDI)(DMA)(2)] DMA}(n) (Co-MOF, H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide, DMA=N,N-dimethylacetamide) was synthesized via a one-pot method, leveraging pi-pi interactions between pyrene and Co-MOF to modulate electrical conductivity. Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes, achieving an overpotential of 246 mV at a current density of 10 mA cm(-2) along with excellent stability. Density functional theory (DFT) calculations reveal that the formation of O* in the second step is the rate-determining step (RDS) during the OER process on Co-MOF, with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH* intermediate for Co sites. CCDC: 2419276.
Metal-exchanged zeolites are cost-effective and environmentally friendly catalysts for non-oxidative propane dehydrogenation (PDH), offering high activity, selectivity, and stability. These characteristics make them promising alternatives to conventional Pt-based or toxic Cr2O3 catalysts. In this study, we demonstrated that experimentally quasi in situ characterized species, such as metal hydrides, influence the formation of propene and hydrogen, exemplified by the CHA zeolite catalyst. Density functional theory (DFT) calculations confirmed that the metal hydride-mediated pathway is more feasible compared to the previously proposed heterolytic "alkyl" pathway. Overall, both the heterolytic "alkyl" pathway and metal hydride-mediated pathway consistently demonstrate that the Ga-CHA zeolite exhibits higher reactivity than the In-CHA zeolite. Moreover, the structure-activity relationship for the PDH process depends on a simple structural descriptor: the radius of the internal tangent circle formed by the triangle [GaH2]+ species within 80 types of zeolite datasets. Notably, the AFV zeolite within the International Zeolite Association shows excellent catalytic performance, surpassing that of the CHA zeolite. Our work provides new insights into the PDH reaction mechanism in metal-exchanged zeolites and offers an efficient approach for screening and guiding the synthesis of novel catalysts.
Engineering the zeolite dimensionality reveals that 2D MWW layers outperform their 3D analogues by enhancing CO 2 /C 2 H 2 separation efficiency.
The [3.3.3]propellane scaffold, present in various natural products, is a three-dimensional structure of interest in synthetic chemistry. Traditionally, these compounds are synthesized through a ring-by-ring strategy that is tedious (long steps of synthesis) and challenging (building two adjacent bridgehead quaternary centers of the target motifs is a formidable task). Herein, we report a nickel-catalyzed one-step, three-ring propellanation reaction that constructs the [3.3.3] propellane core from linear yne-vinylcyclobutanones. This method employs Ni(COD)2 and P(Ad)3 as the catalytic system and exhibits a broad substrate scope. The utility of this reaction has been further demonstrated through the formal synthesis of modhephene, a natural product featuring a [3.3.3] propellane skeleton. This propellanation reaction can be envisioned as biscarbene insertion of alkyne into the C-C bond in cyclobutanone and the C-H of the vinyl group in the substrates, but it actually takes place through oxidative cyclometalation of the alkyne and carbonyl group, Cope rearrangement, β-hydrogen elimination, trienolate cyclization, and reductive elimination, supported by DFT calculations and a deuterium labeling experiment. The detailed ligand exchange reaction (reaction initiation process) from Ni(COD)2 to the Ni complex coordinated by the phosphine ligand and substrate, has also been studied computationally. How the tether group in the substrates affects the propellanation reaction and the side rearrangement reaction of vinylcyclobutanones to cyclohexenones has been analyzed, finding that electron-withdrawing tethers such as NTs and O favor the propellanation reaction, while the electron-neutral tether such as CH2 and NBn tether, which is less electron-withdrawing compared to NTs, reduce this preference.
The development of efficient and stable non-precious bifunctional electrocatalysts for overall water splitting is highly desirable but remains challenging. Herein, a ternary composite material comprising Co (VO3)2, CoO, and Co3O4 phases (denoted as CVO-CoOx) was in-situ constructed on nickel foam via a facile hydrothermal approach. The introduction of vanadium is crucial for directing the formation of a well-defined three-dimensional nanosheet architecture, in sharp contrast to the nanoparticle-aggregated morphology of the vanadium-free CoO/Co3O4 reference. Comprehensive characterization confirms the successful integration of multiple phases and reveals strong electronic interaction among them, characterized by electron transfer from Co to V and an increased concentration of defect-associated oxygen species. Benefiting from these synergistic effects and the optimized electronic structure, the CVO-CoOx/NF electrode delivers outstanding bifunctional electrocatalytic activity in 1.0 M KOH, requiring overpotentials of only 230 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) to reach 100 cm−2. Furthermore, CVO–CoOx/NF exhibits excellent long-term stability over 32 h for HER and 24 h for OER. This work illustrates an effective strategy for designing high-performance non-precious-metal multiphase heterostructures for sustainable electrochemical hydrogen production.
Visible-light-mediated electron donor-acceptor (EDA) complex catalysis has emerged as a powerful strategy for radical transformations under mild conditions, yet EDA donor catalytic systems driven by hydrogen bonding remain largely underexplored. Herein, we report a H-bonded EDA (H-EDA) donor catalysis system, employing thiols as donor catalysts to achieve Markovnikov hydroarylation and hydroxyalkylation of N-acyl enamines under redox-neutral conditions. This protocol proceeds under metal-free, base-free, and redox auxiliary-free conditions with complete atom economy. Mechanistic studies reveal that the reaction proceeds through oxidative nucleophilic coupling enabled by a photoinduced H-EDA complex via SET and 1,5-H-shift. The protocol features broad substrate scope, excellent regioselectivity, and gram-scale scalability. This work establishes a general H-EDA donor catalytic platform and redefines EDA donor catalysis beyond conventional redox auxiliary (RA)-mediated activation.
Herein, we uncover structural dimensionality as a key factor governing CO2/C2H2 separation in MWW zeolites. Exfoliated MWW monolayers outperform 3D frameworks by extended breakthrough interval with higher selectivity. Combined experimental and DFT analyses reveal site-specific adsorption and reduced transport barriers, establishing dimensionality as a new design axis for molecular sieving.
The difunctionalization of alkenes and alkynes offers an efficient route to access two functional groups, making it a cornerstone of modern synthetic methodology. Translating this concept to unactivated beta-bromoethylarenes, however, confronts a fundamental difficulty: the activation of an inert benzylic C(sp(3))-H bond must be orchestrated in the same molecule that contains a labile C-Br bond. In this study, we report a heterogeneous photocatalytic strategy to overcome this challenge based on a distributed activation-synchronous functionalization radical mechanism. This approach employs graphitic carbon nitride (g-C3N4) as a recyclable heterogeneous photocatalyst under visible light, enabling the selective conversion of the common precursor into either alpha-chloroketones or alpha-trifluoromethylketones, with the product outcome controlled by the base. The reaction accommodates a broad range of substrates and functionalized drug-like molecules, is amenable to gram-scale synthesis, and features good catalyst recyclability. The method's utility is underscored by a 3-step synthesis of thyroliberin agonists, significantly outperforming the prior 10-step route. Mechanistic studies reveal that the base governs the quenching of photoexcited g-C3N4 by CF3SO2Cl, thereby diverting the reaction through distinct radical-mediated pathways.
Ethylene is a foundational commodity in the chemical industry, with its derivatives accounting for over 75% of all petrochemical products. Globally, ethylene production capacity is a crucial metric for evaluating a nation's petrochemical development. Consequently, ethylene purification is of paramount importance in the petrochemical sector. In this work, we propose the rational design of an ultramicroporous metal-organic framework (MOF) for the purpose of achieving single-step ethylene purification. We first synthesized a microporous poly-nuclear cobalt-based MOF (Co-MOF) using an aqueous phase method. The phase purity and excellent thermal stability of the Co-MOF were confirmed by PXRD and TGA. Furthermore, its permanent porosity was verified through N2 adsorption at 77 K, yielding a specific surface area of 680.4 m2 g-1 and a pore size of 8.3 & Aring;. Structural analysis revealed a high density of phenyl rings within the Co-MOF. These phenyl rings are anticipated to facilitate interactions with gases containing unsaturated bonds and enable van der Waals forces through interactions between their hydrogen atoms and those of the adsorbates, thereby promoting separation, based on this structural premise, static adsorption measurements were conducted for C2H2, C2H4, and C2H6. At 298 K and 1 bar, the adsorption capacities were 66.5, 57.1, and 58.0 cm3/g, respectively. To validate its potential for singlestep ethylene purification, we first performed breakthrough simulations, which indicated successful separation. Subsequent experimental breakthrough tests confirmed the MOF's efficacy in practical ethylene separation and purification applications. Finally, Density Functional Theory (DFT) calculations were performed to elucidate the adsorption mechanism. The computational results corroborated the initial hypothesis, revealing that the effective separation is primarily attributed to the interactions and hydrogen-mediated van der Waals forces between the phenyl rings in the Co-MOF and the unsaturated bonds of the guest molecules. This work provides a valuable reference for the rational design of MOFs and the establishment of structure-property relationships for selectively capturing target gases.
Developing methods to synthesize various bioisosteres mimicking substituted benzene rings is revolutionizing drug discovery. Many bioisosteres such as bicyclo[1.1.1]pentanes (BCPs) and bicyclo[2.1.1]hexanes (BCHs) have been developed, but methods to synthesize these bioisosteres are limited. We proposed a skeletal editing strategy converting newly designed BCP derivatives, vinyl bicyclo[1.1.1]pentanes (vinyl BCPs) into vinyl bicyclo[2.1.1]hexanones (vinyl BCHones) through Rh-catalyzed [4+1] reaction of vinyl BCPs and carbon monoxide. Vinyl-BCPs and vinyl-BCHones are bioisosteres of di- and tri-substituted benzenes, respectively. The key to the success of this skeletal editing is that the vinyl group in vinyl BCHs can help the C-C cleavage of the four-membered ring in the BCP moiety and then realize carbonyl insertion The mechanism of this [4+1] reaction has also been investigated by DFT calculations.
Hierarchically porous hollow NiCoLDH@HCNFs are synthesized via ZIF-8 templated coaxial electrospinning. This unique architecture accelerates mass transport and exposes abundant active sites, significantly boosting methanol oxidation.
Interfacial effects critically regulate photocatalytic pathways through charge transfer modulation, reactant enrichment, and transition-state stabilization. However, precisely manipulating free electrons to drive efficient O2 reduction to H2O2 remains challenging. To address this, we develop a hydrothermal pretreatment-assisted heterogeneous molten salt strategy to synthesize crystalline carbon nitride (S/Cl-CN). This approach synergistically integrates molten KSCN (enabling rapid mass transfer and in situ generation of electron-withdrawing CN groups) with solid KCl (providing spatial confinement for oriented crystallization). The heterogeneous environment optimally tunes interfacial effects, enhancing structural order and charge separation efficiency. The resulting S/Cl-CN exhibits extended visible-light absorption (narrowed bandgap 2.67 eV), accelerated carrier mobility and optimized O2 adsorption sites via CN-induced electron redistribution. These properties enable record H2O2 production rates of 4.58 mM g-1 h-1 in pure water (17-fold higher than the reference) and 177.1 mM g-1 h-1 with the sacrificial agent. Mechanistic studies confirm interfacial engineering promotes two-step single-electron oxygen reduction (via stabilized OOH⁎ and HOOH⁎ intermediates), complementary water oxidation pathways and reduced energy barriers for O2 activation and conversion. This work resolves electron-manipulation challenges in photocatalytic H2O2 synthesis and establishes a scalable molten salt platform for interface-optimized catalyst design.
The development of efficient and stable bifunctional electrocatalysts for the overall water splitting process is crucial for addressing the energy crisis and environmental challenges. This paper presents the synthesis of isomorphic MOFs, TIT-3-M (M = Co or Ni), through various methods, including hydrothermal synthesis (HS), stirring synthesis (SS), and ultrasonic-assisted synthesis (US), using 4,4 ',4 '-tris(aminobenzoic acid) (H3NTB) and 1,3-bis(4-pyridyl)propane (1,3-BPP). Specifically, the bimetallic material TIT-3-CoNi (US) was synthesized in a 1:1 ratio in an aqueous medium via ultrasonic-assisted method. This material exhibited a current density of 10 mA cm-2 at low overpotentials of 0.79 V for the hydrogen evolution reaction (HER) and 1.99 V for the oxygen evolution reaction (OER). Additionally, an overall water splitting device was assembled using TIT-3-CoNi(US) @NS and TIT-3-CoNi(US)@NS as the anode and cathode, respectively, under alkaline conditions, achieving a current density of 10 mA cm-2 at a cell voltage of 1.37 V. Density functional theory (DFT) calculations indicated that the fixed potential reaction step (PDS) involved the generation of Co active sites (O2) and Ni active sites (O*), corresponding to overpotentials of 0.63 and 0.67 V, respectively. The results suggest that Co is the preferred electrochemical active site for OER. This work paves the way for the development of advanced catalysts with enhanced performance for significant industrial processes, such as water electrolysis or fuel cell technology.
The design of high-efficient photocatalysts is desirable for overall water splitting. In this work, the first-principles calculations are implemented to investigate the component ratio effects on the photocatalytic water splitting of MoS2/MoSe2 lateral heterostructure. MoS2/MoSe2 lateral heterostructure shows a decreased band-gap from 1.84 to 1.61 eV as component ratio n increases, and its band-edge alignments straddle the redox potential of H2O, only with the precondition of n < 0.5. According to the work function difference between the isolated monolayers, a significant charge separation appears across the stitching area, with the maximal charge transfer being 0.187 e/unit from MoSe2 to MoS2 side, and thereby induces a built-in electric field of 0.25 similar to 0.29 eV/unit, promoting the separation of HER and OER. MoS2/MoSe2 lateral heterostructure possesses considerable hole (electron) mobility of about 150 (50) cm(2)V(-1)s(-1), facilitating the charge-transfer and aggregation in the surface reactions. The absorption shows an obvious red-shift, sufficiently improving photon utilization. Additionally, MoS2/MoSe2 lateral heterostructure with n < 0.50 exhibits the reduced energy barriers in both the HER and OER. The strain and pH effects show that MoS2/MoSe2 lateral heterostructure with n < 0.5 behaves enhanced photocatalytic performance under tensile strain, and the heterostructure with n > 0.5 can also possesses suitable band-edge alignments by increasing pH value. These results provide theoretical support for developing efficient photocatalyst by adjusting component ratio in MoS2/MoSe2 lateral heterostructure.