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We introduce an exact-two-component complete active space self-consistent-field (X2C-CASSCF) method formulated under the restricted-magnetic-balance condition. This framework allows for the nonperturbative treatment of static magnetic fields using gauge-including atomic orbitals (GIAOs). The GIAO-X2C-CASSCF methodology effectively captures all microstates within the same 2 J + 1-degenerate manifold and their splitting in a static magnetic field, which are not accessible through single-reference-based methods. We also present mathematical recursive expressions for evaluating one-electron relativistic integrals by using GIAOs in the presence of a finite magnetic field. Benchmark studies include oxygen and nitrogen K-edge X-ray magnetic circular dichroism spectroscopy (XMCD) for closed-shell organic compounds, as well as L-edge XMCD spectroscopy for the high-spin open-shell transition metal ion Mn 2+ and the tetrahedral Mn(II)O 4 6- complex.

Conventional methods for detecting single nucleotide polymorphisms (SNPs) in clinical practice often require substantial time, labor, and specialized equipment, limiting their widespread application. To address this limitation, we refined our previous SNP detection method, IMAS-RPA [introducing an extra mismatched base adjacent to the single-base mutant site by recombinase polymerase amplification (RPA)], resulting in an updated version termed IMAS-RPAv2. We began by introducing a suboptimal protospacer adjacent motif (PAM) sequence, GTTG, into the double-stranded DNA (dsDNA) products using either RPA or reverse transcription RPA. This modification decreased the efficiency with which CRISPR RNA (crRNA) recognizes the PAM and locally unwinds the dsDNA to form an R loop. After a delay, the R loop forms. However, due to the intentional incorporation of a mismatched base on the crRNA relative to the wild-type double-stranded DNA (WT-dsDNA), a continuous two-base mismatch is established between the crRNA and WT-dsDNA. Consequently, WT-dsDNA does not activate CRISPR/Cas12a's cleavage activity within a short time, while variant-type dsDNA continues to activate CRISPR/Cas12a and produce a robust fluorescence signal. This improvement significantly enhances the SNP discrimination sensitivity, allowing for detection at the single-copy level. Results were observed using both a conventional microplate reader and a specially designed portable device created through 3D printing. This device allows a direct fluorescence observation without the need for additional equipment. Consequently, the entire detection process becomes independent of large-scale equipment. This greatly expands its range of applications and offers promising prospects for clinical use.

The genesis, occurrence, and accumulation of coalbed methane (CBM) are critical to the methane exploration and development. Combining the geological and geochemical data from CBM exploration wells and basin modeling, the genesis and accumulation characteristics of CBM in different regions and depths at the eastern margin of Ordos Basin were elucidated. Regional-scale gas content is controlled by depth and coal rank without turning depth occurs, but blocks perform variably. Three CBM genetic types, that is, secondary microbial, thermogenic, and mixed genesis, were identified based on data of gas components and isotopic composition. Under the influences of tectonic and hydrogeological conditions, secondary microbial gas is widely distributed in shallow coal seams (depth <1350 m) showing mixed gas characteristics, while secondary thermogenic gas dominates in deep coal seams. The extensive variations of carbon isotope of methane raised from desorption-diffusion induced by tectonic uplift, dissolution in flowing groundwater, secondary microbial gas generation, and rapid gas generation enhanced by magmatic thermal. Three CBM accumulation modes have been concluded depending on the depth and coal rank. The Baode mode is characterized by a high-ratio secondary microbial gas replenishment, typically occurring at lower ranks and shallow depths. The Linxing mode is distinguished by magmatic thermal influences, and the Daji mode features massive secondary thermogenetic gas associated with higher ranks and deeper depths. Every mode has the potential to form high-gas-content zones., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Dual-ion electrochemical energy storage devices have attracted much attention due to their cost effectiveness and high operating voltage. Electrochemical properties such as the specific capacity of dual-ion energy storage devices are closely related to ion migration. However, the ion migration of dual-ion energy storage devices is slow, especially the cation migration, resulting in limited discharge capacity and poor rate performance. In this study, fluorinated and nonfluorinated ambipolar conductive polymers were prepared as electrode materials. The effects of fluorination on aggregation and solvent were studied as well as its role in improving ion migration. The results show that fluorination can increase the force of fluorination on the solvent, reduce the level of binding of the solvent to the ion, and regulate the aggregation state. Compared with the unfluorinated polymer of PEPOPE, the ion migration and electrochemical kinetics of PEPFEP were significantly improved, and the PEPFPE (71 F/cm 3 ) has a higher negative specific capacity than PEPOPE (24 F/cm 3 ) at a current density of 5 A/cm 3 .

Quasi-two-dimensional (Q-2D) perovskites show great potential in the field of photonic and optoelectronic device applications. However, defects and local lattice dislocation still limit performance and stability improvement by nonradiative recombination, unpreferred phase distribution, and unbonded amines. Here, a low-temperature synergistic strategy for both reconstructing and solidifying the perovskite top and buried interface is developed. By post-treating the 1,4-phenylenedimethanammonium (PDMA) based (PDMA)MA 4 Pb 5 I 16 films with cesium acetate (CsAc) before thermal annealing, a condensation reaction between R-COO - and -NH 2 and ion exchange between Cs + and MA + occur. It converts the unbonded amines to amides and passivates uncoordinated Pb 2+ . Meanwhile, it adjusts film composition and improves the phase distribution without changing the out-of-plane grain orientation. Consequently, performance of 18.1% and much-enhanced stability (e.g., stability for photo-oxygen increased over 10 times, light-thermal for T 90 over 4 times, and reverse bias over 3 times) of (PDMA)MA 4 Pb 5 I 16 perovskite solar cells are demonstrated.

This study addresses the environmental pollution and safety hazards associated with the cyanide leaching process in gold mining, proposing a more environmentally friendly and cost-effective potassium chlorate leaching method. The feasibility of this method was verified through thermodynamic analysis. Building upon single-factor experiments, the study utilized a response surface methodology to investigate the effects of potassium chlorate dosage, liquid-to-solid ratio, reaction temperature, and reaction pH on leaching efficiency. Results indicate that the order of influence on leaching efficiency is KClO 3 dosage > liquid-to-solid ratio > temperature > pH, with significant interactions observed between KClO 3 dosage and temperature. Optimal process parameters were determined as follows: initial potassium chlorate dosage of 21 g, liquid-to-solid ratio of 8.2/1, reaction temperature of 34 °C, and initial reaction pH of 12, achieving a gold leaching rate of 86.37%. To further optimize leaching efficiency, potassium carbonate was introduced to maintain system pH stability, promoting the formation of soluble iron carbonate complexes to reduce the re-encapsulation of minerals by Fe(OH) 3 and prevent gold from existing as Au(OH) 3 , thus hindering gold leaching. Electrochemical studies revealed that increasing the potassium carbonate dosage enhances the dissolution of the passivation film. Under conditions of a potassium carbonate dosage of 0.75 mol/L and initial pH of 12, the gold leaching rate increased to 91.69%, with the system pH maintained above 11.68. Therefore, the addition of potassium carbonate effectively reduces the re-encapsulation of gold during leaching, further improving leaching efficiency., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Sclareolide, a natural product with bioactive and fragrant properties, is not only utilized in the food, healthcare, and cosmetics industries but also serves as a precursor for the production of ambroxide and some bioactive compounds. Currently, there are three primary methods for producing sclareolide: direct extraction from plants, chemical synthesis using sclareol as a precursor, and the biotransformation of sclareol. Here, we established a platform for producing sclareolide through a modular coculture system with Saccharomyces cerevisiae and Cryptococcus albidus ATCC 20918. S. cerevisiae was engineered for de novo sclareol biosynthesis from glucose, while C. albidus enabled the production of sclareolide via sclareol biotransformation. To enhance the supply of sclareol, a recombinant yeast strain was constructed through metabolic engineering to produce 536.2 mg/L of sclareol. Further improvement of the coculture system for sclareolide production was achieved by incorporating Triton X-100 facilitated intermediate permeability, inoculation proportion adjustment, and culture temperature optimization. These refinements culminated in a sclareolide yield of 626.3 mg/L. This study presents a novel streamlined and efficient approach for sclareolide preparation, showcasing the potential of the microbial consortium in sustainable bioproduction.

Photoelectrochemical (PEC) sensing mechanisms based on enzyme-catalyzed strategies primarily achieve the quantitative analysis of biomolecules through the enhancement or attenuation of photocurrent signals. However, there are still no reports that delve into the principles of photocurrent signaling conversion in the reaction between photoactive materials and the biomolecules. In this work, we demonstrated that indium oxysulfide InOS-0.5 heterojunction has excellent peroxidase activity to catalyze the reaction of H 2 O 2 -generated hydroxyl radicals ( • OH) with the self-generated electrons, thereby resulting in synergistic quenching of the photocurrent signal. Based on the above principles, we coupled InOS-0.5 with a sandwich-type immunoassay to introduce H 2 O 2 production catalyzed by glucose oxidase for the development of a PEC immunosensing platform. H 2 O 2 reacted with InOS-0.5 to produce • OH with strong oxidizing properties, thus quenching the photogenerated electrons and realizing the PEC detection of the carcinoembryonic antigen (CEA, as a model analyte). The photocurrent intensity decreases with the logarithmic increase in CEA concentration (0.02-50 ng mL -1 ), with a remarkable limit of detection of 8.9 pg mL -1 (S/N = 3). This study further investigates the mechanism of hydrogen peroxide-induced photocurrent quenching, providing deeper insights into the mechanisms of electron-hole transport in hollow porous semiconductor materials and paving the way for the development of efficient PEC sensors.

Bovine serum albumin (BSA) has been widely used in biosensors as a blocking agent. Herein, conformist BSA was first exploited as an ingenious operator to enhance the photocurrent response of (2 Z ,2' Z )-2,2'-(1,4-phenylene)bis(3-(4-(bis(4-methoxyphenyl)amino)phenyl)acrylonitrile) (TPDCN)-based photoelectrochemical (PEC) platform via manipulating the electron transfer process of the detection system. Concretely, the presence of target molecules triggered catalytic hairpin assembly reaction and subsequently powered terminal deoxynucleotidyl transferase-mediated signal amplification to produce the AgNP@BSA-DNA dendrimer nanostructure. After being treated with HNO 3 , a large amount of BSA could be released from the dendrimer nanostructure. When they were transferred to the TPDCN-based PEC platform, the photocurrent response of the biosensor was largely enhanced because BSA can manipulate the electrons of TPDCN via a well-matched energy level to form a new electron transfer track. Meanwhile, tryptophan (Trp) in BSA could be oxidized to quinone Trp-O under photoirradiation, which can facilitate the oxidation of ascorbate and generate more H + to promote the migration of photogenerated electrons. As a result, the proposed PEC biosensor exhibits excellent analytical performance for detection of miRNA-21 (as a model target) over a wide linear range of 0.01 to 10,000 pM with detection limit as low as 4.7 fM. Overall, this strategy provides a new perspective on constructing efficient PEC biosensors, which expands the potential applications in bioanalysis and clinical diagnosis.

Numerical integration of the exchange-correlation potential is an inherently parallel problem that can be significantly accelerated by graphical processing units (GPUs). In this Letter, we present the first implementation of GPU-accelerated exchange-correlation potential in the GauXC library for relativistic, 2-component density functional theory. By benchmarking against copper, silver, and gold coinage metal clusters, we demonstrate the speed and efficiency of our implementation, achieving significant speedup compared to CPU-based calculations. One GPU card provides computational power equivalent to roughly 400 CPU cores in the context of this work. The speedup further increases for larger systems, highlighting the potential of our approach for future, more computationally demanding simulations. Our implementation supports arbitrary angular momentum basis functions, enabling the simulation of systems with heavy elements and providing substantial speedup to relativistic electronic structure calculations. This advancement paves the way for more efficient and extensive computational studies in the field of density functional theory.

Rapid and accurate detection of human epidermal growth factor receptor 2 (HER2) is crucial for the early diagnosis and prognosis of breast cancer. In this study, we reported an iron-manganese ion N-doped carbon single-atom catalyst (FeMn-NC etch /SAC) bimetallic peroxidase mimetic enzyme with abundant active sites etched by H 2 O 2 and further demonstrated unique advantages of single-atom bimetallic nanozymes in generating hydroxyl radicals by density functional theory (DFT) calculations. As a proof of concept, a portable device-dependent electrochemical-photothermal bifunctional immunoassay detection platform was designed to achieve reliable detection of HER2. In the enzyme-linked reaction, H 2 O 2 was generated by substrate catalysis via secondary antibody-labeled glucose oxidase (GOx), while FeMn-NC etch /SAC nanozymes catalyzed the decomposition of H 2 O 2 to form OH*, which catalyzed the conversion of 3,3',5,5'-tetramethylbenzidine (TMB) to ox-TMB. The ox-TMB generation was converted from the colorimetric signals to electrical and photothermal signals by applied potential and laser irradiation, which could be employed for the quantitative detection of HER2. With the help of this bifunctional detection technology, HER2 was accurately detected in two ways: photothermally, with a linear scope of 0.01 to 2.0 ng mL -1 and a limit of detection (LOD) of 7.5 pg mL -1 , and electrochemically, with a linear scope of 0.01 to 10 ng mL -1 at an LOD of 3.9 pg mL -1 . By successfully avoiding environmental impacts, the bifunctional-based immunosensing strategy offers strong support for accurate clinical detection.

The BioRECIPE (Biological system Representation for Evaluation, Curation, Interoperability, Preserving, and Execution) knowledge representation format was introduced to standardize and facilitate human-machine interaction while creating, verifying, evaluating, curating, and expanding executable models of intra- and intercellular signaling. This format allows a human user to easily preview and modify any model component, while it is at the same time readable by machines and can be processed by a suite of model development and analysis tools. The BioRECIPE format is compatible with multiple representation formats, natural language processing tools, modeling tools, and databases that are used by the systems and synthetic biology communities.

Liquid hydrogen carriers have garnered considerable interest in long-distance and large-scale hydrogen storage owing to their exceptional hydrogen storage density, safety, and compatibility. Nonetheless, their practical application is hampered by the low hydrogen production rate and high cost, stemming from poor thermal utilization and heavy reliance on noble metals in solar bulk dehydrogenation platforms. To conquer these challenges, we devise an economical all-in-one architecture comprising the photothermal catalytic termination-vacant MXene and a highly insulated melamine substrate. This design floats on the air-reactant interface to efficiently drive solar interfacial dehydrogenation. The melamine enables interfacial heat localization to improve the thermal utilization, providing a high reaction temperature. Meanwhile, the MXene with termination vacancies exposes rich active sites for formic acid dehydrogenation, and simultaneously high performance and cost-effectiveness can be realized. This work offers fresh perspectives on the design and application of photothermal catalytic MXene, broadening the prospects for hydrogen storage using liquid hydrogen carriers.

The direct probing of photochemical dynamics by detecting the electronic coherence generated during passage through conical intersections is an intriguing challenge. The weak coherence signal and the difficulty in preparing purely excited wave packets that exclude coherence from other sources make it experimentally challenging. We propose to use time-resolved X-ray magnetic circular dichroism to probe the wave packet dynamics around the conical intersection. The magnetic field amplifies the relative strength of the electronic coherence signal compared to populations through the magnetic field response anisotropy. More importantly, since the excited state relaxation through conical intersections involves a change of parity, the magnetic coupling matches the symmetry of the response function with the electronic coherence, making the coherence signal only sensitive to the conical intersection induced coherence and excludes the pump pulse induced coherence between the ground state and excited state. In this theoretical study, we apply this technique to the photodissociation dynamics of a pyrrole molecule and demonstrate its capability of probing electronic coherence at a conical intersection as well as population transfer. We demonstrate that a magnetic field can be effectively used to extract novel information about electron and nuclear molecular dynamics.

Conical intersections (CIs) are pivotal in many photochemical processes. Traditional quantum chemistry methods, such as the state-average multiconfigurational methods, face computational hurdles in solving the electronic Schrödinger equation within the active space on classical computers. While quantum computing offers a potential solution, its feasibility in studying CIs, particularly on real quantum hardware, remains largely unexplored. Here, we present the first successful realization of a hybrid quantum-classical state-average complete active space self-consistent field method based on the variational quantum eigensolver (VQE-SA-CASSCF) on a superconducting quantum processor. This approach is applied to investigate CIs in two prototypical systems─ethylene (C 2 H 4 ) and triatomic hydrogen (H 3 ). We illustrate that VQE-SA-CASSCF, coupled with ongoing hardware and algorithmic enhancements, can lead to a correct description of CIs on existing quantum devices. These results lay the groundwork for exploring the potential of quantum computing to study CIs in more complex systems in the future.

In this work, we reported a cholesterol oxidase (Chox)-loaded platinum (Pt) nanozyme with the collaborative cascade nanoreactor for the construction of nanozyme-enzyme-linked immunosorbent assay (N-ELSA) models to realize high-throughput rapid evaluation of cancer markers. Considering the high specific surface area and manipulable surface sites, ZIF-8 was used as a substrate for natural enzyme and nanozyme loading. The constructed ZIF-8-Pt nanozyme platform exhibited efficient enzyme-like catalytic efficiency with a standard corrected activity of 60.59 U mg -1 , which was 12 times higher than that of the ZIF-8 precursor, and highly efficient photothermal conversion efficiency (∼35.49%). In N-ELISA testing, developed multienzyme photothermal probes were immobilized in microplates based on antigen-antibody-specific reactions. Cholesterol was reacted in a cascade to reactive oxygen radicals, which attacked 3,3',5,5'-tetramethylbenzidine, causing it to oxidize and color change, thus exhibiting highly enhanced efficient photothermal properties. Systematic temperature evaluations were performed by a hand-held microelectromechanical system thermal imager under the excitation of an 808 nm surface light source to determine the cancer antigen 15-3 (CA15-3) profiles in the samples. Encouragingly, the temperature signal from the microwells increased with increasing CA15-3, with a linear range of 2 mU mL -1 to 100 U mL -1 , considering it to be the sensor with the widest working range for visualization and portability available. This work provides new horizons for the development of efficient multienzyme portable colorimetric-photothermal platforms to help advance the community-based process of early cancer detection.

The methylation modifications of adenosine, especially N 6 -methyladenosine (m 6 A) and N 6 , 2'-odimethyladenosine (m 6 Am), play vital roles in various biological, physiological, and pathological processes. However, current methods for detecting these modifications at single-base resolution have limitations. Mass spectrometry (MS), a highly accurate and sensitive technique, can be utilized to differentiate between m 6 A and m 6 Am by analyzing the molecular weight differences in their fragments during tandem MS analysis. In this study, we present an MS-based method that allows for the simultaneous determination of m 6 A and m 6 Am sites in targeted RNA fragments at single-nucleotide resolution. The approach involves the utilization of tandem MS in conjunction with targeted RNA enrichment and enzymatic digestion, eliminating the need for PCR amplification. By employing this strategy, we can accurately identify m 6 A and m 6 Am sites in targeted RNA fragments with high confidence. To evaluate the effectiveness of our method, we applied it to detect m 6 A and m 6 Am sites in cell and tissue samples. Furthermore, we verified the accuracy of our approach by performing CRISPR/Cas9-mediated knockout of the corresponding methyltransferases. Overall, our MS-based method offers a reliable and precise means for the simultaneous detection of m 6 A and m 6 Am modifications in targeted RNA fragments, providing valuable insights into the functional characterization of these modifications in various biological contexts.

Carboxylesterase (CE), an enzyme widely present in organisms, is involved in various physiological and pathological processes. Changes in the levels of CEs in the liver may predict the presence of type 2 diabetes mellitus (T2DM). Here, a novel dicyanoisophorone (DCI)-based proximity-labeled far-red fluorescent probe DCI2F-Ac with endoplasmic reticulum targeting was proposed for real-time monitoring and imaging of the CEs activity. DCI2F-Ac featured very low cytotoxicity and biotoxicity and was highly selective and sensitive for CEs. Compared with traditional CEs probes, DCI2F-Ac was covalently anchored directly to CEs, thus effectively reducing the loss of in situ fluorescent signals due to diffusion. Through the "on-off" fluorescence signal readout, DCI2F-Ac was able to distinguish cell lines and screen for CEs inhibitors. In terms of endoplasmic reticulum (ER) stress, it was found that thapsigargin (Tg) induced upregulation of CEs levels but not tunicamycin (Tm), which was related to the calcium homeostasis of the ER. DCI2F-Ac could efficiently detect downregulated CEs in the livers of T2DM, and the therapeutic efficacy of metformin, acarbose, and a combination of these two drugs was assessed by tracking the fluctuation of CEs levels. The results showed that combining metformin and acarbose could restore CEs levels to near-normal levels with the best antidiabetic effect. Thus, the DCI2F-Ac probe provides a great opportunity to explore the untapped potential of CEs in liver metabolic disorders and drug efficacy assessment.

Hydraulic fracturing technology has become a common practice to enhance the permeability of coal seams, and its effectiveness significantly impacts the productivity of coalbed methane (CBM) wells. In this study, multiple data sets, including fracturing reports, productivity data, and microseismic monitoring, were utilized to analyze the factors influencing fracturing effectiveness and gas well production at the southern margin of the Qinshui Basin, China, especially the Zhengzhuang and Fanzhuang blocks. Statistics revealed that the fracturing displacement, liquid consumption, and sand consumption were 8 m 3 /min, 17.69-1386.52 m 3 (averaging 728.42 m 3 ), and 28.5-46.1 m 3 (averaging 40 m 3 ), respectively. There were differences in the types of fracturing curves among blocks or well groups, and the natural fracture system was identified as the key factor affecting their characteristics. The coal seams with high density of microfractures in Zhengzhuang reduce the fracture threshold of reservoirs during hydraulic fracturing, resulting in a lower fracture response ratio than that of Fanzhuang (71.0 vs 80.3%). Well groups with higher microfracture width in coal seams (Group-ZC and DS) experienced a further reduction in fracture response (averaging 67.2 vs 80.3%), and the connection of hydraulic fractures (HFs) with these high-permeability microfractures lead to an increase in the proportion of fluctuating fracturing curves (averaging 52.2 vs 33.6%). Regional structural features and fracturing effectiveness jointly affected the production of CBM wells. The productivity in Zhengzhuang was lower than that in Fanzhuang due to the highly developed faults and deeply buried coal seams. Shallow coal seams with a high width of microfractures and a low-stress environment were easily supported by a proppant, forming a complex HF network and yielding a high productivity (Group-ZC and DS). For other deeper well groups, proppant migration became unfavorable once high-angle and complex branch HF clusters formed in coal seams, leading to local low-efficiency wells and fluctuating fracturing curves., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Lung cancer is the main cause of cancer deaths around the world. Nitrosamine 4-(methyl nitrosamine)-1-(3-pyridyl)-1-butanone (NNK) is a tobacco-specific carcinogen of lung cancer. Abundant evidence implicates long noncoding RNAs (lncRNAs) in tumorigenesis. Yet, the effects and mechanisms of lncRNAs in NNK-induced carcinogenesis are still unclear. In this study, we discovered that NNK-induced transformed Beas-2B cells (Beas-2B-NNK) showed increased cell migration and proliferation while decreasing rates of apoptosis. RNA sequencing and differentially expressed lncRNAs analyses showed that lncRNA PSMB8-AS1 was obviously upregulated. Interestingly, silencing the lncRNA PSMB8-AS1 in Beas-2B-NNK cells reduced cell proliferation and migration and produced cell cycle arrest in the G2/M phase along with a decrease in CDK1 expression. Conclusively, our results demonstrate that lncRNA PSMB8-AS1 could promote the malignant characteristics of Beas-2B-NNK cells by regulating CDK1 and affecting the cell cycle, suggesting that it may supply a new prospective epigenetic mechanism for lung cancer.

An important element of antibody-guided vaccine design is the use of neutralizing or opsonic monoclonal antibodies to define protective epitopes in their native three-dimensional conformation. Here, we demonstrate a multimodal mass spectrometry-based strategy for in-depth characterization of antigen-antibody complexes to enable the identification of protective epitopes using the cytolytic exotoxin Streptolysin O (SLO) from Streptococcus pyogenes as a showcase. We first discovered a monoclonal antibody with an undisclosed sequence capable of neutralizing SLO-mediated cytolysis. The amino acid sequence of both the antibody light and the heavy chain was determined using mass-spectrometry-based de novo sequencing, followed by chemical cross-linking mass spectrometry to generate distance constraints between the antibody fragment antigen-binding region and SLO. Subsequent integrative computational modeling revealed a discontinuous epitope located in domain 3 of SLO that was experimentally validated by hydrogen-deuterium exchange mass spectrometry and reverse engineering of the targeted epitope. The results show that the antibody inhibits SLO-mediated cytolysis by binding to a discontinuous epitope in domain 3, likely preventing oligomerization and subsequent secondary structure transitions critical for pore-formation. The epitope is highly conserved across >98% of the characterized S. pyogenes isolates, making it an attractive target for antibody-based therapy and vaccine design against severe streptococcal infections.

Pressure and temperature, as common physical parameters, are important for monitoring human health. In contrast, single-mode monitoring is prone to causing experimental errors. Herein, we innovatively designed a dual-mode flexible sensing platform based on a platinum/zinc-meso-tetrakis(4-carboxyphenyl)porphyrin (Pt/Zn-TCPP) nanozyme for the quantitative monitoring of carcinoembryonic antigen (CEA) in biological fluids with pressure and temperature readouts. The Pt/Zn-TCPP nanozyme with catalytic and photothermal efficiencies was synthesized by means of integrating photosensitizers into porous materials. The flexible sensing system after the antigen-antibody reaction recognized the pressure using a flexible skin-like pressure sensor with a digital multimeter readout, whereas the temperature was acquired via the photoheat conversion system of the Pt/Zn-TCPP nanozyme under 808 nm near-infrared (NIR) irradiation using a portable NIR imaging camera on a smartphone. Meanwhile, the dual-mode flexible sensing system was carried out on a homemade three-dimensional (3D)-printed device. Results revealed that the developed dual-mode immunosensing platform could exhibit good pressure and temperature responses within the dynamic range of 0.5-100 ng mL -1 CEA with the detection limits of 0.24 and 0.13 ng mL -1 , respectively. In addition, the pressure and temperature were sensed simultaneously without crosstalk interference. Importantly, the dual-mode flexible immunosensing system can effectively avoid false alarms during the measurement, thus providing great potential for simple and low-cost development for point-of-care testing.

Semiconductor-based photoelectrochemical (PEC) test protocols offer a viable solution for developing efficient individual health monitoring by converting light and chemical energy into electrical signals. However, slow reaction kinetics and electron-hole complexation at the interface limit their practical application. Here, we reported a triple-engineered CdS nanohierarchical structures (CdS NHs) modification scheme including morphology, defective states, and heterogeneous structure to achieve precise monitoring of the neurotransmitter dopamine (DA) in plasma and noninvasive body fluids. By precisely manipulating the Cd-S precursor, we achieved precise control over ternary CdS NHs and obtained well-defined layered self-assembled CdS NHs through a surface carbon treatment. The integration of defect states and the thin carbon layer effectively established carrier directional transfer pathways, thereby enhancing interface reaction sites and improving the conversion efficiency. The CdS NHs microelectrode fabricated demonstrated a remarkable negative response toward DA, thereby enabling the development of a miniature self-powered PEC device for precise quantification in human saliva. Additionally, the utilization of density functional theory calculations elucidated the structural characteristics of DA and the defect state of CdS, thus establishing crucial theoretical groundwork for optimizing the polymerization process of DA. The present study offers a potential engineering approach for developing high energy conversion efficiency PEC semiconductors as well as proposing a novel concept for designing sensitive testing strategies.

An available and simple electromediated cyclization method for 3-amino-substituted pyrazoles by using α,β-alkynic hydrazone and secondary amine is described. The strategy utilizes KI as an electrolyte in an undivided cell with a constant current, generating the desired products in moderate-to-good yield. The method features selective amination at the 3-position of the pyrazole skeleton. The results indicate that α,β-alkynic hydrazones functionalized with aromatic groups and secondary amines functionalized with electron-rich groups were better tolerated in this transformation.

Nanomaterials have attractive physicochemical properties. A variety of nanomaterials such as inorganic, lipid, polymers, and protein nanoparticles have been widely developed for nanomedicine via chemical conjugation or physical encapsulation of bioactive molecules. Superior to traditional drugs, nanomedicines offer high biocompatibility, good water solubility, long blood circulation times, and tumor-targeting properties. Capitalizing on this, several nanoformulations have already been clinically approved and many others are currently being studied in clinical trials. Despite their undoubtful success, the molecular mechanism of action of the vast majority of nanomedicines remains poorly understood. To tackle this limitation, herein, this review critically discusses the strategy of applying multiomics analysis to study the mechanism of action of nanomedicines, named nanomedomics, including advantages, applications, and future directions. A comprehensive understanding of the molecular mechanism could provide valuable insight and therefore foster the development and clinical translation of nanomedicines.

The volumetric density of the metal atomic site is decisive to the operating efficiency of the photosynthetic nanoreactor, yet its rational design and synthesis remain a grand challenge. Herein, we report a shell-regulating approach to enhance the volumetric density of Co atomic sites onto/into multishell Zn x Cd 1- x S for greatly improving CO 2 photoreduction activity. We first establish a quantitative relation between the number of shell layers, specific surface areas, and volumetric density of atomic sites on multishell Zn x Cd 1- x S and conclude a positive relation between photosynthetic performance and the number of shell layers. The triple-shell Zn x Cd 1- x S-Co 1 achieves the highest CO yield rate of 7629.7 μmol g -1 h -1 , superior to those of the double-shell Zn x Cd 1- x S-Co 1 (5882.2 μmol g -1 h -1 ) and single-shell Zn x Cd 1- x S-Co 1 (4724.2 μmol g -1 h -1 ). Density functional theory calculations suggest that high-density Co atomic sites can promote the mobility of photogenerated electrons and enhance the adsorption of Co(bpy) 3 2+ to increase CO 2 activation (CO 2 → CO 2 * → COOH* → CO* → CO) via the S-Co-bpy interaction, thereby enhancing the efficiency of photocatalytic CO 2 reduction.

Single-atom nanozyme-based catalytic therapy is of great interest in the field of tumor catalytic therapy; however, their development suffers from the low affinity of nanozymes to the substrates (H 2 O 2 or O 2 ), leading to deficient catalytic activity in the tumor microenvironment. Herein, we report a new strategy for precisely tuning the d-band center of dual-atomic sites to enhance the affinity of metal atomic sites and substrates on a class of edge-rich N-doped porous carbon dual-atomic sites Fe-Mn (Fe 1 Mn 1 -NC e ) for greatly boosting multiple-enzyme-like catalytic activities. The as-made Fe 1 Mn 1 -NC e achieved a much higher catalytic efficiency ( K cat / K m = 4.01 × 10 5 S -1 ·M -1 ) than Fe 1 -NC e ( K cat / K ) with an outstanding stability of over 90% activity retention after 1 year, which is the best among the reported dual-atom nanozymes. Theoretical calculations reveal that the synergetic effect of Mn upshifts the d-band center of Fe from -1.113 to -0.564 eV and enhances the adsorption capacity for the substrate, thus accelerating the dissociation of H m = 2.41 × 10 4 S -1 ·M -1 ) with an outstanding stability of over 90% activity retention after 1 year, which is the best among the reported dual-atom nanozymes. Theoretical calculations reveal that the synergetic effect of Mn upshifts the d-band center of Fe from -1.113 to -0.564 eV and enhances the adsorption capacity for the substrate, thus accelerating the dissociation of H 2 O 2 and weakening the O-O bond on O 2 . We further demonstrated that the superior enzyme-like catalytic activity of Fe 1 Mn 1 -NC e combined with photothermal therapy could effectively inhibit tumor growth in vivo, with an inhibition rate of up to 95.74%, which is the highest value among the dual-atom artificial enzyme therapies reported so far.

Asthma is recognized as a chronic respiratory illness characterized by airway inflammation and airway hyperresponsiveness. Wogonoside, a flavonoid glycoside, is reported to significantly alleviate the inflammation response and oxidative stress. Herein, this study aimed to investigate the therapeutic effect and underlying mechanism of wogonoside on airway inflammation and mucus hypersecretion in a murine asthma model and in human bronchial epithelial cells (16HBE). BALB/c mice were sensitized and challenged with ovalbumin (OVA). Pulmonary function and the number of cells in the bronchoalveolar lavage fluid (BALF) were examined. Pathological changes in lung tissue in each group were evaluated via hematoxylin and eosin and periodic acid-Schiff staining, and changes in levels of cytokines in BALF and of immunoglobulin E in serum were determined via an enzyme-linked immunosorbent assay. The expression of relevant genes in lung tissue was analyzed via real-time PCR. Western blotting and immunofluorescence were employed to detect the expression of relevant proteins in lung tissue and 16HBE cells. Treatment with 10 and 20 mg/kg wogonoside significantly attenuated the OVA-induced increase of inflammatory cell infiltration, mucus secretion, and goblet cell percentage and improved pulmonary function. Wogonoside treatment reduced the level of T-helper 2 cytokines including interleukin (IL)-4, IL-5, and IL-13 in BALF and of IgE in serum and decreased the mRNA levels of cytokines (IL-4, IL-5, IL-6, IL-13, and IL-1β and tumor necrosis factor-α), chemokines (CCL-2, CCL-11, and CCL-24), and mucoproteins (MUC5AC, MUC5B, and GOB5) in lung tissues. The expression of MUC5AC and the phosphorylation of STAT6 and NF-κB p65 in lung tissues and 16HBE cells were significantly downregulated after wogonoside treatment. Thus, wogonoside treatment may effectively decrease airway inflammation, airway remodeling, and mucus hypersecretion via blocking NF-κB/STAT6 activation.

Different from prevalent approaches such as immunological recognition, complementary base pairing, or enzymatic regulation in current photoelectrochemical (PEC) sensing, this study reported an excited-state intramolecular proton transfer (ESIPT)-driven photon-gating PEC sensor. The sensor is developed for the detection of CO-releasing molecule-3 (CORM-3) by modifying an ESIPT-switched organic fluorescent probe molecule (NDAA) onto the surface of a p-type semiconductor (BiOI). The NDAA can be excited and exhibit strong green fluorescence after responding with CORM-3, resulting in an electrode-interface photon competitive absorption effect due to the switch on ESIPT and considerably reducing the photocurrent signal. The experimental results revealed that the as-developed PEC sensor achieved good analytical performance with high selectivity and sensitivity, with a linear range of 0.01-1000 μM and a lower detection limit of 6.5 nM. This work demonstrates the great potential of the organic fluorescent probe molecule family in advancing PEC analysis. It is anticipated that our findings will stimulate the creation of diverse functional probes possessing distinctive characteristics for inventive PEC sensors.

Micro(nano)plastics (MNPs) are emerging pollutants that can adsorb pollutants in the environment and biological molecules and ultimately affect human health. However, the aspects of adsorption of intracellular proteins onto MNPs and its biological effects in cells have not been investigated to date. The present study revealed that 100 nm polystyrene nanoplastics (NPs) could be internalized by THP-1 cells and specifically adsorbed intracellular proteins. In total, 773 proteins adsorbed onto NPs with high reliability were identified using the proteomics approach and analyzed via bioinformatics to predict the route and distribution of NPs following cellular internalization. The representative proteins identified via the Kyoto Encyclopedia of Genes and Genomes pathway analysis were further investigated to characterize protein adsorption onto NPs and its biological effects. The analysis revealed that NPs affect glycolysis through pyruvate kinase M (PKM) adsorption, trigger the unfolded protein response through the adsorption of ribophorin 1 (RPN1) and heat shock 70 protein 8 (HSPA8), and are chiefly internalized into cells through clathrin-mediated endocytosis with concomitant clathrin heavy chain (CLTC) adsorption. Therefore, this work provides new insights and research strategies for the study of the biological effects caused by NPs.

This study explores the room-temperature synthesis of porous materials and the immobilization of CO 2 without the use of metals. The porous aromatic frameworks synthesized at room temperature retain the important functional group structure, and the abundance of carbon-chlorine bonds creates an excellent environment for imidazole linkage. Consequently, a catalyst conducive to the cycloaddition of carbon dioxide is obtained. Hexachloro- p -xylene is explored as the precursor, and a catalyst conducive to carbon dioxide cycloaddition is obtained. The functionalized porous aromatic frameworks (PAF-280-I/B) possess a conversion of 99.6% with a selectivity of 98.9% toward styrene carbonate (SC). The findings of this study can help mitigate the impact of greenhouse gases and enable the production of organic compounds in the circular carbonate platform, turning waste into valuable resources.

Electrochemical capacitors have faced the limitations of low energy density for decades, owing to the low capacity of electric double-layer capacitance (EDLC)-type positive electrodes. In this work, we reveal the functions of interlayer confined water in iron vanadate (FeV 3 O 8.7 · n H 2 O) for sodium-ion storage in nonaqueous electrolyte. Using an electrochemical quartz crystal microbalance, in situ Raman, and ex situ X-ray diffraction and X-ray photoelectron spectroscopy, we demonstrate that both nonfaradaic (surficial EDLC) and faradaic (pseudocapacitance-dominated Na + intercalation) processes are involved in the charge storages. The interlayer confined water is able to accelerate the fast Na + intercalations and is highly stable (without the removal of water or co-intercalation of [Na-diglyme] + ) in the nonaqueous environment. Furthermore, coupling the pseudocapacitive FeV 3 O 8.7 · n H 2 O with EDLC-type activated carbon (FeVO-AC) as the positive electrode brings comprehensive enhancements, displaying the enlarged compaction density of ∼2 times, specific capacity of ∼1.5 times, and volumetric capacity of ∼3 times compared to the AC electrode. Furthermore, the as-assembled hybrid sodium-ion capacitor, consisting of an FeVO-AC positive electrode and a mesocarbon microbeads negative electrode, shows a high energy density of 108 Wh kg -1 at 108 W kg -1 and 15.3 Wh kg -1 at 8.3 kW kg -1 . Our results offer an emerging route for improving both specific and volumetric energy densities of electrochemical capacitors.

In order to elucidate the origin of coalbed methane (CBM) in the Jiergalangtu block of Erlian Basin, Inner Mongolia of China, gas components, stable isotope tests of 22 gas samples, radioisotope dating measurements, and water quality analysis of 15 coproduced water samples were evaluated. On account of the geochemical data and genetic indicators, including C 1 /C 1- n , C 1 /(C 2 + C 3 ), and CO 2 /(CO 2 + CH 4 ) (CDMI) values, δ 13 C(CO 2 ), Δδ 13 C( CO 2 -CH 4 ), δ 15 N, and 3 He/ 4 He combined with vitrinite reflectance (Ro) (0.29-0.48%, avg. 0.35%) of Saihantala formation, the results indicate that methane in the Jiergalangtu block is mostly dominated by primary and secondary biological gas, 40.91% of the gas samples are secondary biogas and primary biogas accounts for 59.19%. Among them, methyl-type fermentation accounts for 31.82%, and carbon dioxide (CO 2 ) reduction makes up 68.18%. CO 2 reduction generally occurs region-wide but is mainly associated with the central part of the block, where CO 2 depletion and 13 C enrichment take place correspondingly. Methane and CO 2 δ 13 C almost tend to isotopically light along the margin of the block, indicating that gas generation is significantly affected by the methyl-type fermentation pathway. Meanwhile, the genesis analysis of other gas components in CBM is also investigated, CO 2 is mainly the associated product of microbial methanogenesis, and nitrogen (N 2 ) is primarily from the atmosphere with a little amount from the earth's crust. Furthermore, the formation time of coalbed water has been dissected based on the hydrogeochemical properties of the coproduced water samples. The coalbed water exhibit a Na-HCO 3 and Na-HCO 3 -Cl type and have a total dissolved solid (TDS) value ranging from 2458.58 to 5579.1 mg/L, with an average of 3440.55 mg/L. Moreover, comprehensive analysis of δD(H 2 O), δ 18 O(H 2 O), δ 13 C DIC , and the radioisotope dating index [ 3 H, 14 C(Fm) and 14 C(BP)] indicates that the coalbed water was formed in the Quaternary Pleistocene and rarely replenished by the present surface water. The mechanism of CBM accumulation is basically sorted out by synthesizing the history of burial, heat, and hydrocarbon generation. The CBM formation can be divided into four stages. That is, microbial gas production approximately began at the beginning of the Early Cretaceous and reached the peak of thermogenic gas production in the middle and late Early Cretaceous. At the end of the Early Cretaceous, strata possibly began to uplift, and denudation led to gas escape. From Neogene to Pleistocene, glacial meltwater tended to penetrate into coalbed on a large scale, and N 2 and CO 2 also entered the coal seams, stimulating abundant secondary biological gas generation. Since Holocene, geological conditions including temperature and TDS have become hostile to biogas generation, and biogas generation tends to stop. Therefore, the Jiergalangtu block mainly represents sealed primary biological gas and secondary biological gas in CBM reservoirs., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

In this work, the aggregation-induced emission ligand 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene (H 4 TCBPE) was rigidified in the Ti-O network to form novel electrochemiluminescence (ECL) emitter H 4 TCBPE-TiO 2 nanospheres, which acted as an effective ECL emitter to construct an "on-off" ECL biosensor for ultrasensitive detection of malathion (Mal). H 4 TCBPE-TiO 2 exhibited excellent ECL responses due to the Ti-O network that can restrict the intramolecular free motions within H 4 TCBPE and then reduce the nonradiative relaxation. Moreover, TiO 2 can act as an ECL co-reaction accelerator to promote the generation of sulfate radical anion (SO 4 •- ), which interacts with H 4 TCBPE in the Ti-O network to produce enhanced ECL response. In the presence of Mal, numerous ligated probes (probe 1 to probe 2, P1-P2) were formed and released by copper-free click nucleic acid ligation reaction, which then hybridized with hairpin probe 1 (H1)-modified H 4 TCBPE-TiO 2 -based electrode surface. The P1-P2 probes can initiate the target-assisted terminal deoxynucleoside transferase (TdTase) extended reaction to produce long tails of deoxyadenine with abundant biotin, which can load numerous streptavidin-functionalized ferrocenedicarboxylic acid polymer (SA-PFc), causing quenching of the ECL signal. Thus, the ultrasensitive ECL biosensor based on H 4 TCBPE-TiO 2 ECL emitter and click chemistry-actuated TdTase amplification strategy presents a desirable range from 0.001 to 100 ng/mL and a detection limit low to 9.9 fg/mL. Overall, this work has paved an avenue for the development of novel ECL emitters, which has opened up new prospects for ECL biosensing.

Background: Systemic lupus erythematosus (SLE) is a severe systemic autoimmune disease with multiple manifestations. Lysine crotonylation (Kcr) is a newly discovered posttranslational modification epigenetic pattern that may affect gene expression and is linked to diseases causally., Methods: We collected blood samples from 11 SLE individuals and 36 healthy subjects. Then, we used highly sensitive liquid chromatography-mass spectrometry technology to carry out proteomics and quantitative crotonylome analysis of SLE peripheral blood mononuclear cells in this investigation, which indicated the unique etiology of SLE. Finally, we verified the expression of critical protein in the leukocyte extravasation pathway by online database analysis and Western blot., Results: There were 618 differentially expressed proteins (DEPs), and 612 crotonylated lysine sites for 272 differentially modified proteins (DMPs) found. These DEPs and DMPs are primarily enriched in the leukocyte extravasation signaling pathway, such as MMP8, MMP9, and ITGAM., Conclusions: This is the first study of crotonylated modification proteomics in SLE. The leukocyte extravasation signaling pathway had a considerable concentration of DEPs and DMPs, indicating that this pathway may be involved in the pathogenic development of SLE., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Lignans are a group of phenolic compounds found in plant-based diets. The human body can obtain lignans through diet, which are then metabolized into enterolignans. The enterolignans have been linked to several health benefits, including anticancer, anti-inflammatory, antioxidant effects, and estrogen effects. This review explores the relationship between the estrogenic effects of lignans and health. This review not only considers the estrogen-like activity of lignans but also discusses the safe dosage of lignans at different life stages. In addition, this review also identified other types of bioactive compounds that can act synergistically with lignans to promote health. Studies have shown that lignan administration during pregnancy and lactation reduces the risk of breast cancer in offspring. Further studies are needed to investigate the estrogenic safety effects of lignan on pregnant women and children. Whether lignans combine with other nutrients in complex food substrates to produce synergistic effects remains to be investigated. This review provides a basis for future studies on the safe dose of lignan and recommended dietary intake of lignan. We believe that the acquired as discussed here has implications for developing dietary therapies that can promote host nutrition and modulate estrogenic diseases.

Cation exchange (CE) is a burgeoning method for controlled crystal synthesis; however, its applications in bioanalysis are still in their infancy. Herein, we explored the transformation of ZnIn 2 S 4 in properties after the CE reaction with Cu 2+ ions; furthermore, the discrepancy was employed to design a dual-readout detection system of photothermal and polarity-switchable photoelectrochemical (PEC) immunoassays to realize reliable detection of carcinoembryonic antigen (CEA). In the presence of CEA, the CuO nanoparticles (CuO NPs) employed as dual-signal response probes would bond to the microplates and be acidolyzed by HCl to release Cu 2+ , which could replace Zn 2+ and In 3+ via the CE reaction. After the CE reaction is completed, the photocurrent would switch from a weak anodic photocurrent to a cathode one by using a 635 nm laser as a signal amplifier, while the photothermal signal would be enhanced with 808 nm laser illumination. On the basis of the polarity-switchable PEC strategy, CEA could be accurately detected from 0.1 to 50 ng mL -1 with a limit of detection (LOD) of 48 pg mL -1 (S/N = 3). Moreover, the photothermal assay for CEA detection possesses a linear range from 0.5 to 100 ng mL -1 with a LOD of 0.21 ng mL -1 . In addition, the designed sensing platform only relies on devices with portability that are permitted for point-of-care detection.

Based on the controllable instantaneous self-assembly ability of long-chain branched DNA nanostructures and the synergistic effect between nucleic acid amplification without enzymes, a highly sensitive and highly specific self-powered biosensing platform is developed. Two-dimensional graphdiyne is prepared, modified on flexible carbon cloth, and then functionalized with gold nanoparticles. When DNA mi-tubes are applied on it, target thalassemia gene CD122 triggers a dual-catalytic hairpin assembly reaction. The generated nanoscale DNA is precisely captured by the DNA mi-tube, exposing binding sites and activating the hybridization chain reaction to form long-chain branched DNA. Double-stranded DNA, along with dendritic DNA carrying a large number of guanine bases, precisely captures the signal molecule methylene blue (MB), generating a significant electrochemical signal. The redox reaction of MB also causes a proportional change in the system's color, achieving a colorimetric detection functionality. An efficient dual-mode self-powered sensing platform, therefore, is established for detecting the thalassemia gene CD122. The linear response range of target concentration to open-circuit voltage and RGB Blue value is 0.0001-10,000 pM. The detection limit under electrochemical mode is 36.3 aM ( S / N = 3), and under colorimetric mode, it is as low as 12.1 aM ( S / N = 3). The new method exhibits high sensitivity, excellent selectivity, and high accuracy, providing a universal strategy for designing novel biosensing platforms that can be extended to the detection of other biomolecules.

Accelerating proton transfer has been demonstrated as key to boosting water oxidation on semiconductor photoanodes. Herein, we study proton-coupled electron transfer (PCET) of water oxidation on five typical photoanodes [i.e., α-Fe 2 O 3 , BiVO 4 , TiO 2 , plasmonic Au/TiO 2 , and nickel-iron oxyhydroxide (Ni 1- x Fe x OOH)-modified silicon (Si)] by combining the rate law analysis of H 2 O molecules with the H/D kinetic isotope effect (KIE) and operando spectroscopic studies. An unexpected and universal half-order kinetics is observed for the rate law analysis of H 2 O, referring to a sequential proton-electron transfer pathway, which is the rate-limiting factor that causes the sluggish water oxidation performance. Surface modification of the Ni 1- x Fe x OOH electrocatalyst is observed to break this limitation and exhibits a normal first-order kinetics accompanied by much enhanced H/D KIE values, facilitating the turnover frequency of water oxidation by 1 order of magnitude. It is the first time that Ni 1- x Fe x OOH is found to be a PCET modulator. The rate law analysis illustrates an effective strategy for modulating PCET kinetics of water oxidation on semiconductor surfaces.

The poisoning of catalysts has always been a vital issue in catalytic reactions. In this study, direct observation of the interaction of CO and oxygen-poisoned Co(0001) has been achieved with scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density functional theory calculation. A two-stage adsorption process of CO on a well-prepared p(2×2)-O layer covered Co(0001) was directly visualized. With increasing annealing time at a certain temperature after the CO dosage, the ordered (2 × 2) pattern formed in the first stage can be recovered, suggesting the weak interaction of CO with the O-covered Co(0001) surface in the latter stage. Compared to the clean Co(0001) surface, on an oxygen-poisoned surface, no further reaction was observed, illustrating the poisoning of the catalyst. Moreover, TPD results are in good agreement with the STM observation; a desorption energy of 0.35 eV is evaluated with a simple but accurate scheme.

Biodegradable polylactic acid (PLA) nanofibrous membranes (NFMs) hold great potential to address the increasing airborne particulate matter (PM) and dramatic accumulation of plastic/microplastic pollution. However, the field of PLA NFM-based filters is still in its infancy, frequently dwarfed by the bottlenecks regarding relatively low surface activity, poor electroactivity, and insufficient PM capturing mechanisms. This effort discloses a microwave-assisted approach to minute-level synthesis of dielectric ZIF-8 nanocrystals with high specific surface area (over 1012 m 2 /g) and ultrasmall size (∼240 nm), which were intimately anchored onto PLA nanofibers (PLA@ZIF-8) by a combined "electrospinning-electrospray" strategy. This endowed the PLA@ZIF-8 NFMs with largely increased electroactivity in terms of elevated dielectric coefficient (an increase of 202%), surface potential (up to 5.8 kV), and triboelectric properties (output voltage of 30.8 V at 10 N, 0.5 Hz). Given the profound control over morphology and electroactivity, the PLA@ZIF-8 NFMs exhibited efficient filtration of PM 0.3 (97.1%, 85 L/min) with a decreased air resistance (592.5 Pa), surpassing that of the pure PLA counterpart (88.4%, 650.9 Pa). This was essentially ascribed to realization of multiple filtration mechanisms for PLA@ZIF-8 NFMs, including enhanced physical interception, polar interactions, and electrostatic adsorption, and the unique self-charging function triggered by airflow vibrations. Moreover, perfect antibacterial performance was achieved for PLA@ZIF-8, showing ultrahigh inhibition rates of 99.9 and 100% against E. coli and S. aureus , respectively. The proposed hierarchical structuring strategy, offering the multifunction integration unattainable with conventional methods, may facilitate the development of biodegradable long-term air filters.

Noble-metal nanozymes have demonstrated great potential in various fields. However, aggregation of single-particle nanoparticles severely affects their exposed catalytically active sites to the extent of exhibiting weak enzyme-like activity. Here, we present an organic block surfactant (polyvinylpyrrolidone, PVP) to construct monodisperse water-stable Pt nanoclusters (Pt NCs) for an enhanced immunoassay of cardiac troponin I (cTnI). The PVP-modified Pt NC nanozyme exhibited up to 16.3 U mg -1 peroxidase-mimicking activity, which was mainly attributed to the ligand modification on the surface and the electron-absorbing effect of the ligand on the Pt NCs. The PVP-modified Pt NCs have a lower OH-transition potential, as determined by density functional theory. Under optimized experimental conditions, the enhanced nanozyme immunoassay strategy exhibited an ultrawide dynamic response range of 0.005-50 ng mL -1 for cTnI targets with a detection limit of 1.3 pg mL -1 , far superior to some reported test protocols. This work provides a designable pathway for the design of artificial enzymes with high enzyme-like activity to further expand the practical range of enzyme alternatives.

Adsorption-based separations using metal-organic frameworks (MOFs) are promising candidates for replacing common energy-intensive separation processes. The so-called adsorption space formed by the combination of billions of possible molecules and thousands of reported MOFs is vast. It is very challenging to comprehensively evaluate the performance of MOFs for chemical separation through experiments. Molecular simulations and machine learning (ML) have been widely applied to make predictions for adsorption-based separations. Previous ML approaches to these issues were typically limited to smaller molecules and often had poor accuracy in the dilute limit. To enable exploration of a wider adsorption space, we carefully selected a diverse set of 45 molecules and 335 MOFs and generated single-component isotherms of 15,075 MOF-molecule pairs by grand canonical Monte Carlo. Using this database, we successfully developed accurate ( r 2 > 0.9) machine learning models predicting adsorption isotherms of diverse molecules in large libraries of MOFs. With this approach, we can efficiently make predictions of large collections of MOFs for arbitrary mixture separations. By combining molecular simulation data and ML predictions with Ideal Adsorbed Solution Theory, we tested the ability of these approaches to make predictions of adsorption selectivity and loading for challenging near-azeotropic mixtures., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The underlying mechanism of common limited lattice thermal conductivity (κ) in energy-related host-guest crystalline compounds has been an ongoing topic in recent decades. Here, the guest-triggered intrinsic ultralow κ of the representative xenon clathrate hydrate was investigated using the time domain thermoreflectance technique and theoretical calculations. The localized guest modes were observed to hybridize with acoustic branches and severely limit the acoustic κ contribution. Besides, the strong mode coupling enables the reshaping of the overall lattice dynamics, especially for optical branches. More importantly, we identified that guest fillers prompt great phonon scattering in wide frequencies, which originates from both the guest-frequency-controlled enhancement of phase space and the host-guest-interaction-governed lattice anharmonicity. The extremely low guest frequency and strong host-guest interaction and coupling were thereby underlined to play vital but distinct roles in κ minimization. Our results unveil the dominant factors of guest reduction effects and facilitate the design of efficient thermoelectric or other thermal-related materials.

Rapid, specific, and on-site detection of virulent foodborne pathogenic strains plays a key role in controlling food safety. In this work, an ultrasensitive and specific Phage@DNAzyme signal probe was designed to detect foodborne pathogens. The proposed sensing probe was composed of the selected phage and functionalized DNAzyme, which realized the specific recognition of target foodborne pathogens at the strain level and the efficient catalysis of copper(II) based azide-alkyne cycloaddition (CuAAC) click reaction with fluorescent signal, respectively. As a proof of concept, the virulent Escherichia coli O157:H7 ( E. coli O157:H7) as the representative analyte was first enriched and purified from the complex food samples by a 4-mercaptophenylboronic acid-modified gold slide. Following, the Phage@DNAzyme probes were specifically combined with the captured E. coli O157: H7 and catalyzed the click reaction between 3-azido-7-hydroxycoumarin and 3-butyn-1-ol with the assistance of Cu(II) to generate a visual fluorescent signal. Finally, the corresponding fluorescent signals were measured by a smartphone to quantify the target concentrations. Under optimized conditions, the bioassay exhibited a wide linear range from 10 2 to 10 8 CFU/mL and the detection limit was 50 CFU/mL ( S / N = 3). It was further extended to the detection of another foodborne pathogen Salmonella typhimurium with satisfying sensing performances. This work gives a new path for developing rapid, specific, and on-site detection methods for trace levels of pathogenic strains in foods.

A major obstacle for machine learning (ML) in chemical science is the lack of physically informed feature representations that provide both accurate prediction and easy interpretability of the ML model. In this work, we describe adsorption systems using novel two-dimensional energy histogram (2D-EH) features, which are obtained from the probe-adsorbent energies and energy gradients at grid points located throughout the adsorbent. The 2D-EH features encode both energetic and structural information of the material and lead to highly accurate ML models (coefficient of determination R 2 ∼ 0.94-0.99) for predicting single-component adsorption capacity in metal-organic frameworks (MOFs). We consider the adsorption of spherical molecules (Kr and Xe), linear alkanes with a wide range of aspect ratios (ethane, propane, n -butane, and n -hexane), and a branched alkane (2,2-dimethylbutane) over a wide range of temperatures and pressures. The interpretable 2D-EH features enable the ML model to learn the basic physics of adsorption in pores from the training data. We show that these MOF-data-trained ML models are transferrable to different families of amorphous nanoporous materials. We also identify several adsorption systems where capillary condensation occurs, and ML predictions are more challenging. Nevertheless, our 2D-EH features still outperform structural features including those derived from persistent homology. The novel 2D-EH features may help accelerate the discovery and design of advanced nanoporous materials using ML for gas storage and separation in the future.

Pursuing effective and generalized strategies for modulating the electronic structures of atomically dispersed nanozymes with remarkable catalytic performance is exceptionally attractive yet challenging. Herein, we developed a facile "formamide condensation and carbonization" strategy to fabricate a library of single-atom (M 1 -NC; 6 types) and dual-atom (M 1 /M 2 -NC; 13 types) metal-nitrogen-carbon nanozymes (M = Fe, Co, Ni, Mn, Ru, Cu) to reveal peroxidase- (POD-) like activities. The Fe 1 Co 1 -NC dual-atom nanozyme with Fe 1 -N 4 /Co 1 -N 4 coordination displayed the highest POD-like activity. Density functional theory (DFT) calculations revealed that the Co atom site synergistically affects the d-band center position of the Fe atom site and served as the second reaction center, which contributes to better POD-like activity. Finally, Fe 1 Co 1 NC was shown to be effective in inhibiting tumor growth both in vitro and in vivo , suggesting that diatomic synergy is an effective strategy for developing artificial nanozymes as novel nanocatalytic therapeutics.

Poly(lactic acid) (PLA)-based nanofibrous membranes (NFMs) hold great potential in the field of biodegradable filters for air purification but are largely limited by the relatively low electret properties and high susceptibility to bacteria. Herein, we disclosed a facile approach to the fabrication of electroactive and antibacterial PLA NFMs impregnated with a highly dielectric photocatalyst. In particular, the microwave-assisted doping (MAD) protocol was employed to yield Zn-doped titanium dioxide (Zn-TIO), featuring the well-defined anatase phase, a uniform size of ∼65 nm, and decreased band gap (3.0 eV). The incorporation of Zn-TIO (2, 6, and 10 wt %) into PLA gave rise to a significant refinement of the electrospun nanofibers, decreasing from the highest diameter of 581 nm for pure PLA to the lowest value of 264 nm. More importantly, dramatical improvements in the dielectric constants, surface potential, and electret properties were simultaneously achieved for the composite NFMs, as exemplified by a nearly 94% increase in surface potential for 3-day-aged PLA/Zn-TIO (90/10) compared with that of pure PLA. The well regulation of morphological features and promotion of electroactivity contributed to a distinct increase in the air filtration performance, as demonstrated by 98.7% filtration of PM 0.3 with the highest quality factor of 0.032 Pa -1 at the airflow velocity of 32 L/min for PLA/Zn-TIO (94/6), largely surpassing pure PLA (89.4%, 0.011 Pa -1 ). Benefiting from the effective generation of reactive radicals and gradual release of Zn 2+ by Zn-TIO, the electroactive PLA NFMs were ready to profoundly inactivate Escherichia coli and Staphylococcus epidermidis . The exceptional combination of remarkable electret properties and excellent antibacterial performance makes the PLA membrane filters promising for healthcare.

Triple-negative breast cancer is particularly difficult to treat because of its high degree of malignancy and poor prognosis. A fluorescence resonance energy transfer (FRET) nanoplatform plays a very important role in disease diagnosis and treatment due to its unique detection performance. Combining the properties of agglomeration-induced emission fluorophore and FRET pair, a FRET nanoprobe (HMSN/DOX/RVRR/PAMAM/TPE) induced by specific cleavage was designed. First, hollow mesoporous silica nanoparticles (HMSNs) were used as drug carriers to load doxorubicin (DOX). HMSN nanopores were coated with the RVRR peptide. Then, polyamylamine/phenylethane (PAMAM/TPE) was combined in the outermost layer. When Furin cut off the RVRR peptide, DOX was released and adhered to PAMAM/TPE. Finally, the TPE/DOX FRET pair was constituted. The overexpression of Furin in the triple-negative breast cancer cell line (MDA-MB-468 cell) can be quantitatively detected by FRET signal generation, so as to monitor cell physiology. In conclusion, the HMSN/DOX/RVRR/PAMAM/TPE nanoprobes were designed to provide a new idea for the quantitative detection of Furin and drug delivery, which is conducive to the early diagnosis and treatment of triple-negative breast cancer.