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Issues concerning the study of the rate of sublimation of a solid organic film on smooth surfaces by use of atomic force microscopy techniques are reported.

The platinum copper alloy nanocrystals(NCs) have generated muchinterest because of their wide applications in fuel cells due primarilyto their good catalytic performance and to decreasing sensitivitytoward CO poisoning. The exact atomic-level morphology of platinumcopper alloy NCs is still not clear in the literature, and researchto understanding the poisoning mechanism is still insufficient todate. In this article, we report on density functional calculationsof small PtnCu clusters and their adsorptionof a CO molecule that provide evidence for degrading adsorption ofthe CO molecule compared to pure platinum clusters. The lowest-energygeometries of PtnCu and PtnCuCO clusters have been identified. The CO moleculeprefers to be adsorbed on the nearest platinum atom by the C-end-onmode, forming linear or quasi-linear O–C–Pt structures.The adsorption energies indicate that the introduction of a copperatom decreases the adsorption ability of the CO molecule. The localdensity of states of the representative clusters is used to characterizethe adsorption properties of the CO molecule on the PtnCu clusters. Results from our theoretical calculationscan be helpful for understanding the poisoning mechanism of the COmolecule on the platinum copper alloy NCs. [ABSTRACT FROM AUTHOR]

Using density functional theory (DFT), we have systematically calculated the equilibrium geometries, electronic structure, and electron detachment energies of Al(BH4)n=1→4 and Al(BF4)n=1→4 at the B3LYP/6-311+G(2d,p) level of theory. The electron affinities of Al(BH4)n not only exhibit odd--even alternation, just as seen in (BH4)n, but also, for n = 3 and 4, show a remarkable behavior: whereas the electron affinities of BH3 and BH4 are, respectively, 0.06 and 3.17 eV, those of Al(BH4)3 and Al(BH4)4 are 0.71 and 5.56 eV. Results where H is replaced by F are also very different. The electron affinities of BF3 and BF4 are, respectively, -0.44 and +6.86 eV, and those of Al(BF4)3 and Al(BF4)4 are 1.82 and 8.86 eV. The results demonstrate not only marked difference when H is replaced by F but also substantially enhanced electron affinities by almost 2 eV when BH4 and BF4 units are allowed decorate a metal atom, confirming the recently observed hyperhalogen behavior of superhalogen building blocks. [ABSTRACT FROM AUTHOR]

Benefiting from highly tunable pore environments, some metal-organic frameworks (MOFs) have recently shown promising prospects in the separation of methanol-to-olefin (MTO) products (mainly C 3 H 6 and C 2 H 4 ). However, the "trade-off" between gas storage capacity and selectivity always results in inefficient separation. In addition, poor stability of MOFs also limits practical separation applications. Herein, we have successfully assembled a layered Y-MOF ( FJI-W9 ) with bent diisophthalate ligands (H 4 L), Y-O chains, and 2-fluorobenzoic acids. As expected, FJI-W9 not only exhibits good chemical stability but also shows significant potential for C 3 H 6 /C 2 H 4 separation. For FJI-W9 , the C 3 H 6 uptake at 298 K and 10 kPa is 63 cm 3 /g, and the IAST selectivity of FJI-W9 for C 3 H 6 /C 2 H 4 (V/V = 50/50) is calculated to be 20.5. To the best of our knowledge, both C 3 H 6 uptake and selectivity of FJI-W9 surpass most porous materials. GCMC simulation indicates that the special supramolecular binding sites in FJI-W9 have much stronger interactions with C 3 H 6 than C 2 H 4 molecules. More importantly, practical breakthrough experiments demonstrate that FJI-W9 can effectively separate C 3 H 6 /C 2 H 4 (50/50) mixtures, thus obtaining high-purity C 2 H 4 and C 3 H 6 , respectively.

Dhilirane-type meroterpenoids (DMs) featuring a 6/6/6/5/5 ring system represent a rare group of fungal meroterpenoids. To date, merely 11 DMs have been isolated or derived, leaving their chemical diversity predominantly unexplored. Herein, we leverage an understanding of biosynthesis to develop a workflow for discovery of DMs by genome mining, metabolite analysis, and tailoring enzyme catalysis. Twenty-three new DMs, including seven unprecedented scaffolds, were consequently identified. An α-ketoglutarate (α-KG)-dependent oxygenase DhiD was found to catalyze the stereodivergent ring contraction of dhilirolide D to form the dhilirane skeleton; while the cytochrome P450 DhiH reshaped the structural diversity by establishing diverse C-C bonds and oxidation. Crystallographic and mutagenesis experiments provide a molecular basis for the DhiD reaction and its stereodivergent products. Notably, DhiD exhibits substrate-controlled catalytic versatility in the chemical expansion of DMs through ring contraction, hydroxylation, dehydrogenation, epoxidation, isomerization, epimerization, and α-ketol cleavage. Bioassay results demonstrated that the obtained meroterpenoids exhibited anti-inflammatory and insecticidal activities. Our work provides insight into nature's arsenal for DM biosynthesis and the functional versatility of α-KG-dependent oxygenase and P450, which can be applied for target discovery and diversification of DM-type natural products.

Antibiotic resistance is a major challenge in modern medicine. The unique double membrane structure of Gram-negative bacteria limits the efficacy of many existing antibiotics and adds complexity to antibiotic development by limiting transport of antibiotics to the bacterial cytosol. New methods to mimic this barrier would enable high-throughput studies for antibiotic development. In this study, we introduce an innovative approach to modify outer membrane vesicles (OMVs) from Aggregatibacter actinomycetemcomitans , to generate planar supported lipid bilayer membranes. Our method first involves the incorporation of synthetic lipids into OMVs using a rapid freeze-thaw technique to form outer membrane hybrid vesicles (OM-Hybrids). Subsequently, these OM-Hybrids can spontaneously rupture when in contact with SiO 2 surfaces to form a planar outer membrane supported bilayer (OM-SB). We assessed the formation of OM-Hybrids using dynamic light scattering and a fluorescence quenching assay. To analyze the formation of OM-SBs from OM-Hybrids we used quartz crystal microbalance with dissipation monitoring (QCM-D) and fluorescence recovery after photobleaching (FRAP). Additionally, we conducted assays to detect surface-associated DNA and proteins on OM-SBs. The interaction of an antimicrobial peptide, polymyxin B, with the OM-SBs was also assessed. These findings emphasize the capability of our platform to produce planar surfaces of bacterial outer membranes, which in turn, could function as a valuable tool for streamlining the development of antibiotics.

Hematopoietic progenitor kinase 1 (HPK1, MAP4K1), a serine/threonine (SER/THR) kinase, has been identified as a negative immune regulator of T-cell receptor signaling. Deprivation of the HPK1 function suppresses tumor growth, providing an attractive strategy for cancer immunotherapy. Herein, we present a novel PROTAC-based HPK1 degrader compound DD205-291 with high selectivity and potency. DD205-291 showed a dose-dependent inhibition of SLP-76 phosphorylation and an induction of IL-2 and IFN-γ. Compared with other inhibitors, DD205-291 exhibited good efficacy and a favorable safety profile in the MC38 model. Specifically, oral administration of DD205-291 at 0.5 mg/kg in combination with anti-PD1 resulted in significant suppression with a TGI value of 91.0%. Furthermore, DD205-291 exhibited a low risk of cardiotoxicity and a wide safety window. This research effort demonstrates that DD205-291 is a promising preclinical candidate (PCC) for potential mono- and comboimmunotherapy of cancer.

Single-atom catalysts (SACs) have exhibited exceptional atomic efficiency and catalytic performance in various reactions but suffer poor stability. Understanding the structure-stability relation is the prerequisite for stability optimization but has been rarely explored due to complexity of the degradation process and reaction environments. Herein, we successfully established the structure-stability relation of N-doped carbon-supports SACs (MN 4 SACs) under working conditions of CO 2 reduction, by using advanced constant-potential density functional theory calculations. Systematic mechanism investigation that considered different factors identifies the key role of initial hydrogen adsorption on the coordination N atom in catalytic stability, where the feasibility of the adsorption eventually determines the leaching of the metal atom. On this basis, a simple descriptor consisting of electron number and electronegativity is constructed, realizing accurate and rapid prediction of the stability of SACs. Furthermore, strategies via modifying the local geometric structure to improve the stability without changing the active centers are proposed accordingly, which are supported by related experiments. These findings fill the current void in understanding SAC stability under practical working conditions, potentially advancing the widespread application of SACs in sustainable energy conversion systems.

Pressure-induced emission (PIE) is a compelling phenomenon that can activate luminescence within nonemissive materials. However, PIE in nonemissive organic materials has never been achieved. Herein, we present the first observation of PIE in an organic system, specifically within nonemissive azobenzene derivatives. The emission of 1,2-bis(4-(anthracen-9-yl)phenyl)diazene was activated at 0.52 GPa, primarily driven by local excitation promotion induced by molecular conformational changes. Complete photoisomerization suppression of the molecule was observed at 1.5 GPa, concurrently accelerating the emission enhancement to 3.53 GPa. Differing from the key role of isomerization inhibition in conventional perception, our findings demonstrate that the excited-state constituent is the decisive factor for emission activation, providing a potentially universal approach for high-efficiency azobenzene emission. Additionally, PIE was replicated in the analogue 1,2-bis(4-(9 H -carbazol-9-yl)phenyl)diazene, confirming the general applicability of our findings. This work marks a significant breakthrough within the PIE paradigm and paves the novel high-pressure route for crystalline-state photoisomerization investigation.

Modulating the electronic structure is essential for improving the anchoring and catalytic capabilities of catalysts in lithium-sulfur batteries (LSBs). This study delves into the modulation of d -orbitals in transition metal dual-atom catalysts (DACs) supported by boron nitride and graphene (BNC) hybrid sheets for LSBs. This study reveals that the d -band center of the DACs, a key determinant of material chemical properties, is primarily determined by the electronic configuration of the d yz and d x 2 - y 2 orbitals. Furthermore, the interaction between d z 2 of transition metals and S_3 p orbitals is critical for the binding strength of LiPSs. By understanding these interactions, the functionality of DACs can be customized for optimal performance in LSBs. For example, the MnCrBNC catalyst with 10 d -electrons exhibits the optimal d -band center and demonstrates exceptional LiPSs binding capability, the lowest Li 2 S decomposition energy barrier, and the lowest Gibbs free energy of reaction for the rate-determining step of sulfur reduction. This study elucidates the fundamental mechanisms for designing high-performance LSB catalysts through electronic structure modulation.

Proteolysis targeting chimeras (PROTACs) represent a transformative class of therapeutic agents that leverage the intrinsic protein degradation machinery to modulate the hemostasis of key disease-associated proteins selectively. Although several PROTACs have been approved for clinical application, suboptimal therapeutic efficacy and potential adverse side effects remain challenging. Benefiting from the enhanced targeted delivery, reduced systemic toxicity, and improved bioavailability, nanomedicines can be tailored with precision to integrate with PROTACs which hold significant potential to facilitate PROTAC nanomedicines (nano-PROTACs) for clinical translation with enhanced efficacy and reduced side effects. In this review, we provide an overview of the recent progress in the convergence of nanotechnology with PROTAC design, leveraging the inherent properties of nanomaterials, such as lipids, polymers, inorganic nanoparticles, nanohydrogels, proteins, and nucleic acids, for precise PROTAC delivery. Additionally, we discuss the various categories of PROTAC targets and provide insights into their clinical translational potential, alongside the challenges that need to be addressed.

Traditional macromolecules or nanoscale Mn 2+ chelate-based magnetic resonance imaging (MRI) contrast agents (CAs) suffer from complicated and laborious synthesis processes, relatively low kinetic stability and T 1 relaxivity, limiting their clinical applications. Herein, we fabricated a series of kinetically inert Mn 2+ chelate-backboned polymers, P(MnL-PEG), through a facile and one-pot polymerization process. Particularly, P(MnL-PEG)-3 demonstrates a significantly higher T 1 relaxivity of 23.9 Mn mM -1 s -1 at 1.5 T than that of previously reported small molecules and macromolecules or nanoscale Mn 2+ chelate-based CAs. Due to its high T 1 relaxivity, extended blood circulation, hepatocyte-specific uptake, and kidneys metabolism, P(MnL-PEG)-3 presents significantly enhanced contrast in blood vessel, liver, and kidneys imaging compared to clinical Gd 3+ -based CAs (Gd-EOB-DTPA and Gd-DOTA) at a dosage of 0.05 mmol Mn/Gd kg -1 BW, and can accurately diagnose orthotopic H22 liver tumors in vivo in animal models. We anticipate that this work will promote the development of clinically relevant MRI CAs.

The fluorescence high-throughput screening method is of importance for new antioxidant drug candidate discovery for the treatment of serious hepatorenal syndrome, which displayed an obvious upregulated peroxynitrite level. However, most of the current ONOO - probes possessed incomplete fluorescence quenching efficiency, which can result in non-negligible probe inherent fluorescence. Hence, we utilized the probe conjugated structure disruption strategy to construct hydrogenation phosphorus-substituted rhodamine ( H-PRh ) with "zero" probe inherent fluorescence character. Based on the precursor, a series of natural products were screened for identifying antioxidant drug candidates. Luteolin was screened out by activating the Sirt1-Nrf2-HO-1 signaling pathway to regulate the accumulation of ONOO - in the hepatorenal syndrome. Overall, the "zero" probe inherent fluorescence ONOO - sensor constructed here applies for a promising and versatile toolbox for illuminating the ONOO - -related pathological process in the hepatorenal syndrome. Besides, this strategy of constructing highly sensitive sensors could serve as a valuable reference for further fluorescent probes.

Iodine derived from edible seaweed significantly enhances the formation of iodinated disinfection byproducts (I-DBPs) during household cooking. Reactions of chlorine with monoiodotyrosine (MIT) and diiodotyrosine (DIT) derived from seaweed were investigated. Species-specific second-order rate constants (25 °C) for the reaction of hypochlorous acid with neutral and anionic MIT were calculated to be 23.87 ± 5.01 and 634.65 ± 75.70 M -1 s -1 , respectively, while the corresponding rate constants for that with neutral and anionic DIT were determined to be 12.51 ± 19.67 and 199.12 ± 8.64 M -1 s -1 , respectively. Increasing temperature facilitated the reaction of chlorine with MIT and DIT. Based on the identification of 59 transformation products/DBPs from iodotyrosines by HPLC/Q-Orbitrap HRMS, three dominant reaction pathways were proposed. Thermodynamic results of computational modeling using density functional theory revealed that halogen exchange reaction follows a stepwise addition-elimination pathway. Among these DBPs, 3,5-diiodo-4-hydroxy-benzaldehyde and 3,5-diiodo-4-hydroxy-benzacetonitrle exhibited high toxic risk. During chlorination of MIT and DIT, iodinated trihalomethanes and haloacetic acids became dominant species at common cooking temperature (80 °C). These results provide insight into the mechanisms of halogen exchange reaction and imply important implications for the toxic risk associated with the exposure of I-DBPs from household cooking with iodine-containing food.

Glioblastoma multiforme (GBM), a common malignant neurological tumor, has boundaries indistinguishable from those of normal tissue, making complete surgical removal ineffective. The blood-brain barrier (BBB) further impedes the efficacy of radiotherapy and chemotherapy, leading to suboptimal treatment outcomes and a heightened probability of recurrence. Hydrogels offer multiple advantages for GBM diagnosis and treatment, including overcoming the BBB for improved drug delivery, controlled drug release for long-term efficacy, and enhanced relaxation properties of magnetic resonance imaging (MRI) contrast agents. Hydrogels, with their excellent biocompatibility and customizability, can mimic the in vivo microenvironment, support tumor cell culture, enable drug screening, and facilitate the study of tumor invasion and metastasis. This paper reviews the classification of hydrogels and recent research for the diagnosis and treatment of GBM, including their applications as cell culture platforms and drugs including imaging contrast agents carriers. The mechanisms of drug release from hydrogels and methods to monitor the activity of hydrogel-loaded drugs are also discussed. This review is intended to facilitate a more comprehensive understanding of the current state of GBM research. It offers insights into the design of integrated hydrogel-based GBM diagnosis and treatment with the objective of achieving the desired therapeutic effect and improving the prognosis of GBM.

A copper-catalyzed oxidative annulation of sydnones with perfluorocarboxylic anhydride for the synthesis of 3-aryl-5-fluoroalkyl-1,3,4-oxadiazol-2(3 H )-ones is developed. A diverse array of 3-aryl-5-fluoroalkyl-1,3,4-oxadiazol-2(3 H )-ones are prepared with good yields (>73 examples, yields up to 95%). The synthetic utility of the developed protocol was demonstrated by gram-scale synthesis, and the synthetic transformation to 1,2,4-triazol-3-one products. A mechanistic study suggests that the reaction proceeds via the extrusion of carbon dioxide to generate the hydrazide intermediate, which then undergoes intramolecular cyclization and oxidation.

Rechargeable aqueous Zn-ion batteries (AZIBs) have been recognized as competitive devices for large-scale energy storage due to their characteristics of low cost, safe operation, and environmental friendliness. Nevertheless, their practical applications are greatly limited by zinc dendrite growth and side reactions occurring at the anode/electrolyte interface. Herein, we propose an effective and simple electrolyte engineering strategy, which is the introduction of l-lysine additive containing two amino groups and one carboxyl group into a ZnSO 4 electrolyte to achieve stable and reversible Zn depositions. Theoretical calculations and experimental results reveal that the l-lysine can adsorb on the Zn anode surface due to the strong coordination effects between amino groups and Zn metal (Zn-N binding) and induce the reduction of ZnSO 4 into inorganic ZnS, which can not only prevent interfacial side reactions but also regulate interfacial electric field on the zinc electrode surface to guide uniform Zn 2+ electrodeposition to inhibit zinc dendrites. Consequently, the l-lysine additive in the electrolyte enables Zn||Zn symmetric cells to achieve an ultralong stable cycling up to 2400 h at 1 mA cm -2 with a low polarization of only about 16 mV and Zn||Cu asymmetric cells to obtain a high average Coulombic efficiency of 99.80% after stably cycling for more than 2000 h at 2 mA cm -2 (1 mAh cm -2 ). In addition, the Zn||MnO 2 @CNT full cell in an l-lysine-containing electrolyte also exhibits good cycling performance. This study offers a new perspective on multifunctional electrolyte additive for achieving highly reversible Zn metal anodes in AZIBs.

Herein, a Y-type compound ( 67dMeOTPA-FQ ) and a T-type compound ( 58dMeOTPA-FQ ) based on furo[2,3- b ]quinoxaline were synthesized. The theory calculation shows the S 1 and T 1 of both compounds own a charge-transfer feature while their T 2 states have a local excitation feature. The calculated k RISC(T2-S1) is one to 2 orders of magnitude larger than k RISC(T1-S1) is up to 104215 cd·m 2 , and the external quantum efficiency (EQE) keeps in the 8.2-8.0% range with the luminance changed from 55.0 cd·m 67dMeOTPA-FQ to 90000 cd·m -2 , and the external quantum efficiency (EQE) keeps in the 8.2-8.0% range with the luminance changed from 55.0 cd·m -2 , a slightly lower EQE of 7.1-6.7% with the luminance range of 1-40000 cd·m -2 , only 2.4% efficiency roll-off. As for 58dMeOTPA-FQ , a slightly lower EQE of 7.1-6.7% with the luminance range of 1-40000 cd·m -2 was achieved for orange-red emission. Both the reverse intersystem crossing (RISC) and triplet-triplet annihilation mechanisms are supposed to concurrently contribute to the utilization of triplet excitons and suppress the notorious efficiency roll-off observed in TADF-based devices.

PD-L1-positive extracellular vesicles (PD-L1 + EVs) play a pivotal role as predictive biomarkers in cancer immunotherapy. These vesicles, originating from immune cells (I-PD-L1 + EVs) and tumor cells (T-PD-L1 + EVs), hold distinct clinical predictive values, emphasizing the importance of deeply differentiating the PD-L1 + EV subtypes for effective liquid biopsy analyses. However, current methods such as ELISA lack the ability to differentiate their cellular sources. In this study, a novel step-wedge microfluidic chip that combines magnetic microsphere separation with single-layer fluorescence counting is developed. This chip integrates magnetic microspheres modified with anti-PD-L1 antibodies and fluorescent nanoparticles targeting EpCAM (tumor cell marker) or CD45 (immunocyte marker), enabling simultaneous quantification and sensitive analysis of PD-L1 + EV subpopulations in oral squamous cell carcinoma (OSCC) patients' saliva without background interference. Analysis results indicate reduced levels of I-PD-L1 + EVs in OSCC patients compared to those in healthy individuals, with varying levels of heterogeneous PD-L1 + EVs observed among different patient groups. During immunotherapy, responders exhibit decreased levels of total PD-L1 + EVs and T-PD-L1 + EVs, accompanied by reduced levels of I-PD-L1 + EVs. Conversely, nonresponders show increased levels of I-PD-L1 + EVs. Utilizing the step-wedge microfluidic chip allows for simultaneous detection of PD-L1 + EV subtypes, facilitating the precise prediction of oral cancer immunotherapy outcomes.

To achieve large-scale hydrogen storage for growing high energy density and long-life demands in end application, the 2LiBH 4 -MgH 2 (LMBH) reactive hydride system attracts huge interest owing to its high hydrogen capacity and thermodynamically favorable reversibility. The sluggish dehydrogenation kinetics and unsatisfactory cycle life, however, remain two challenges. Herein, a bimetallic titanium-niobium oxide with a two-dimensional nanoflake structure (2D TiNb 2 O 7 ) is selected elaborately as an active precursor that in situ transforms into TiB 2 and NbB 2 with ultrafine size and good dispersion in the LMBH system as highly efficient catalysts, giving rise to excellent kinetic properties with long-term cycling stability. For the LMBH system added with 5 wt% 2D TiNb 2 O 7 , 9.8 wt% H 2 can be released within 20 min at 400 °C, after which the system can be fully hydrogenated in less than 5 min at 350 °C and 10 MPa H 2 . Moreover, a dehydrogenation capacity of 9.4 wt% can be maintained after 50 cycles corresponding to a retention of 96%, being the highest reported to date. The positive roles of TiB 2 and NbB 2 for kinetics and recyclability are from their catalytic nucleation effects for MgB 2 , a main dehydrogenation phase of LMBH, thus reducing the apparent activation energy, suppressing the formation of thermostable Li 2 B 12 H 12 byproducts, and inhibiting the hydride coarsening. This work develops an advanced LMBH system, bringing hope for high-capacity, fast-response, and long-life hydrogen energy storage.

Electrocatalytic water splitting is a crucial strategy for advancing hydrogen energy and addressing the global energy crisis. Despite its significance, the need for a straightforward and swift method to synthesize electrocatalysts with exceptional performance remains pressing. In this study, we demonstrate a novel approach for the preparation of multimetal-based electrocatalysts in a continuous flow reactor, enabling the quick synthesis of a large number of products through a streamlined process. The resultant NiFe-LDH comprises nanoflakes with a high specific surface area and requires only 255.4 mV overpotential to achieve a current density of 10 mA·cm -2 in 1 M KOH, surpassing samples fabricated by conventional hydrothermal methods. Our method can also be applied to craft a spectrum of other multimetal-based electrocatalysts, including CoFe-LDH, CoAl-LDH, NiMn-LDH, and NiCoFe-LDH. Additionally, the NiFe-LDH electrocatalyst is further applied to anodic methanol electrooxidation coupled with cathodic hydrogen evolution. Moreover, the simplicity and generality of our fabrication method render it applicable for the facile preparation of various multimetal-based electrocatalysts, offering a scalable solution to the quest for high-performance catalysts in advancing sustainable energy technologies.

Many reported proteasome inhibitors, including the three clinically approved inhibitors, bortezomib, carfilzomib, and ixazomib, have peptidic structures. In this study, using a hybrid and versatile strategy for covalent virtual screening by combining warhead screening and preprocessing with GOLD and CovDock software that were applied to the ZINC virtual library, we identified multiple proteasome inhibitors with new nonpeptidic structural scaffolds. Proteasome inhibition assays confirmed the inhibitory activities of these new compounds. These results demonstrate the effectiveness of our computational strategy for large-scale covalent virtual screening. Furthermore, these identified proteasome inhibitors may serve as starting points for the development of a new class of nonpeptidic therapeutic agents., Competing Interests: The authors declare no competing financial interest., (© 2024 American Chemical Society.)

This paper presents a quantitative risk assessment (QRA) study of an oil-gas-hydrogen-electricity integrated energy station in China. A comprehensive assessment of the station was made in terms of consequences and risks, respectively. Consequence analysis shows that the severity of hazardous chemical leakage accidents in the station is in the order of natural gas, hydrogen, gasoline, and diesel fuel, especially in the liquefied natural gas (LNG) and compressed natural gas (CNG) storage tank areas, which may cause major accidents in the event of leakage. The results of the risk assessment showed that the individual and societal risks of the integrated oil-gas-hydrogen-electricity energy station exceeded the risk acceptance criteria. Moreover, the catastrophic rupture of LNG and CNG storage tanks is the main cause of the unacceptable risk. Additional mitigation measures for them, mainly including the installation of emergency manual shut-off valves, the installation of combustible gas detection and alarm devices, and pressure relief protection devices, can effectively reduce the risk to an acceptable level., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

As a new type of wound dressing, hydrogels have attracted more and more attention. However, traditional hydrogel wound dressings lack inherent antibacterial properties and are difficult to match irregular wounds, which leads to an easy wound bacterial infection. To solve the problems associated with traditional hydrogels, in this research, a thermosensitive hydrogel (PFLD) for wound dressings was developed based on Poloxamer 407 (PF127), lysine (Lys), and 3,4-dihydroxyphenylacetic acid (DOPAC). Rheological tests indicated that the PFLD hydrogel possesses injectability, adaptability to deformation, and sufficient mechanical strength for wound dressing applications. In addition, it could in situ gel at 33 °C, which indicated that the hydrogel could undergo sol-to-gel transition under body temperature. Upon using it in wound treatment, it could adapt to irregular wounds to achieve full coverage of the wound and promote the rapid hemostasis of wound bleeding. Due to the presence of DOPAC in the hydrogel, it exhibited excellent antibacterial and antioxidant properties on the wounds. The skin defect model showed that the wound shrinkage was the fastest after PFLD hydrogel treatment. On day 14, the wound shrinkage rates were 81.68 and 99.77% for the control and PFLD hydrogel groups, respectively. Therefore, the PFLD hydrogel has a broad application prospect as a dressing for the treatment of irregular wounds.

Exosomes are increasingly being regarded as emerging and promising biomarkers for cancer screening, diagnosis, and therapy. The downstream molecular analyses of exosomes were greatly affected by the isolation efficiency from biosamples. Among the current exosome isolation strategies, affinity nanomaterials performed comparably better with selectivity and specificity. However, these techniques did not take the structure and size of exosomes into account, which may lead to a loss of isolation efficiency. In this article, a framework nucleic acid was employed to prepare a well-designed nanosized bead Fe 3 O 4 @pGMA@DNA TET@Ti 4+ for enrichment of exosomes. The abundant phosphate groups in the framework nucleic acid provide binding sites to immobilize Ti 4+ , and its rigid three-dimensional skeleton makes them act as roadblocks to barricade exosomes and provide affinity interactions on a three-dimensional scale, resulting in the improvement of isolation efficiency. The model exosomes can be effectively isolated with 92% recovery in 5 min. From 100 μL of HeLa cell culture supernatant, 34 proteins out of the top 100 commonly identified exosomal proteins were identified from the isolated exosomes by the novel beads, which is obviously more than that by TiO 2 (19 proteins), indicating higher isolation efficiency and exosome purity by Fe 3 O 4 @pGMA@DNA TET@Ti 4+ beads. The nanobeads were finally applied for comparing exosomal proteomics analysis from real clinical serum samples. Twenty-five upregulated and 10 downregulated proteins were identified in the lung cancer patients group compared to the health donors group, indicating that the novel nanobeads have great potential in isolation of exosomes for exosomal proteomics analysis in cancer screening and diagnosis.

Fiber-shaped electrochemical capacitors (FSECs) have garnered substantial attention to emerging portable, flexible, and wearable electronic devices. However, achieving high electronic and ionic conductivity in fiber electrodes while maintaining a large specific surface area is still a challenge for enhancing the capacitance and rapid response of FSECs. Here, we present an electric-field-assisted cold-wall plasma-enhanced chemical vapor (EFCW-PECVD) method for direct growth of vertical graphene (VG) on fiber electrodes, which is incorporated in the FSECs. The customized reactor mainly consists of two radio frequency coils: one for plasma generation and the other for substrate heating. Precise temperature control can be achieved by adjusting the conductive plates and the applied power. With induction heating, only the substrate is heated to above 500 °C within just 5 min, maintaining a low temperature in the gas phase for the growth of VG with a high quality. Using this method, VG was easily grown on metallic fibers. The VG-coated titanium fibers for FSECs exhibit an ultrahigh rate performance and quick ion transport, enabling the conversion of an alternating current signal to a direct current signal and demonstrating outstanding filtering capabilities.

Flexible pressure sensors have attracted great interest due to their bendable, stretchable, and lightweight characteristics compared to rigid pressure sensors. However, the contradictions among sensitivity, detection limit, thickness, and detection range restrict the performance of flexible pressure sensors and the scope of their applications, especially for scenarios requiring conformal fitting, such as rough surfaces such as the human skin. This paper proposes a novel flexible pressure sensor by combining the nanoengineering strategy and nanocomposite structures. The nanoengineering strategy utilizes the bending deformation of nanofilm instead of the compression of the active layer to achieve super high sensitivity and low detection limit; meanwhile, the nanocomposite structures introduce distributed microbumps that delay the adhesion of nanofilm to enlarge the detection range. As a result, this device not only ensures an ultrathin thickness of 1.6 μm and a high sensitivity of 84.29 kPa -1 but also offers a large detection range of 20 kPa and an ultralow detection limit of 0.07 Pa. Owing to the ultrathin thickness as well as high performance, this device promotes applications in detecting fingertip pressure, flexible mechanical gripping, and so on, and demonstrates significant potential in wearable electronics, human-machine interaction, health monitoring, and tactile perception. This device offers a strategy to resolve the conflicts among thickness, sensitivity, detection limit, and detection range; therefore, it will advance the development of flexible pressure sensors and contribute to the community and other related research fields.

HPK1, a well-known negative regulator of T cell receptors, can cause T cell dysfunction when abnormally activated. In this study, a PROTAC C3 was designed and synthesized by optimizing the physicochemical properties of the warhead, linker, and CRBN ligand. C3 demonstrated significant HPK1 degradation with a DC 50 of 21.26 nM, excellent oral absorption with a C max of 10,899.92 ng/mL, and a bioavailability ( F %) of 81.7%. C3 also showed degradation selectivity and potent immune activation effects. Proteomic and WB analyses revealed that immune-activating effect of C3 is attributed to the inhibition of SLP76 and NF-κB signaling pathways, as well as the enhancement of MAPK signaling pathway transduction. In vivo efficacy study demonstrated that oral administration of C3 in combination with anti-PDL1 antibody significantly inhibited tumor growth (tumor growth inhibition = 65.58%). These findings suggest that C3 , a novel HPK1 PROTAC, holds promise as a therapeutic agent for tumor immunotherapy.

Defective carbon nitride (DCN- x ) was synthesized through a dual-surface engineering process consisting of nitric acid treatment followed by high-temperature calcination. This process endowed DCN- x with a porous structure and a larger surface area than that of pure graphite carbon nitride (CN), enhancing its visible light absorption and reducing the electron-hole recombination rate. Consequently, DCN- x demonstrated a significantly more efficient photocatalytic hydrogen evolution, with the optimum sample, DCN-600, achieving an activity 55.9 times greater than that of pure CN, while maintaining excellent photocatalytic stability. Furthermore, the presence of tri-s-triazine (heptazine) structures within the CN's in-plane structure was identified as a critical factor for band gap optimization, suggesting new avenues for the synthesis of carbon nitride variants with enhanced photocatalytic performance.

The coefficients of piezoelectricity and thermal expansion are generally positive due to the bond anharmonicity. For converse piezoelectricity, the electrostrain obtained in prevalent ceramics is only around 1%. Here we propose that the coordination transition of metal cations may make a paradigm shift. Through first-principles calculations, we predict a series of low-energy phases with distinct coordinations for Ag ions in superionic conductor AgCrX 2 (X = S, Se), including ferroelectric and nonpolar phases with distinct interlayer distances. The mobile feature of Ag ions, which can be attributed to its complex coordination chemistry, can facilitate transformation between various coordination phases. Such facile transitions with ultralow barriers can be driven by applying either pressure, an electric field, or a change in temperature, giving rise to various exotic effects, including electrostrain, negative piezoelectricity, and negative thermal expansion. All with unprecedented giant constants, those mechanisms stem from the coordination transitions, distinct from the weak linear effects in previous reports.

Respiratory pathogens pose significant challenges to public health, demanding efficient diagnostic methods. This study presents an integrated microfluidic chip for the simultaneous detection of multiple respiratory pathogens. The chip integrates magnetic bead-based nucleic acid extraction and purification, acoustic streaming-driven mixing, liquid equalization, and multiplex PCR amplification with in situ fluorescence detection. Nucleic acid extraction takes only 12 min, yielding results comparable to commercial kits. Efficient mixing of magnetic beads is achieved through a combination of designed micropillars and bubble-trapping array structures. The micropillars maintain the aqueous phase in the mixing chamber, while the bubble-trapping arrays enable stable formation of bubbles, serving as a micromixer under the acoustic field. To prevent cross-contamination, an oil-encapsulated water droplet system is incorporated throughout nucleic acid extraction and PCR amplification. This assay displays remarkable multiplex analysis capability on a single chip, enabling the simultaneous detection of 12 common respiratory pathogens with a low detection limit of 10 copies/μL. Moreover, this method demonstrates excellent practical applicability in clinical nasal samples. Compared to many microfluidic chip-based molecular biology methods, the assay exhibits comparable or superior multipathogen analysis capability, sensitivity, and speed, completing the sample-to-answer process in approximately 70 min. This integrated microfluidic device offers a promising multiplex molecular diagnosis platform for on-site simultaneous detection of multiple pathogens.

A battery is composed of two electrodes that depend on and interact with each other. However, galvanostatic charging-discharging measurement, the most widely used method for battery evaluation, cannot simultaneously reflect performance metrics [capacity, Coulombic efficiency (CE), and cycling stability] of both electrodes because the result is generally governed by the lower-capacity electrode of the cell, namely the limiting reagent of the battery reaction. In studying stoichiometric Li-S cells operating under application-relevant high-mass-loading and lean-electrolyte conditions, we take advantage of the two-stage discharging behavior of sulfur to construct a simple framework that allows us to analyze both electrodes simultaneously. The cell capacity and its decay are anode performance descriptors, whereas the first plateau capacity and cell CE are cathode performance descriptors. Our analysis within this frame identifies Li stripping/plating and polysulfide shuttling to be the limiting factors for the cycling performance of the stoichiometric Li-S cell. Using our newly developed framework, we examine various previously reported strategies to mitigate these bottleneck problems and find modifying the separator with a reduced graphene oxide layer to be an effective means, which improves the capacity retention rate of the cell to 99.7% per cycle.

The heterogeneity of hepatocellular carcinoma (HCC) can prevent effective treatment, emphasizing the need for more effective therapies. Herein, we employed arsenene nanosheets coated with manganese dioxide and polyethylene glycol (AMPNs) for the degradation of Pin1, which is universally overexpressed in HCC. By employing an "AND gate", AMPNs exhibited responsiveness toward excessive glutathione and hydrogen peroxide within the tumor microenvironment, thereby selectively releasing As x O y to mitigate potential side effects of As 2 O 3 . Notably, AMPNs induced the suppressing Pin1 expression while simultaneously upregulation PD-L1, thereby eliciting a robust antitumor immune response and enhancing the efficacy of anti-PD-1/anti-PD-L1 therapy. The combination of AMPNs and anti-PD-1 synergistically enhanced tumor suppression and effectively induced long-lasting immune memory. This approach did not reveal As 2 O 3 -associated toxicity, indicating that arsenene-based nanotherapeutic could be employed to amplify the response rate of anti-PD-1/anti-PD-L1 therapy to improve the clinical outcomes of HCC patients and potentially other solid tumors (e.g., breast cancer) that are refractory to anti-PD-1/anti-PD-L1 therapy.

The printing and dyeing industry is currently accelerating toward a direction of high efficiency, energy conservation, environmental protection, and integration with digitalization. Disperse dye wash-free digital inkjet dyeing is a revolutionary breakthrough for cleaning and coloring polyester fabric. Based on the solubility parameters and the hot-melt dyeing characteristics of disperse dyes, soft, hard, and functional monomers of acrylate were used as the main body. Moreover, single-vinyl fluorinated polysiloxane and divinyl polysiloxane with low solubility parameters were used as modified monomers. A modified polyacrylate (PFSMA) adhesive containing silicon in the main chain and fluorine silicon in the side chain was prepared via miniemulsion polymerization. Using disperse digital inkjet dyeing of polyester fabric without washing can realize energy saving, emission reduction, and carbon reduction. Results showed that the optimum preparation conditions of PFSMA were as follows: DVFS molecular weight of 957 g/mol and DVFS content of 2.5 wt %. Compared with that of polyacrylate (PA), the glass-transition temperature of PFSMA film decreased, and its water resistance, toughness, and adhesion enhanced. When the PFSMA content in the wash-free disperse red ink was 8 wt %, the color yields of the front and back of the PFSMA jet-dyed polyester fabric were 18.86 and 13.28, respectively. Moreover, the color yield of the front of PFSMA jet-dyed polyester fabric was 39.9% higher than that of the pure liquid disperse red jet-dyed fabric. The simulated fixation rate was 87.9%, approximately 2.9 times higher than that of the PA wash-free jet-dyed fabric. The color fastness to dry rubbing reached level 4 and the color fastness to wet rubbing reached level 3-4, which was one level higher than that of pure liquid disperse red jet-dyed fabrics. The color fastness to soaping reached grade 5 and the color fastness to heat compression reached grades 4-5 and above. The fabric was a little firmer but smoother. The color properties, color fastness, and hand feeling of the PFSMA wash-free jet-dyed polyester fabric exceeded the levels of commercially available adhesives.

Spodoptera frugiperda is a significant global pest, and chlorantraniliprole (CAP) is extensively used in China for its control. Understanding CAP resistance in S. frugiperda is crucial for effective management of this pest. Field populations exhibited varying degrees of resistance to CAP (RR = 1.74-5.60-fold). After 10 generations of selection, the CAP-resistant strain developed over 10-fold resistance, with a realized heritability ( h 2 ) of 0.10. Genetic analysis reveals inheritance patterns as autosomal, incomplete recessive, and monofactorial. The CAP-resistant strain showed limited cross-resistance to lufenuron and tetrachlorantraniliprole, negative cross-resistance to spinetoram, and no observed cross-resistance to other insecticides. Biochemical analysis suggested that P450-mediated detoxification is the primary resistance mechanism, with 26 genes overexpressed in the CAP-resistant strain. Additionally, the knockdown of CYP4L13 , CYP6B39 , CYP6B40 , and CYP4G74 significantly increased the sensitivity of the resistant larvae to CAP. These findings highlight the resistance risk of CAP in S. frugiperda and emphasize the crucial role of P450 enzymes in resistance.

Intraperitoneal co-delivery of chemotherapeutic drugs (CDs) and immune checkpoint inhibitors (ICIs) brings hope to improve treatment outcomes in patients with peritoneal metastasis from ovarian cancer (OC). However, current intraperitoneal drug delivery systems face issues such as rapid drug clearance from lymphatic drainage, heterogeneous drug distribution, and uncontrolled release of therapeutic agents into the peritoneal cavity. Herein, we developed an injectable nanohydrogel by combining carboxymethyl chitosan (CMCS) with bioadhesive nanoparticles (BNPs) based on polylactic acid-hyperbranched polyglycerol. This system enables the codelivery of CD and ICI into the intraperitoneal space to extend drug retention. The nanohydrogel is formed by cross-linking of aldehyde groups on BNPs with amine groups on CMCS via reversible Schiff base bonds, with CD and ICI loaded separately into BNPs and CMCS network. BNP/CMCS nanohydrogel maintained the activity of the biomolecules and released drugs in a sustained manner over a 7 day period. The adhesive property, through the formation of Schiff bases with peritoneal tissues, confers BNPs with an extended residence time in the peritoneal cavity after being released from the nanohydrogel. In a mouse model, BNP/CMCS nanohydrogel loaded with paclitaxel (PTX) and anti-PD-1 antibodies (αPD-1) significantly suppressed peritoneal metastasis of OC compared to all other tested groups. In addition, no systemic toxicity of nanohydrogel-loaded PTX and αPD-1 was observed during the treatment, which supports potential translational applications of this delivery system.

Activatable probes with a higher signal-to-background ratio and accuracy are essential for monitoring liver cancer as well as intraoperative fluorescence navigation. However, the presence of only one biomarker is usually not sufficient to meet the high requirement of a signal-to-background ratio in cancer surveillance, leading to the risk of misdiagnosis. In this work, a dual-locked activation response probe, Si-NTR-LAP , for nitroreductase and leucine aminopeptidase was reported. This dual-locked probe provides better tumor recognition and a higher signal-to-noise ratio than that of single-locked probes ( Si-LAP and Si-NTR ). In both the subcutaneous tumor model and the more complex orthotopic hepatocellular carcinoma model, the probe was able to identify tumor tissue with high specificity and accurately differentiate the boundaries between tumor tissue and normal tissue. Therefore, the dual-locked probe may provide a new and practical strategy for applying to real patient tumor tissue samples.

The phenomenon of methane oxidation linked to perchlorate reduction has been reported in multiple studies; yet, the underlying microbial mechanisms remain unclear. Here, we enriched suspended cultures by performing methane-driven perchlorate reduction under oxygen-limiting conditions in a membrane bioreactor (MBR). Batch test results proved that perchlorate reduction was coupled to methane oxidation, in which acetate was predicted as the potential intermediate and oxygen played an essential role in activating methane. By combining DNA-based stable isotope probing incubation and high-throughput sequencing analyses of 16S rRNA gene and functional genes ( pmoA , pcrA , and narG ), we found that synergistic interactions between aerobic methanotrophs ( Methylococcus and Methylocystis ) and perchlorate-reducing bacteria (PRB; Denitratisoma and Dechloromonas ) played active roles in mediating methane-driven perchlorate reduction. This partnership was further demonstrated by coculture experiments in which the aerobic methanotroph could produce acetate to support PRB to complete perchlorate reduction. Our findings advance the understanding of the methane-driven perchlorate reduction process and have implications for similar microbial consortia linking methane and chlorine biogeochemical cycles in natural environments.

Photodynamic therapy (PDT) emerges as a promising strategy for combating bacteria with minimal drug resistance. However, a significant hurdle lies in the ineffectiveness of most photosensitizers against Gram-negative bacteria, primarily attributable to their characteristic impermeable outer membrane (OM) barrier. To tackle this obstacle, we herein report an amphipathic peptide-photosensitizer conjugate (PPC) with intrinsic outer membrane disruption capability to enhance PDT efficiency against Gram-negative bacteria. PPC is constructed by conjugating a hydrophilic ultrashort cationic peptide to a hydrophobic photosensitizer. PPC could efficiently bind to the OM of Gram-negative bacteria through electrostatic adsorption, and subsequently disrupt the structural integrity of the OM. Mechanistic investigations revealed that PPC triggers membrane disruption by binding to both lipopolysaccharide (LPS) and phospholipid leaflet in the OM, enabling effective penetration of PPC into the Gram-negative bacteria interior. Upon light irradiation, PPC inside bacteria generates singlet oxygen not only to effectively decrease the survival of Gram-negative bacteria P. aeruginosa and E. coli to nearly zero in vitro, but also successfully cure the full-thickness skin infection and bacterial keratitis (BK) induced by P. aeruginosa in animal models. Thus, this study provides a broad-spectrum antibacterial phototherapeutic design strategy by the synergistic action of membrane disruption and PDT to combat Gram-negative bacteria.

Accurate coordination of chromosome replication and cell division is essential for cellular processes, yet the regulatory mechanisms governing the bacterial cell cycle remain contentious. The lack of quantitative data connecting key cell cycle players at the single-cell level across large samples hinders consensus. Employing high-throughput flow cytometry, we quantitatively correlated the expression levels of key cell cycle proteins (FtsZ, MreB, and DnaA) with DNA content in individual bacteria. Our findings reveal distinct correlations depending on the chromosome number (CN), specifically whether CN ≤2 or ≥4, unveiling a mixed regulatory scenario in populations where CN of 2 or 4 coexist. We observed function-dependent regulations for these key proteins across nonoverlapping division cycles and various nutrient conditions. Notably, a logarithmic relationship between total protein content and replication origin number across nutrient conditions suggests a unified mechanism governing cell cycle progression, confirming the applicability of Schaechter's growth law to cells with CN ≥4. For the first time, we established a proportional relationship between the synthesis rates of key cell cycle proteins and chromosome dynamics in cells with CN ≥4. Drug experiments highlighted CN 2 and 4 as pivotal turning points influencing cellular resource allocation. This high-throughput, single-cell analysis provides interconnected quantitative insights into key molecular events, facilitating a predictive understanding of the relationship between cell growth and cell cycle.