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Structural-functional integrated polymer fibers with exciting properties are increasingly important for next-generation technologies. Herein, we report the structural-functional integrated graphene-skinned aramid fiber (GRAF) featuring high conductivity, high strength, and light weight, which is weaved for efficient electromagnetic interference (EMI) shielding. Graphene was self-assembled onto the surface of aramid fibers through a dip-coating strategy using an aramid polyanion (APA) as the binder and the etchant. The molecular dynamics (MD) simulation results show that the binding energy of the APA-modified aramid chain and graphene (1.3 J/m 2 ) is superior to that of the aramid chain and graphene (0.2 J/m 2 ). The APA has a higher surface energy (55.2 mJ/m 2 ) and can etch the fiber surface, forming grooves, which enables effective adsorption and self-assembly of graphene onto the fiber surface. The GRAF exhibits a high conductivity of 1062.04 ± 116.78 S/m, along with excellent strength (4.66 ± 0.16 GPa) and modulus (106.33 ± 8.21 GPa), outperforming most reported conductive composite fibers (e.g., natural fibers, polymer-based fibers, inorganic fibers, etc.). The weaved functional fabric using the structural-functional integrated GRAF shows an EMI shielding efficiency (SE) of up to 67.86 dB in the X-band and can rapidly heat up to 200 °C within 40 s at 12 V voltage. In addition, the GRAF fabric can maintain its electrical conductivity after a long-term washing, showing excellent washing resistance. This study demonstrates an effective method to fabricate structural-functional integrated materials and shows the promise of carbonene fibers for EMI shielding.

Antibiotic-induced inflammation involves the release of myeloperoxidase (MPO), an enzyme whose expression in tissues is associated with the inflammatory pathway. However, existing methods for detecting MPO in cells are limited. In this study, a DNAzyme nanorobot was developed using a scaffold of gold nanoparticles (AuNPs) decorated with functional DNAzyme strands and their fluorophore-labeled substrate strands. The DNAzyme remains inactive due to a self-assembled hairpin structure, with a phosphorothioate (PT) modification inserted into the stem domain. When MPO is present, it triggers a halogenation process that generates hypochlorous acid (HClO). HClO specifically catalyzes the cleavage of the PT-site, releasing free DNAzyme strands to cleave their substrates and generating an increasing fluorescent signal. The detection limit for MPO and its primary product, HClO, were determined to be 0.038 μg/mL and 0.013 μM, respectively. The DNAzyme nanorobot can be readily introduced into cells and function autonomously to differentiate increased MPO/HClO levels caused by antibiotics. This approach was applied to image RAW264.7 cells exposed to four prevalent antibiotics found in the environment (phorbol 12-myristate 13-acetate, erythromycin, penicillin, and tetracycline) as well as antibiotic production wastewater. This nanorobot offers novel strategies for monitoring inflammation to evaluate the health impacts of antibiotic exposure.

Three-dimensional (3D) imaging enables high-precision and high-resolution axial positioning, which is crucial for biological imaging, semiconductor defect monitoring, and other applications. Conventional implementations rely on bulky optical elements or scanning mechanisms, resulting in low speed and complicated setups. Here, we generate the double-helix (DH) point spread function with an all-dielectric metasurface and thus innovate the 3D imaging microscope (hence dubbed meta-microscope), both in 4f and 2f imaging systems. The 4f-meta-microscope with a numerical aperture of 0.7 achieves an axial localization accuracy below 0.12 μm within a 15.47 μm detection range, while the 2f-DH meta-microscope with a numerical aperture of 0.3 shows a 1.12 μm accuracy within a 227.33 μm range. We also demonstrate single-shot and accurate 3D biological imaging of the mouse kidney tissue and peach anther, providing a comprehensive and efficient approach for 3D bioimaging and other applications through a single-shot 3D meta-microscope.

This study presents a bioinspired ion host featuring continuous binding sites arranged in a tunnel-like structure, closely resembling the selectivity filter of natural ion channels. Our investigation reveals that ions traverse these sites in a controlled, sequential manner due to the structural constraints, effectively mimicking the ion translocation process observed in natural channels. Unlike systems with open binding sites, our model facilitates sequential ion recognition state transitions, enabled by the deliberate design of the tunnel. Notably, we observe dual ion release kinetics, highlighting the system's capacity to maintain ion balance in complex environments and adapt to changing conditions. Additionally, we demonstrate selective binding of two different ions-a challenging task for systems lacking structured tunnels., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Lysine lactylation has recently been discovered and demonstrated to be an essential player in immunity, cancer and neurodegenerative diseases. Genetic code expansion (GCE) technique is powerful in uncovering lactylation functions, since it allows site-specific incorporation of lactyllysine (Klac) into proteins of interest (POIs) in living cells. However, the inefficient uptake of Klac into cells, due to its high hydrophilicity, results in limited expression of lactylated POIs. To address this challenge, here we designed esterified Klac derivatives, exemplified by ethylated Klac (KlacOEt), to enhance Klac's lipophilicity and improve its cellular uptake. The expression level of site-specifically lactylated POIs was doubled using KlacOEt in both Escherichia coli and HEK293T cells. Immunoprecipitation mass spectrometry analysis verified the significantly increased yield of the precisely lactylated fructose-bisphosphate aldolase A using KlacOEt. Furthermore, in conjunction with the Target Responsive Accessibility Profiling approach, we found that lactylation at ALDOA-K147 altered the protein's conformation, which may explain the lactylation-induced reduction in enzyme activity. Together, we demonstrate that, through enhancing the yield of lactylated proteins with Klac esters via GCE, we are able to site-specifically reveal the effects of lactylation on POIs' interactions, conformations and activities using a suite of functional proteomics and biochemical tools.

The design of mutifunctional protein films for large-area spatially ordered arrays of functional components holds great promise in the field of biomedical applications. Herein, interfacial electrostatic self-assembly was employed to construct a large-scale protein thin film by inducing electrostatic interactions between three bovine serum albumin (BSA)-coated nanoclusters and cetyltrimethylammonium bromide (CTAB), leading to their spontaneous organization and uniform distribution at the oil-water interface. This protein film demonstrated excellent multienzyme functions, high antibacterial activity, and pH-responsive drug release capability. Therefore, it can accelerate the wound closure process through a synergistic effect that includes reducing local blood glucose levels, regulating cellular oxidative stress, eradicating bacteria, and promoting cell proliferation.

Developing low-cost and multifunctional adsorbents for adsorption separation to obtain high-purity (>99.9%) gases is intriguing yet challenging. Notably, the ongoing trade-off between adsorption capacity and selectivity in separating multicomponent mixed gases still persists as a pressing scientific challenge requiring urgent attention. Herein, the ultrastable TJT-100 exhibits unique structural characteristics including uncoordinated carboxylate oxygen atoms, coordinated water molecules directed toward the pore surface, and sufficient Me 2 NH 2 + cations in channels. TJT-100 H 2 H 2 capacity of 127.7 cm 3 H 2 H 2 selectivity over CO 2 (5.4) and CH 4 H 2 H 2 /CO 2 mixture (v/v = 50/50), TJT-100 H 2 H 2 productivity of 69.33 L/kg with a purity of 99.9%. Additionally, TJT-100 demonstrates its effectiveness in separating CO 2 from natural gas and flue gas. Its exceptional selectivity for CO 2 /CH 4 (10.7) and CO 2 /N 2 (11.9) results in a high CO 2 productivity of 21.23 and 22.93 L/kg with 99.9% purity from CO 2 /CH 4 (v/v = 50/50) and CO 2 /N 2 (v/v = 15/85) mixtures, respectively.

For solving the trade-off relationship of the polarization and breakdown electric field, ferroelectric films with high polarization are playing a critical role in energy storage capacitor applications, especially at moderate/low electric fields. In this work, we propose a multiscale structure (including defect, domain, and grain structures) synergetic optimization strategy to optimize the polarization behavior and energy storage performances of BiMg 0.5 Ti 0.5 O 3 (BMT) ferroelectric films by introducing Sr 0.7 La 0.2 TiO 3 (SLT) without compromising the breakdown strength. At a moderate electric field of 2917 kV/cm, a high discharge density of 72.2 J/cm 3 has been achieved in 0.9BMT-0.1SLT films, together with good frequency, thermal, and cycle stabilities for energy storage. Importantly, the phase difference Δφ is utilized to quantitatively evaluate the polarization switching mobility of the ferroelectric domain/PNRs at an external electric field stimulation. This research demonstrates that a multiscale structure optimization strategy could effectively regulate the energy storage performance, and ecofriendly BMT-based materials are promising candidates for next-generation energy storage capacitors, especially at moderate/low electric fields.

Self-driving laboratories (SDLs) promise an accelerated application of the scientific method. Through the automation of experimental workflows, along with autonomous experimental planning, SDLs hold the potential to greatly accelerate research in chemistry and materials discovery. This review provides an in-depth analysis of the state-of-the-art in SDL technology, its applications across various scientific disciplines, and the potential implications for research and industry. This review additionally provides an overview of the enabling technologies for SDLs, including their hardware, software, and integration with laboratory infrastructure. Most importantly, this review explores the diverse range of scientific domains where SDLs have made significant contributions, from drug discovery and materials science to genomics and chemistry. We provide a comprehensive review of existing real-world examples of SDLs, their different levels of automation, and the challenges and limitations associated with each domain.

The effectiveness of the room-temperature strengthening strategy for aluminum (Al) is compromised at increased temperatures due to grain and precipitate phase coarsening. Overcoming the heightened activity of grain boundaries and dislocations poses a significant challenge in enhancing the high-temperature strength through traditional precipitation strengthening. This study presents novel strengthening strategies that integrate intergranular reinforcements, intragranular reinforcements, refined grain, and stacking faults within an (Al 2 O 3 +Al 3 Ti)/Al composite prepared using sol-gel and powder metallurgy technology. Excellent high-temperature tensile properties are achieved; also, a remarkable fatigue performance at increased temperatures that surpasses those of other existing Al alloys and composites is revealed. These superior characteristics can be attributed to its exceptionally stable microstructure and the synergistic strengthening mechanisms mentioned above. This work offers new insights into designing and fabricating thermally stable Al matrix composites for high-temperature applications.

Exploring nucleation pathways has been a research hot spot in the fields of crystal engineering. In this work, vanillin as a model compound was utilized to explore the factors influencing different nucleation pathways with or without liquid-liquid phase separation (LLPS). A thermodynamic phase diagram of vanillin in the mixed solvent system of water and acetone from 10 to 55 °C was determined. It was found that the occurrence of LLPS might be related to different nucleation pathways. Under the guidance of a thermodynamic phase diagram, Raman spectroscopy and molecular simulation were applied to investigate the influencing factors of different nucleation paths. It was found that the degree of solvation is a key factor determining the nucleation path, and strong solvation could lead to LLPS. Additionally, the molecular self-assembly evolution during the crystallization process was further investigated by using small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS). The findings indicate that larger clusters with a diffuse transition layer may lead to LLPS during the nucleation process.

In recent years, piezo-photocatalysis has become a promising strategy for solving environmental pollution problems by adding additional mechanical energy to the photocatalysis process. This work reported the effective synthesis of a variety of HKUST-1/BiVO 4 heterogeneous materials by combining monoclinic BiVO 4 and porous HKUST-1 semiconductors. The piezo-photocatalytic properties of HKUST-1/BiVO 4 were studied by the reduction of hexavalent chromium (Cr(VI)) under visible-light irradiation and ultrasonic waves. In the piezo-photocatalysis process, the best reduction rates among as-prepared HKUST-1/BiVO 4 composites were up to 96.20% of 10 ppm Cr(VI) solution, which was approximately 1.80 times that under visible light and about 4.13 times that under ultrasound. Under the action of the piezoelectric potential, the availability of free radicals increased the reduction rate of Cr(VI) and reached a synergistic effect of 1.14-fold.

The increasing resistance of agricultural pests to existing acaricides presents a significant challenge to sustainable agriculture. Therefore, this study introduced FM-1088 , a novel isoindolinone-based phenyl trifluoroethyl thioether derivative generated through an innovative design strategy combining bioisosterism and novel cyclization methods. We synthesized several compounds and evaluated their acaricidal efficacy against Tetranychus cinnabarinus in greenhouses and Panonychus citri in field settings. FM-1088 emerged as a standout candidate, demonstrating a lower median lethal concentration (LC 50 ) of 0.722 mg/L compared to the commercial acaricide, cyetpyrafen. Notably, 30 days after application, FM-1088 showed a field control efficacy of 96.4% against P. citri , highlighting its potential for broader applications. The results underscore the utility of the isoindolinone scaffold in pesticide development, offering a promising solution to combat pest resistance with implications for enhanced crop protection and agricultural productivity. Future studies should explore the detailed mode of action of FM-1088 and its potential applicability across diverse agricultural settings, further confirming its role as a sustainable solution for pest management.

Dysfunction of voltage-gated sodium channel Nav1.2 causes various epileptic disorders, and inhibition of the channel has emerged as an attractive therapeutic strategy. However, currently available Nav1.2 inhibitors exhibit low potency and limited structural diversity. In this study, a novel series of pyrimidine-based derivatives with Nav1.2 inhibitory activity were designed, synthesized, and evaluated. Compounds 14 and 35 exhibited potent activity against Nav1.2, boasting IC 50 values of 120 and 65 nM, respectively. Compound 14 displayed favorable pharmacokinetics ( F = 43%) following intraperitoneal injection and excellent brain penetration potency (B/P = 3.6). Compounds 14 and 35 exhibited robust antiepileptic activities in the maximal electroshock test, with ED 50 values of 3.2 and 11.1 mg/kg, respectively. Compound 35 also demonstrated potent antiepileptic activity in a 6 Hz (32 mA) model, with an ED 50 value of 18.5 mg/kg. Overall, compounds 14 and 35 are promising leads for the development of new small-molecule therapeutics for epilepsy.

Self-assembled supermolecular hydrogels of therapeutic agents without structural modification are of great significance in biomedical applications. Nevertheless, the complex conformations and elusive interactions of therapeutic molecules limit the controlled assembly of hydrogels. Molecules at the interface might have different arrangements and assemblies compared to those in bulk aqueous solution, which could potentially alter the selectivity of supramolecular polymorphs. However, this effect is still not well understood. Here, we demonstrate the interface-induced self-assembly of fibers for hydrogels, which is distinct from the spherical aggregates in the bulk aqueous solution, using cephradine (CEP) as a model compound. This phenomenon is caused by the packing of anisotropic molecules at the interface, and it can be applied to control the supramolecular polymorphism for the direct self-assembly of hydrogels of therapeutic agents. The interface-induced hydrogel exhibits a high degree of adjustable release and a long-acting bactericidal effect.

This article used Carboniferous-Permian coals from the Jungar, Hedong, and Weibei Coalfields in the east of the Ordos Basin as research samples. Characteristics of coal quality, petrology, mineralogy, and geochemistry were analyzed by proximate analysis, inductively coupled plasma mass spectrometry, X-ray fluorescence spectroscopy, X-ray diffraction analysis, scanning electron microscopy-energy spectrum analysis, and incident light microscope. The enrichment regulations, distribution patterns, and occurrences of REY (rare earth element and yttrium) in coal under different geological conditions were compared. Geological significance and the influence of REY were then discussed. The average REY of Permian coal in the eastern margin of the basin is 127.9 μg/g, CC = 1.87, and the average REY of Carboniferous coal is 117.49 μg/g, CC = 1.72, which are within the normal enrichment range. The inorganic affinity of REYs in the study area is strong and mainly occurs in clay minerals and detrital phosphates and correlates well with LREY. The Permian coal sedimentary environment is more oxidized than the Taiyuan formation, and the Carboniferous coal sedimentary environment is noticeably more affected by marine water. With an increasing degree of coalification, the concentration of rare earth elements (REE) in high-rank coal vitrinite is lower than that in inertinite. In contrast, the concentration of REEs in low-rank coal is the opposite. This is because the oxygen-containing functional groups that can combine with REEs in vitrinite reduce significantly, resulting in the loss of trace elements into other forms. The provenance of the northern and central regions of the study area is mainly sedimentary rocks, granite, alkaline basalt, and continental tholeiite, while the southern region is mainly granite and sedimentary rocks., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Chiral materials are the focus of research in a variety of fields such as chiroptical sensing, biosensing, catalysis, and spintronics. Twisted two-dimensional (2D) materials are rapidly developing into a class of atomically thin chiral materials that can be effectively modulated through interlayer twist. However, chirality transfer in chiral 2D materials has not been reported. Here, we show that the chirality from the twist interface of graphene can directly transfer to achiral few-layer graphene and lead to a strong chiroptical response probed with circularly polarized Raman spectroscopy. Distinct Raman optical activity (ROA) for the interlayer shear modes in achiral few-layer graphene is observed, with the degree of polarization reaching as high as 0.5. These findings demonstrate the programmability of chiroptical response through stacking and twist engineering in 2D materials and offer insights into the transfer of chirality in atomically thin chiral materials for optical and electronic applications.

Twisted bilayer graphene (tBLG) possesses intriguing physical properties including unconventional superconductivity, enhanced light-matter interaction due to the formation of van Hove singularities (vHS), and a divergence of density of states in the electronic band structures. The vHS energy band gap provides optical resonant transition channels that can be tuned by the twist angle and interlayer coupling. Raman spectroscopy provides rich information on the vHS structure of tBLG. Here, we report the discovery of an ultralow-frequency Raman mode at ∼49 cm -1 in tBLG. This mode is assigned to the combination of ZA (an out-of-plane acoustic phonon) and TA (a transverse acoustic phonon) phonons, and the Raman scattering is proposed to occur at the so-called mini-valley. This mode is found to be particularly sensitive to the change in vHS in tBLG. Our findings may deepen the understanding of Raman scattering in tBLG and help to reveal vHS-related electron-phonon interactions in tBLG.

Nonalcoholic fatty liver disease (NAFLD) is a clinicopathological condition characterized by intrahepatic ectopic steatosis. Due to the increase in high-calorie diets and sedentary lifestyles, NAFLD has surpassed viral hepatitis and become the most prevalent chronic liver disease globally. Silibinin, a natural compound, has shown promising therapeutic potential for the treatment of liver diseases. Nevertheless, the ameliorative effects of silibinin on NAFLD have not been completely understood, and the underlying mechanism is elusive. Therefore, in this study, we used high-fat diet (HFD)-induced mice and free fatty acid (FFA)-stimulated HepG2 cells to investigate the efficacy of silibinin for the treatment of NAFLD and elucidate the underlying mechanisms. In vivo , silibinin showed significant efficacy in inhibiting adiposity, improving lipid profile levels, ameliorating hepatic histological aberrations, healing the intestinal epithelium, and restoring gut microbiota compositions. Furthermore, in vitro , silibinin effectively inhibited FFA-induced lipid accumulation in HepG2 cells. Mechanistically, we reveal that silibinin possesses the ability to ameliorate hepatic lipotoxicity by suppressing the heat shock protein 90 (Hsp90)/peroxisome proliferator-activated receptor- γ (PPAR γ ) pathway and alleviating gut dysfunction by inhibiting the Hsp90/NOD-like receptor pyrin domain-containing 3 (NLRP3) pathway. Altogether, our findings provide evidence that silibinin is a promising candidate for alleviating the "multiple-hit" in the progression of NAFLD., Competing Interests: The authors declare no competing financial interest., (© 2024 American Chemical Society.)

Liquid crystal wet-spun carbon nanotube fibers (CNTFs) offer notable advantages, such as precise alignment and scalability. However, these CNTFs usually suffer premature failure through intertube slippage due to the weak interfacial interactions between adjacent shells and bundles. Herein, we present a microwave (MW) welding strategy to enhance intertube interactions by partially carbonizing interstitial heterocyclic aramid polymers. The resulting CNTFs exhibit ultrahigh static tensile strength (6.74 ± 0.34 GPa) and dynamic tensile strength (9.52 ± 1.31 GPa), outperforming other traditional high-performance fibers. This work provides a straightforward yet effective approach to strengthening CNTFs for advanced engineering applications.

Chiral materials possess broken inversion and mirror symmetry and show great potential in the application of next-generation optic, electronic, and spintronic devices. Two-dimensional (2D) chiral crystals have planar chirality, which is nonsuperimposable on their 2D enantiomers by any rotation about the axis perpendicular to the substrate. The degree of freedom to construct vertical stacking of 2D monolayer enantiomers offers the possibility of chiral manipulation for designed properties by creating multilayers with either a racemic or enantiomerically pure stacking order. However, the rapid recognition of the relative proportion of two enantiomers becomes demanding due to the complexity of stacking orders of 2D chiral crystals. Here, we report the unambiguous identification of racemic and enantiomerically pure stackings for layered ReSe 2 and ReS 2 using circular polarized Raman spectroscopy. The chiral Raman response is successfully manipulated by the enantiomer proportion, and the stacking orders of multilayer ReSe 2 and ReS 2 can be completely clarified with the help of second harmonic generation and scanning transmission electron microscopy measurements. Finally, we trained an artificial intelligent Spectra Classification Assistant to predict the chirality and the complete crystallographic structures of multilayer ReSe 2 from a single circular polarized Raman spectrum with the accuracy reaching 0.9417 ± 0.0059.

Genetically encoding proximal-reactive unnatural amino acids (PrUaas), such as fluorosulfate-l-tyrosine (FSY), into natural proteins of interest (POI) confer the POI with the ability to covalently bind to its interacting proteins (IPs). The PrUaa-incorporated POIs hold promise for blocking undesirable POI-IP interactions. Selecting appropriate PrUaa anchor sites is crucial, but it remains challenging with the current methodology, which heavily relies on crystallography to identify the proximal residues between the POIs and the IPs for the PrUaa anchorage. To address the challenge, here, we propose a footprinting-directed genetically encoded covalent binder (footprinting-GECB) approach. This approach employs carbene footprinting, a structural mass spectrometry (MS) technique that quantifies the extent of labeling of the POI following the addition of its IP, and thus identifies the responsive residues. By genetically encoding PrUaa into these responsive sites, POI variants with covalent bonding ability to its IP can be produced without the need for crystallography. Using the POI-IP model, KRAS/RAF1, we showed that engineering FSY at the footprint-assigned KRAS residue resulted in a KRAS variant that can bind irreversibly to RAF1. Additionally, we inserted FSY at the responsive residue in RAF1 upon footprinting the oncogenic KRAS G12D /RAF1, which lacks crystal structure, and generated a covalent binder to KRAS G12D . Together, we demonstrated that by adopting carbene footprinting to direct PrUaa anchorage, we can greatly expand the opportunities for designing covalent protein binders for PPIs without relying on crystallography. This holds promise for creating effective PPI inhibitors and supports both fundamental research and biotherapeutics development.

Nanocarriers have been researched comprehensively for the development of novel boron-containing agents in boron neutron capture therapy (BNCT). We designed and synthesized a multifunctional mesoporous silica nanoparticle (MSN)-based boron-containing agent. The latter was coated with a lipid bilayer (LB) and decorated with SP94 peptide (SFSIIHTPILPL) on the surface as SP94-LB@BA-MSN. The latter incorporated boric acid (BA) into hydrophobic mesopores, coated with an LB, and modified with SP94 peptide on the LB. SP94-LB@BA-MSN enhanced nano interface tumor-targeting ability but also prevented the premature release of drugs, which is crucial for BNCT because adequate boron content in tumor sites is required. SP94-LB@BA-MSN showed excellent efficacy in the BNCT treatment of HepG-2 cells. In animal studies with tumor-bearing mice, SP94-LB@BA-MSN exhibited a satisfactory accumulation at the tumor site. The boron content reached 40.18 ± 5.41 ppm in the tumor site 4 h after injection, which was 8.12 and 15.51 times higher than those in mice treated with boronated phenylalanine and those treated with BA. For boron, the tumor-to-normal tissue ratio was 4.41 ± 1.13 and the tumor-to-blood ratio was 5.92 ± 0.45. These results indicated that nanoparticles delivered boron to the tumor site effectively while minimizing accumulation in normal tissues. In conclusion, this composite (SP94-LB@BA-MSN) shows great promise as a boron-containing delivery agent for the treatment of hepatocellular carcinoma using BNCT. These findings highlight the potential of MSNs in the field of BNCT.

Sorption to activated carbon is a common approach to reducing environmental risks of waterborne perfluorooctanoic acid (PFOA), while effective and flexible approaches to PFOA sorption are needed. Variations in temperature or the use of electrokinetic phenomena (electroosmosis and electromigration) in the presence of external DC electric fields have been shown to alter the contaminant sorption of contaminants. Their role in PFOA sorption, however, remains unclear. Here, we investigated the joint effects of DC electric fields and the temperature on the sorption of PFOA on activated carbon. Temperature-dependent batch and column sorption experiments were performed in the presence and absence of DC fields, and the results were evaluated by using different kinetic sorption models. We found an emerging interplay of DC and temperature on PFOA sorption, which was linked via the liquid viscosity (η) of the electrolyte. For instance, the combined presence of a DC field and low temperature increased the PFOA loading up to 38% in 48 h relative to DC-free controls. We further developed a model that allowed us to predict temperature- and DC field strength-dependent electrokinetic benefits on the drivers of PFOA sorption kinetics (i.e., intraparticle diffusivity and the film mass transfer coefficient). Our insights may give rise to future DC- and temperature-driven applications for PFOA sorption, for instance, in response to fluctuating PFOA concentrations in contaminated water streams.

Milk-derived extracellular vesicles can improve intestinal health and have antiosteoporosis potential. In this paper, we explored the effects of bovine raw milk-derived extracellular vesicles (mEVs) on ovariectomized (OVX) osteoporotic mice from the perspective of the gut-bone axis. mEVs could inhibit osteoclast differentiation and improve microarchitecture. The level of osteoporotic biomarkers in OVX mice was restored after the mEVs intervened. Compared with OVX mice, mEVs could enhance intestinal permeability, reduce endotoxin levels, and improve the expression of TNF-α, IL-17, and IL-10. 16S rDNA sequencing indicated that mEVs altered the composition of gut microbiota, specifically for Bacteroides associated with short-chain fatty acids (SCFAs). In-depth analysis of SCFAs demonstrated that mEVs could restore acetic acid, propionic acid, valeric acid, and isovaleric acid levels in OVX mice. Correlation analysis revealed that changed gut microbiota and SCFAs were significantly associated with gut inflammation and osteoporotic biomarkers. This study demonstrated that mEVs could inhibit osteoclast differentiation and improve osteoporosis by reshaping the gut microbiota, increasing SCFAs, and decreasing the level of pro-inflammatory cytokines and osteoclast differentiation-related factors in OVX mice. These findings provide evidence for the use of mEVs as a food supplement for osteoporosis.

Chemiluminescence is a powerful analytical technique with many advantages, while aptamers are well-known as good molecular recognition units. However, many aptamer-based chemiluminescence assays employed interface sensing, which often needed several immobilization, separation, and washing steps. To minimize the risks of contamination and false-positive, we for the first time proposed a photocatalytic aptamer chemiluminescent system for a homogeneous, label-free, generic assay of small molecules. After binding to a DNA aptamer, thioflavin T has a unique photocatalytic oxidase activity to activate the system's luminol chemiluminescence. Then, the specific binding between the aptamer and target molecules will compete with the above process. Therefore, we can realize the efficient assay of different analytes including estradiol and adenosine. Such a homogeneous chemiluminescent system allowed a direct assay of small molecules with limits of detection in a nM level. Several control tests were carried out to avoid possible false-positive results, which were originated from the interactions between analytes and sensing interfaces previously. This homogeneous chemiluminescent system provides a useful strategy to reliably assay various analytes in the pharmacy or biology field.

Improving the efficiency of the oxygen evolution reaction (OER) is crucial for advancing sustainable and environmentally friendly hydrogen energy. Layered double hydroxides (LDHs) have emerged as promising electrocatalysts for the OER. However, a thorough understanding of the impact of structural disorder and defects on the catalytic activity of LDHs remains limited. In this work, a series of NiAl-LDH models are systematically constructed, and their OER performance is rigorously screened through theoretical density functional theory. The acquired results unequivocally reveal that the energy increase induced by structural disorder is effectively counteracted at the defect surface, indicating the coexistence of defects and disorder. Notably, it is ascertained that the simultaneous presence of defects and disorder synergistically augments the catalytic activity of LDHs in the context of the OER. These theoretical findings offer valuable insights into the design of highly efficient OER catalysts while also shedding light on the efficacy of LDH electrocatalysts.

In view of the problems of low liquid production, a high proportion of high water cut wells, and poor development effect in the late stage of water flooding in the special sandstone reservoir of Niuquanhu "low permeability and medium viscosity crude oil", we carried out the research on hydrocarbon gas oil recovery and its influencing factors. First, the influence of different injected gas media on the physical properties of crude oil was analyzed. Second, the core displacement experiments of different gas injection media including CO 2 , CH 4 , and hydrocarbon gas were carried out by using the method of oil recovery comparison and optimization. Third, the indoor experimental study on the oil recovery of different influencing factors was carried out by using the method of controlling variables of influencing factors. Finally, the influence degree of different influencing factors on oil recovery was analyzed by a Spearman rank correlation coefficient analysis. The experimental results showed that the oil recovery of hydrocarbon gas is higher than that of CO 2 and CH 4 , which were 57, 51, and 18% respectively. This is mainly because hydrocarbon gas is similar to the components of crude oil and is more easily dissolved in crude oil. The experimental results of influencing factors showed that the higher the content of C 2 -C 4 , the higher the oil recovery, and the content of C 2 -C 4 will affect its dissolution with crude oil and its interaction with heavy component crude oil. The larger the permeability ratio, the lower the oil recovery, which was mainly due to the uneven distribution of injected gas in different regions. The higher the permeability, the lower the oil recovery, which was also due to the serious heterogeneity of the low permeability core of Niuquanhu; The results of Spearman rank correlation coefficient analysis based on different influencing factors and oil recovery showed that the order of influence of different factors on oil recovery was C 2 -C 4 content > permeability ratio > permeability > back pressure > gas injection rate. In the development process of hydrocarbon gas injection, we should control the C 2 -C 4 content, back pressure, and injection rate. The research in this study not only provides theoretical support for gas injection enhanced oil recovery technology in "low permeability and medium viscosity crude oil" reservoirs but also provides a new idea for the ranking of influencing factors., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Polymer based low evaporation enthalpy materials have become a universal selection for improving the efficiency of solar steam generation. Although water cluster and intermediate water mechanisms have been proposed to explain the low evaporation enthalpy, the production process and microstructure of activated water are still unclear. Here, crystal plane engineering is used to investigate the intermediate water state and the water cluster activation mechanism. The unique open-closed coordination structure on the optimized crystal surface promotes the generation of firm water clusters by optimizing the intermediate water state. Under the similar solar energy absorption of all materials, crystal plane engineering increased the solar steam generation rate of the evaporator by 31.2% and increased the energy efficiency to 94.8%. Exploring the micro-evaporation process and activated water structure is expected to stimulate the development of the next generation low evaporation enthalpy materials.

The separation of C 8 aromatic isomers ( o X: o -xylene, p X: p -xylene, m X: m -xylene, and EB: ethylbenzene) remains an enormous challenge in industrial production due to their similar molecular structures and physical properties. Porous materials with suitable pore structures and selective recognition sites to discriminate the slight structural differences of isomers are imminently needed. In this paper, MIL-47(V) with a three-dimensional (3D) grid structure of 10.5 × 10.5 Å 2 and a one-dimensional (1D) diamond channel was selected as the adsorbent. However, the mechanism of the adsorption and separation of C 8 aromatic isomers in porous materials still needs to be understood. Given the importance of C 8 aromatic isomers' confinement in MIL-47(V) for adsorption and diffusion applications, it is important to understand C 8 aromatic isomers' behavior in MIL-47(V) . Here, we demonstrated from a simulation perspective that metal-organic frameworks MIL-47(V) with one-dimensional (1D) diamond channels can identify C 8 aromatic isomers. Molecular dynamics (MD) simulations have shown that organic ligands with guest response sites of MIL-47(V) can effectively distinguish between C 8 aromatic isomers by adaptation to the shape of a specific isomer. MIL-47(V) has high adsorption and an excellent separation sequence between C 8 aromatic isomers: o X > p X ≈ m X > EB. Significant differences exist in π-π superposition interactions between C 8 aromatic isomers and between C 8 aromatic isomers and the skeletons. This phenomenon is mainly caused by the unique pore structure and guest response characteristics of MIL-47(V) . This work is identified as a supplementary instruction to experimental research and is expected to provide profound insights into research on developing C 8 aromatic isomers' adsorption and separation and theoretical support.

One 3D Cd-MOF, namely, {[(HDMA) 2 ][Cd 3 (L) 2 ]·5H 2 O·2DMF} n ( LCU-124 , LCU indicates Liaocheng University), was synthesized from an ether-containing ligand 1,3-bis(3,5-dicarboxylphenoxy)benzene (H 4 L). Its Ln 3+ -postmodified samples, Eu 3+ @LCU-124 and Tb 3+ @LCU-124 , were obtained through cation exchange of dimethylamine cation (HDMA) with Eu 3+ and Tb 3+ . The successful entry of rare earth into LCU-124 by cation exchange modification was verified by IR, XRD, XPS, EDS mapping, and luminescence spectra. The proportion of Eu 3+ /Tb 3+ was adjusted during the modification process, leading to fluorescent materials with different emissions. Luminescence measurements indicated that these complexes exhibited interesting multiresponsive sensing activities toward biomarkers urine acid (UA), quinine (QN), and quinidine (QND). First, LCU-124 has a pronounced quenching effect toward UA with the detection limit of 31.01 μM. After modification, the visualization of the detection was improved significantly and the detection limit of Eu 3+ @LCU-124 was reduced to 0.868 μM. Second, when QN and QND were present in the suspensions of Eu 3+ @LCU-124 and Tb 3+ @LCU-124 , strong blue light emission peaks occurred, while the characteristic emission of Eu 3+ /Tb 3+ decreased, forming ratiometric fluorescent sensors with the detection limit in the range of 0.199-9.49 μM. The fluorescent probes have high selectivity, excellent sensitivity recycling, and fast response time (less than 1 min). Besides, a simple logic gate circuit and a range of luminescent mixed matrix membranes were designed to provide simple and fast detection of above biomarkers. Our work indicated that modification of Eu 3+ /Tb 3+ could improve the detection ability significantly.

Hypoxia is a pervasive feature of solid tumors, which significantly limits the therapeutic effect of photodynamic therapy (PDT) and further influences the immunotherapy efficiency in breast cancer. However, the transient alleviation of tumor hypoxia fails to address the underlying issue of increased oxygen consumption, resulting from the rapid proliferation of tumor cells. At present, studies have found that the reduction of the oxygen consumption rate (OCR) by cytochrome C oxidase (COX) inhibition that induced oxidative phosphorylation (OXHPOS) suppression was able to solve the proposed problem. Herein, we developed a specific mitochondrial-targeting nanotrapper (I@MSN-Im-PEG), which exhibited good copper chelating ability to inhibit COX for reducing the OCR. The results proved that the nanotrapper significantly alleviated the hypoxic tumor microenvironment by copper chelation in mitochondria and enhanced the PDT effect in vitro and in vivo. Meanwhile, the nanotrapper improved photoimmunotherapy through both enhancing PDT-induced immunogenetic cell death (ICD) effects and reversing Treg-mediated immune suppression on 4T1 tumor-bearing mice. The mitochondrial-targeting nanotrapper provided a novel and efficacious strategy to enhance the PDT effect and amplify photoimmunotherapy in breast cancer.

The superamphiphiles exhibit broad prospects for fabricating stimuli-responsive emulsions. Because the superamphiphiles are assembled via noncovalent interactions, they have the advantage of fast response and high efficiency. Recently, a series of switchable emulsions using CO 2 -responsive superamphiphiles have been developed, which extends the applications of CO 2 -responsive materials in widespread field. However, there is still a lack of fundamental understanding on the switching mechanism related to the assembled structure of superamphiphiles at the oil-water interface. We employed molecular dynamics (MD) simulations to investigate the reversible emulsification/demulsification process of a responsive emulsion system stabilized by a recently developed responsive superamphiphile (BTOA), which consists of oleic acid (OA) and cationic amine (named 1,3-bis(aminopropyl)tetramethyldisiloxane, BT). The simulation results present the morphologies in both the emulsion and demulsification states. It is found that the ionized OA - and the protonated BT + together form an adsorption layer at the oil-water interface. The hydrophobic parts of BT + are inserted into the adsorption layer, and the two amine groups contact the water phase. This adsorption layer reduces the interfacial tension and stabilizes the emulsion. After the bubbling of CO 2 , the surfactants were fully protonated to OA and BT 2+ . Because of the changes in the molecular polarity, OA and BT 2+ entered the oil and water phases, respectively, resulting in demulsification. The structural and dynamical properties were analyzed to reveal the different intermolecular interactions that were responsible for the reversible reversibility of the emulsion. The observations are considered to be complementary to experimental studies and are expected to provide deeper insights into studies on developing responsive materials via supramolecular assemblies.

Adding hydrophilic ligands into aqueous solutions for the selective binding of actinides(III) is acknowledged as an advanced strategy in Ln(III)/An(III) separation. In view of the recycling and radioactive waste disposal of the minor actinide, there remains an urgent need to design and develop the appropriate ligand for selective separation of An(III) from Ln(III). Herein, four novel hydrophilic ligands with hard-soft hybrid donors, derived from the pyridine and phenanthroline skeletons, were designed and synthesized as masking agents for selective complexation of An(III) in the aqueous phase. The known N , N , N ', N '-tetraoctyl diglycolamide (TODGA) was used as lipophilic extractant in the organic phase for extraction of Ln(III), and a new strategy for the competitive extraction of An(III) and Ln(III) was developed based on TODGA and the above hydrophilic ligands. The optimal hydrophilic ligand of N , N '-bis(2-hydroxyethyl)-2,9-dicarboxamide-1,10-phenanthroline (2OH-DAPhen) displayed exceptional selectivity toward Am(III) over Ln(III), with the concentrations of HNO 3 ranging from 0.05 to 3.0 M. The maximum separation factors were up to 1365 for Eu/Am, 417.66 for Eu/Cm, and 42.38 for La/Am. The coordination mode and bonding property of 2OH-DAPhen with Ln(III) were investigated by 1 H NMR titration, UV-vis spectrophotometric titration, luminescence titration, FT-IR, ESI-HRMS analysis, and DFT calculations. The results revealed that the predominant species formed in the aqueous phase was a 1:1 ligand/metal complex. DFT calculations also confirmed that the affinity of 2OH-DAPhen for Am(III) was better than that for Eu(III). The present work using a competitive extraction strategy developed a feasible alternative method for the selective separation of trivalent actinides from lanthanides.

The design and development of proton conduction materials for clean energy-related applications is obviously important and highly desired but challenging. An ultrastable cobalt-based metal-organic framework Co-MOF , formulated as [Co 2 (btzip) 2 (μ 2 -OH 2 )] (namely, LCUH-103 , H 2 btzip = 4, 6-bis(triazol-1-yl)-isophthalic acid) had been successfully synthesized via the hydrothermal method. LCUH-103 exhibits a three-dimensional framework and a one-dimensional microporous channel structure with scu topology based on the binuclear metallic cluster {Co 2 }. LCUH-103 indicated excellent chemical and thermal stability; peculiarly, it can retain its entire framework in acid and alkali solutions with different pH values for 24 h. The excellent stability is a prerequisite for studying its proton conductivity, and its proton conductivity σ can reach up to 1.25 × 10 -3 S·cm - 1 at 80 °C and 100% relative humidity (RH). In order to enhance its proton conductivity, the proton-conducting material Im@ LCUH-103 had been prepared by encapsulating imidazole molecules into the channels of LCUH-103 . Im@ LCUH-103 indicated an excellent proton conductivity of 3.18 × 10 -2 S·cm - 1 at 80 °C and 100% RH, which is 1 order of magnitude higher than that of original LCUH-103 . The proton conduction mechanism was systematically studied by various detection means and theoretical calculations. Meanwhile, LCUH-103 is also an excellent carrier for palladium nanoparticles (Pd NPs) via a wetness impregnation strategy, and the nitrophenols (4/3/2-NP) reduction in aqueous solution by Pd@ LCUH-103 indicated an outstanding conversion efficiency, high rate constant ( k ), and exceptional cycling stability. Specifically, the k value of 4-NP reduction by Pd@ LCUH-103 is superior to many other reported catalysts, and its k value is as high as 1.34 min -1 and the cycling stability can reach up to 6 cycles. Notably, its turnover frequency (TOF) value is nearly 196.88 times more than that of Pd/C (wt 5%) in the reaction, indicating its excellent stability and catalytic activity.

It is well-known that the potency of a drug is heavily associated with its kinetic and thermodynamic properties with the target. Nuclear receptors (NRs), as an important target family, play important roles in regulating a variety of physiological processes in vivo . However, it is hard to understand the drug-NR interaction process because of the closed structure of the ligand-binding domain (LBD) of the NR proteins, which apparently hinders the rational design of drugs with controllable kinetic properties. Therefore, understanding the underlying mechanism of the ligand-NR interaction process seems necessary to help NR drug design. However, it is usually difficult for experimental approaches to interpret the kinetic process of drug-target interactions. Therefore, in silico methods were utilized to explore the optimal binding/dissociation pathways of the NR ligands. Specifically, farnesoid X receptor (FXR) is considered here as the target system since it has been an important target for the treatment of bile acid metabolism-associated diseases, and a series of structures cocrystallized with diverse scaffold ligands were resolved. By using random acceleration molecular dynamics (RAMD) simulation and umbrella sampling (US), 5 main dissociation pathways (pathways I-V) were identified in 11 representative FXR ligands, with most of them (9/11) preferring to go through Pathway III and the remaining two favoring escaping from Pathway I and IV. Furthermore, key residues functioning in the three main dissociation pathways were revealed by the kinetic residue energy analysis (KREA) based on the US trajectories, which may serve as road-marker residues for rapid identification of the (un)binding pathways of FXR ligands. Moreover, the preferred pathways explored by RAMD simulations are in good agreement with the minimum free energy path identified by the US simulations with the Pearson R = 0.76 between the predicted binding affinity and the experimental data, suggesting that RAMD is suitable for applying in large-scale (un)binding-pathway exploration in the case of ligands with obscure binding tunnels to the target.

Anastomotic leakage (AL), one of the most severe complications in rectal surgery, is often diagnosed late because of the low specificity of the clinical symptoms and limitations of current clinical investigations. Identification of patients with early AL remains challenging. Here, we explored the protein expression profiles of AL patients to provide potential biomarkers to identify AL in patients who undergo surgery for rectal cancer. We screened differentially expressed proteins (DEPs) in drainage fluid from AL and non-AL patients using a tandem mass tag method. A total of 248 DEPs, including 98 upregulated and 150 downregulated proteins, were identified between AL and non-AL groups. Gene ontology and Kyoto Encyclopedia of Genes and Genomes enrichment analyses suggested that DEPs were enriched in neutrophil degranulation, bacterial infection, proteolysis, hemostasis, and complement and coagulation cascades. The results of enzyme-linked immunosorbent assay validated that the expression of the top three upregulated DEPs, AMY2A, RETN, and CELA3A, was significantly increased in the drainage fluid of AL patients, compared with that of non-AL patients (AMY2A, P = 0.001; RETN, P < 0.0001; and CELA3A, P = 0.023). Thus, our findings provide several potential biomarkers for the early diagnosis of AL after rectal cancer resection.

Once nanoparticles enter into the biological milieu, nanoparticle-biomacromolecule complexes, especially the protein corona, swiftly form, which cause obvious effects on the physicochemical properties of both nanoparticles and proteins. Here, the thermodynamic parameters of the interactions between water-soluble GSH-CdSe/ZnS core/shell quantum dots (GSH-QDs) and human serum albumin (HSA) were investigated with the aid of labeling fluorescence of HSA. It was proved that the labeling fluorescence originating from a fluorophore (BDP-CN for instance) could be used to investigate the interactions between QDs and HSA. Gel electrophoresis displayed that the binding ratio between HSA and QDs was ∼2:1 by direct visualization. Fluorescence resonance energy transfer (FRET) results indicated that the distance between the QDs and the fluorophore BDP-CN in HSA was 7.2 nm, which indicated that the distance from the fluorophore to the surface of the QDs was ∼4.8 nm. Fluorescence correlation spectroscopy (FCS) results showed that HSA formed a monolayer of a protein corona with a thickness of 5.5 nm. According to the spatial structure of HSA, we could speculate that the binding site of QDs was located at the side edge (not the triangular plane) of HSA with an equilateral triangular prism. The elaboration of the thermodynamic parameters, binding ratio, and interaction orientation will highly improve the fundamental understanding of the formation of protein corona. This work has guiding significance for the exploration of the interactions between proteins and nanomaterials.

Wide-field photobleaching imprinting microscopy (PIM) can improve fluorescence image contrast by cleverly exploiting the fluorophores' photobleaching properties. However, as conventional wide-field PIM commonly adopts Gaussian illumination with a nonuniform lateral fluence distribution, the field-of-view (FOV) and sampling density are largely reduced. In addition, the slow axial fluence gradient of Gaussian illumination limits the signal-to-background ratio (SBR) improvement and optical sectioning capability of PIM. Here, we present flat-field photobleaching imprinting microscopy (ffPIM) with a uniform lateral excitation fluence and sharp axial intensity gradient at the focal plane. ffPIM demonstrates low background, large FOV, and thin optical section. More importantly, compared to either conventional wide-field PIM or light-sheet microscopy, ffPIM shows much better balance for FOV, sampling density, SBR, and optical sectioning capability. The performance of ffPIM is characterized by simulation and resolving multiple cellular structures. Finally, ffPIM can be easily implemented to a standard commercial wide-field microscope and, thereby, allow general laboratories to benefit from this technique., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Co-published by Nanjing University and American Chemical Society.)

Homogeneous assays often obviate any separation and washing steps, thus minimizing the risks of contamination and false positive. DNA toehold exchange is a homogeneous, reversible process whose thermodynamic properties can be finely tuned for various assay applications. However, the developed probes often rely on direct interactions of analytes with DNA strands involved in toehold exchange, limiting the versatility of probe design. Here, the coaxial adjacent stacking between one auxiliary strand and another invading strand offers a favorable Δ G to shift one DNA balance, while the auxiliary strand is independent of the DNA balance itself. Therefore, such a DNA balance allowed fine tuning of the equilibrium via adjustment of the auxiliary strand alone. The energy contribution of base stacking can be quantified in a homogeneous solution based on the difference in the equilibrium constant. Besides, the proof of concept for DNA balance allows effective assay of a small molecule or ribonuclease in a homogeneous solution. This novel DNA balance via adjacent base stacking provides an interesting alternative to homogeneously assay various analytes.

Lost circulation events during drilling operations are known for their abruptness and are difficult to control. Traditional diagnostic methods rely on qualitative indicators, such as mud pit volume changes or anomalous logging curve patterns. However, these methods are subjective and rely heavily on empirical knowledge, resulting in delayed or inaccurate predictions. To address this problem, there is an urgent need to develop efficient methods for a timely and accurate lost circulation prediction. In this study, a novel approach is proposed by combining principal component analysis (PCA) and empirical analysis to reduce the dimensionality of the model data. This dimensionality reduction helps to streamline the analysis process and improve prediction accuracy. The predictive model also incorporates an improved fruit fly optimization algorithm (IFOA) in conjunction with support vector machine (SVM) techniques. The actual instances of lost circulation serve as the evaluation criteria for this integrated method. To overcome the challenges associated with irregular population distribution within randomly generated individuals, a tent map strategy is introduced to ensure a more balanced and representative sample. In addition, the model addresses issues such as premature convergence and slow optimization rates by employing a sine-cosine search strategy. This strategy helps to achieve optimal results and speeds up the prediction process. The improved prediction model demonstrates exceptional performance, achieving accuracy, precision, recall, and F1 scores of 96.8, 97, 96, and 96%, respectively. These results indicate that the IFOA-SVM approach achieves the highest accuracy with a reduced number of iterations, proving to be an efficient and fast method for predicting the lost circulation events. Implementation of this methodology in drilling operations can lead to improved efficiency, reliability, and overall performance., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The discharge of harmful and toxic pollutants in water is destroying the ecosystem balance and human being health at an alarming rate. Therefore, the detection and removal of water pollutants by using stable and efficient materials are significant but challenging. Herein, three novel lanthanide metal-organic frameworks (Ln-MOFs), [La(L)(DMF) 2 (H 2 O) 2 ]·H 2 O ( LCUH-104 ), [Nd(L)(DMF) 2 (H 2 O) 2 ]·H 2 O ( LCUH-105 ), and [Pr(L)(DMF) 2 (H 2 O) 2 ]·H 2 O ( LCUH-106 ) [H 3 L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid (H 3 TZI)] were solvothermally constructed and structurally characterized. In the three Ln-MOFs, dinuclear metallic clusters {Ln 2 } were connected by deprotonated tetrazol-containing dicarboxylate TZI 3- to obtain a 2D layered framework with a point symbol of {4 2 ·8 4 }·{4 6 }. Their excellent chemical and thermal stabilities were beneficial to carry out fluorescence sensing and achieve the catalytic nitrophenols (NPs) reduction. Especially, the incorporation of the nitrogen-rich tetrazole ring into their 2D layered frameworks enables the fabrication of Pd nanocatalysts (Pd NPs@ LCUH-104/105/106 ) and have dramatically enhanced catalytic activity by using the unique metal-support interactions between three Ln-MOFs and the encapsulating palladium nanoparticles (Pd NPs). Specifically, the reduction of NPs (2-NP, 3-NP, and 4-NP) in aqueous solution by Pd NPs@ LCUH-104 exhibits exceptional conversion efficiency, remarkable rate constants ( k ), and outstanding cycling stability. The catalytic rate of Pd NPs@ LCUH-104 for 4-NP is nearly 8.5 times more than that of Pd/C (wt 5%) and its turnover frequency value is 0.051 s -1 , which indicate its excellent catalytic activity. Meanwhile, LCUH-105 , as a multifunctional fluorescence sensor, exhibited excellent fluorescence detection of norfloxacin (NFX) (turn on) and Cr 2 O 7 2- (turn off) with high selectivity and sensitivity at a low concentration, and the corresponding fluorescence enhancement/quenching mechanism has also been systematically investigated through various detection means and theoretical calculations.

The high-temperature reservoir (105 °C) in the Liubei block of Jidong Oilfield, with severe longitudinal heterogeneity, has entered a high water-cut stage. After a preliminary profile control, the water management of the oilfield still faces serious water channeling problems. To strengthen water management, N 2 foam flooding combined with gel plugging for enhanced oil recovery was studied. In this work, considering a high-temperature reservoir of 105 °C, a composite foam system and starch graft gel system with high temperature resistance were screened out, and displacement experiments in one-dimensional heterogeneous cores were carried out. Through the three-dimensional experimental model and numerical model of a 5-spot well pattern, physical experiments and numerical simulations were carried out respectively to study water control and oil increase. The experimental results showed that the foam composite system had good temperature resistance up to 140 °C and oil resistance up to 50% oil saturation and was helpful to adjust the heterogeneous profile in a high temperature of 105 °C. The starch graft gel system had good injection performance, with a solution viscosity of 18.15 mPa·s, and its gel strength could effectively seal the high-permeability layer, with a gel viscosity of 34950.92 mPa·s. The displacement test results showed that after a preliminary implementation of N 2 foam flooding, N 2 foam flooding combined with gel plugging could still improve oil recovery by 5.26%. Compared with preliminary N 2 foam flooding, gel plugging could control the water channeling in the high-permeability zone near the production wells. The combination of foam and gel made N 2 foam flooding and subsequent waterflooding divert to flow mainly along the low-permeability layer, which was conducive to enhance water management and improve oil recovery. This method can be used as an effective technology to manage similar heterogeneous reservoirs., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The characterization of interlayer coupling in two-dimensional van der Waals heterostructures (vdWHs) is essential to understand their quantum behaviors and structural functionalities. Interlayer shear and layer-breathing (LB) phonons carry rich information on interlayer interaction, but they are usually too weak to be detected via standard Raman spectroscopy due to the weak electron-phonon coupling (EPC). Here, we report a universal strategy to enhance LB modes of vdWHs based on twisted bilayer graphene (tBLG). In both tBLG/hBN and tBLG/MoS 2 vdWHs, the resonantly excited electrons in tBLG can strongly couple to LB phonons extended over the entire layers in the vdWHs, whose resonance condition is tunable by the twist angle of tBLG. In vdWHs containing twisted graphene layers with multiple twisted interfaces, the EPC of LB phonons coming from the collective LB vibrations of entire heterostructure layers can be tuned by resonant excitation of programmable van Hove singularities according to each twisted interface. The universality and tunability of enhanced LB phonons by tBLG make it a promising method to investigate EPC and interlayer interaction in related vdWHs.

With the increase of the burial depth of the no. 3 coal seam in the Zhengzhuang minefield of Qinshui Basin, the production of surface coal bed methane (CBM) vertical wells was low. By means of theoretical analysis and numerical calculation, the causes of low production of CBM vertical wells were studied from the aspects of reservoir physical properties, development technology, stress conditions, and desorption characteristics. It was found that the high in situ stress conditions and stress state changes were the main controlling factors of the low production in the field. On this basis, the mechanism of increasing production and reservoir stimulation was explored. An L-type horizontal well was constructed alternately among the existing vertical wells on the surface to initiate a method to increase the regional production of fish-bone-shaped well groups. This method has the advantages of a large fracture extension range and a wide pressure relief area. It could also effectively connect the pre-existing fracture extension area of surface vertical wells, realizing the overall stimulation of the low-yield area and increasing the regional production. Through the optimization of the favorable stimulation area in the minefield, 8 L-type horizontal wells that adopted this method were constructed in the area with high gas content (greater than 18 m 3 /t), a thick coal seam (thicker than 5 m), and relatively rich groundwater in the north of the minefield. The average production of a single L-type horizontal well reached 6000 m 3 /d, which was about 30 times that of the surrounding vertical wells. The length of the horizontal section and the original gas content of the coal seam had a significant influence on the production of the L-type horizontal wells. This method for increasing the regional production of fish-bone-shaped well groups was an effective and feasible low-yield well stimulation technology, which provided a reference for increasing the production and efficiently developing CBM under the high-stress conditions in mid-deep high-rank coal seams., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

As one of the most important processes in the process of crystallization, nucleation determines the physicochemical properties of the crystal products. The mechanism of nucleation has not been sufficiently understood due to the complexity of the molecular assembly process. In this work, a rigid molecule of 3,5-dinitrobenzoic acid (DNBA) was selected as the model compound to investigate the connection between nucleation kinetics and solution chemistry and to investigate the mechanism of nucleation. The nucleation induction period was determined by the nonrandom method, and the parameters including interfacial energy γ and collision frequency f 0 C 0 were calculated. FTIR, NMR, and MS were used to analyze the existing form of DNBA molecules in solutions. It was found that the solute exists in the form of monomer, multimers, and solvates in different solvents. Besides, molecular simulation and calculation were also used to investigate the intermolecular interactions of DNBA in different solvents, and the relationship between the molecular existing form and the nucleation kinetics was revealed. Finally, a possible nucleation mechanism of DNBA molecules in solution was proposed.

There is increasing evidence linking long-term fine particulate matter (PM 2.5 ) exposure to negative health effects. However, the relative influence of each component of PM 2.5 on health risk is poorly understood. In a cohort study in the contiguous United States between 2000 and 2017, we examined the effect of long-term exposure to PM 2.5 main components and all-cause mortality in older adults who had to be at least 65 years old and enrolled in Medicare. We estimated the yearly mean concentrations of six key PM 2.5 compounds, including black carbon (BC), organic matter (OM), soil dust (DUST), nitrate (NO 3 - ), sulfate (SO 4 2- ), and ammonium (NH 4 + ), using two independently sourced well-validated prediction models. We applied Cox proportional hazard models to evaluate the hazard ratios for mortality and penalized splines for assessing potential nonlinear concentration-response associations. Results suggested that increased exposure to PM 2.5 mass and its six main constituents were significantly linked to elevated all-cause mortality. All components showed linear concentration-response relationships in the low exposure concentration ranges. Our research indicates that long-term exposure to PM 2.5 mass and its essential compounds are strongly connected to increased mortality risk. Reductions of fossil fuel burning may yield significant air quality and public health benefit.

The rational design and preparation of stable and multifunctional metal-organic frameworks (MOFs) with excellent catalysis and adsorption properties are desirable but are great challenges. The nitrophenol (NP) reduction to aminophenols (APs) by using the catalyst Pd@MOFs is an effective strategy, which has attracted extensive attention in recent years. Here, we report four stable isostructural two-dimensional (2D) rare earth metal-organic frameworks [RE 4 (AAPA) 6 (DMA) 2 (H 2 O) 4 ][DMA] 3 [H 2 O] 8 (namely LCUH - 101 , RE = Eu, Gd, Tb, Y; AAPA 2- = 5-[(anthracen-9-yl-methyl)-amino]-1,3-isophthalate), which feature a 2D layer structure with sql topology of point symbol {4 4 ·6 2 } and exhibit excellent chemical stability and thermostability. The as-synthesized Pd@ LCUH - 101 was utilized for the catalytic reduction of 2/3/4-nitrophenol, which indicates high catalytic activity and recyclability attributed to the synergistic effect between Pd nanoparticles and the 2D layered structure. Of note, the turnover frequency (TOF), the reaction rate constant ( k ), and the activation energy ( E a ) of Pd@ LCUH - 101 (Eu) in the reduction of 4-NP, respectively, are 1.09 s -1 , 2.17 min -1 , and 50.2 kJ·mol -1 , which show that it has superior catalytic activity. Remarkably, LCUH - 101 ( Eu, Gd, Tb, and Y) are multifunctional MOFs that can effectively absorb and separate mixed dyes. The appropriate interlayer spacing enables them to efficiently adsorb methylene blue (MB) and rhodamine B (RhB) in aqueous solution, with adsorption capacities of 0.97 and 0.41 g·g -1 , respectively, which is one of the highest values among those of the reported MOF-based adsorbers. Meanwhile, LCUH - 101 (Eu) can be used for the separation of the dye mixture MB/MO and RhB/MO, and the excellent reusability enables LCUH - 101 (Eu) to be used as chromatographic column filters to quickly separate and recover dyes. Therefore, this work provides a new strategy for the exploitation of stable and efficient catalysts for NP reduction and adsorbents for dyes.

Most of the oilfields are currently experiencing intermediate to late stages of oil recovery by waterflooding. Channels were created between the wells by water injection and its effect on the oil recovery is less. The use of water plugging profile control is required to control excessive water production from an oil reservoir. First, the well selection for profile control using the fuzzy evaluation method (FEM) and improvement by random forest (RF) classification model is investigated. To identify wells for profile control operation, a fuzzy model with four factors is established; then, a machine learning RF algorithm was applied to create the factor weight with high accuracy decision-making. The data source consists of 18 injection wells, with 70% of the well data being utilized for training and 30% for model testing. Following the fitting of the model, the new factor weight is determined and decisions are made. As a consequence, FEM selects 7 out of 18 wells for profile control, and by using the factor weight developed by RF, 4 out of 18 wells are chosen. Then, the profile control is conducted through a foam system proposed by laboratory experiments. A computer molding group numerical simulation model is created to profile the wells being selected by both methods, FEM and RF. The impact of foam system plugging on daily oil production, water cut, and cumulative oil production of both methods are contrasted. According to the study, the reservoir performed better when four wells were chosen by the weighting system developed by RF as opposed to seven wells that were chosen using the FEM model during the effective period. The weighting model developed by RF accurately increased the profile control wells' decision-making skills., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Computational quantum chemistry can be more than just numerical experiments when methods are specifically adapted to investigate chemical concepts. One important example is the development of energy decomposition analysis (EDA) to reveal the physical driving forces behind intermolecular interactions. In EDA, typically the interaction energy from a good-quality density functional theory (DFT) calculation is decomposed into multiple additive components that unveil permanent and induced electrostatics, Pauli repulsion, dispersion, and charge-transfer contributions to noncovalent interactions. Herein, we formulate, implement, and investigate decomposing the forces associated with intermolecular interactions into the same components. The resulting force decomposition analysis (FDA) is potentially useful as a complement to the EDA to understand chemistry, while also providing far more information than an EDA for data analysis purposes such as training physics-based force fields. We apply the FDA based on absolutely localized molecular orbitals (ALMOs) to analyze interactions of water with sodium and chloride ions as well as in the water dimer. We also analyze the forces responsible for geometric changes in carbon dioxide upon adsorption onto (and activation by) gold and silver anions. We also investigate how the force components of an EDA-based force field for water clusters, namely MB-UCB, compare to those from force decomposition analysis.