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Chromatin structure under normal circumstances can be studied with the atomic force microscope (AFM). Chromatin fibers were recreated using histone octamers and an alternatively repeated 208-bp nucleosome positioning DNAa series (208-18) to reveal single nucleosome cores and linker DNA. Constant compaction of the 3780-bp DNA due to varying loadings of histone octamers was revealed by AFM measurements. The formation of the 11-nm nucleosome core was done by wrapping 146-bp of DNA around the histone octamer. Enmeshed beaded fibers are seen in AFM images of recreated chromatin, which use circular DNA.

Bubble drainage (BD) occurs in various natural phenomena and industrial activities, in which bubbles rise toward the water surface and create a progressively thinned two-sided liquid film, called a lamella. Surfactant, as an important regulator in the BD process, not only assembles on both sides of the lamellae, generating a configuration of lamellae sandwiched by monolayers of surfactants (lamellae/MS), but also induces interfacial deformation by lowering interfacial tension. Herein, we developed a strategy of BD assisted interfacial polymerization for the fabrication of polyamide (PA) membranes. The regulated interfacial deformation at the water-oil interface produced a membrane with crater-like structures, which greatly increased the surface area of the PA membrane. Moreover, the lamellae/MS configuration served as a reservoir to spontaneously enrich amine monomers and thus modulate the diffusion-reaction kinetics. The resulting PA membranes exhibited superior separation performance with a water permeance of 44.7 L m -2 h -1 bar -1 and a Na 2 SO 4 rejection of 99.2%.

Laccase, a multipurpose biocatalyst, is widely distributed across all kingdoms of life and plays a key role in essential biological processes such as lignin synthesis, degradation, and pigment formation. These functions are critical for fungal growth, plant-pathogen interactions, and maintenance of soil health. Due to its broad substrate specificity, multifunctional nature, and environmentally friendly characteristics, laccase is widely employed as a catalyst in various green chemistry initiatives. With its ability to oxidize a diverse range of phenolic and nonphenolic compounds, laccase has also been found to be useful as a food additive and for assessing food quality parameters. Ongoing advancements in research and technology are continually expanding the recognition of laccase's potential to address global environmental, health, and energy challenges. This review aims to provide critical insights into the applications of laccases in the biotechnology and food industry.

The dehydrofluorination effect of poly(vinylidene fluoride) (PVDF) induced by ceramic fillers with an alkaline surface compromises the comprehensive properties of the solid composite electrolyte (SCE) and leads to the deficient performance of the solid-state lithium metal batteries (SLMBs). In this work, a unique PVDF-based double-layer solid electrolyte was fabricated, which consisted of a Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO)-filled SCE with poly(acrylic acid) (PAA) as an alkalinity-scavenging agent in contact with the Li anode, and another SCE with lithium difluoro(oxalato)borate (LiDFOB) as a film-formation additive facing the cathode. It is found that a moderate amount of PAA relieves the dehydrofluorination degree of the PVDF matrix and improves the Li plating/stripping reversibility, and the addition of LiDFOB is involved in the formation of a stable passivation film on the cathode. Consequently, the resultant double-layer SCE holds favorable overall properties, especially being well-compatible with both electrodes, endowing the SLMBs with superior cycle and rate performance at room temperature.

High-performance Co-based catalysts were derived by pyrolysis using synthesized MOFs as self-sacrificial templates. Various catalytic systems were constructed by peroxymonosulfate (PMS) to degrade tetracycline hydrochloride (TC). Adsorption-degradation efficiencies, cycle performance, dynamics, and the adsorption catalytic mechanism of various catalytic systems for TC were studied. The effects of different synthetic solvents, pyrolysis temperatures, and single/bimetallic element compositions on degradation efficiency were innovatively compared. The optimal catalyst and PMS dosage for the experiment were determined to be 10 mg and 0.1 mL, respectively. The results indicated that all catalytic systems could efficiently degrade TC and have a high acid-base resistance. The catalyst activity was significantly influenced by the pyrolysis temperature. The optimum pyrolysis temperatures for Zn@Co-N-C- T , CH 3 OH@Co-N-C- T , and H 2 O@Co-N-C- T were 1000, 900 and 900 °C, respectively. More abundant pore structures and active sites were generated in Zn@Co-N-C-1000, exhibiting an excellent TC degradation efficiency and adsorption capacity, achieving 94.73% and 167.564 mg/g, respectively. Meanwhile, the total organic carbon (TOC) of TC (50 mL, 50 mg/L) achieved a removal rate (TOC/TOC 0 ) of 50.28%. Zn@Co-N-C-1000/PMS maintained over 83.27% TC degradation after five cycles. The adsorption mechanism of the catalyst for TC was investigated through the analysis of adsorption kinetics and isotherm models. The quenching test and EPR results indicated that TC was primarily degraded through the nonradical pathway. The efficient degradation of TC is attributed to the rapid electron transfer processes occurring at the two-phase interface and the redox cycling of Co 0 /Co 2+ /Co 3+ . Finally, LC-MS was used to analyze the intermediate products of TC degradation in the Zn@Co-N-C-1000/PMS system, and two degradation pathways were proposed.

Microbial oxidizers of trace gases such as hydrogen (H 2 ) and carbon monoxide (CO) are widely distributed in soil microbial communities and play a vital role in modulating biogeochemical cycles. However, the contribution of trace gas oxidizers to soil carbon fixation and the driving environmental factors remain unclear, especially on large scales. Here, we utilized biogeochemical and genome-resolved metagenomic profiling, assisted by machine learning analysis, to estimate the contributions of trace gas oxidizers to soil carbon fixation and to predict the key environmental factors driving this process in soils from five distinct ecosystems. The results showed that phylogenetically and physiologically diverse H 2 and CO oxidizers and chemosynthetic carbon-fixing microbes are present in the soil in different terrestrial ecosystems. The large-scale variations in soil carbon fixation were highly positively correlated with both the abundance and the activity of H 2 and CO oxidizers ( p < 0.05-0.001). Furthermore, soil pH and moisture-induced shifts in the abundance of H 2 and CO oxidizers partially explained the variation in soil carbon fixation (55%). The contributions of trace gas oxidizers to soil carbon fixation in the different terrestrial ecosystems were estimated to range from 1.1% to 35.0%. The estimated rate of trace gas carbon fixation varied from 0.04 to 1.56 mg kg -1 d -1 . These findings reveal that atmospheric trace gas oxidizers may contribute to soil carbon fixation driven by key soil environmental factors, highlighting the non-negligible contribution of these microbes to terrestrial carbon cycling.

The "shuttle effect" and several issues related to it are seen as "obstacles" to the study and development of lithium-sulfur batteries (LSBs). This work aims at finding how to fully expose bimetallic sites and quicken the battery reaction kinetics. Here, a bimetallic NiCo-MOF and its derivative NiCo@C with a hollow sea urchin structure are produced. The obtained NiCo@C possesses a micromesoporous structure and fully disclosed bimetallic active sites because of its distinctive structure. The experimental findings demonstrate that fully exposed bimetallic active sites take on chemical adsorbents and collaborate with micromesopores as physical constraints to effectively suppress the "shuttle effect". Furthermore, the hollow sea urchin structure of NiCo@C enables a highly conductive grid, which provides channels to facilitate the movement of solvated Li + . Thanks to these advantages, the NiCo@C-based sulfur cathode offers a high initial discharge specific capacity of 924.41 mAh g -1 at 0.1 C and sustains 390.35 mAh g -1 discharge specific capacity after 100 cycles. The quick transfer of solvated lithium ions ( D Li+ = 1.81 × 10 -8 cm 2 s -1 ) enables the battery to still contribute a discharge specific capacity of 367.54 mAh g -1 at 1 C. This work provides a new understanding for the structural design of positive electrodes in LSBs.

How to fundamentally suppress charge transport is one of the essential issues in polymer dielectrics. This work reports significant charge transport suppression by glycidyl methacrylate (GMA) side group modification on polypropylene (PP). Experimental and computational investigations discover for the first time a quasi-hydrogen bond effect generated by carbonyl and epoxide of GMA in PP inter/intramolecular structure, while introducing trap energy levels within the HOMO-LUMO gap. These energy levels suppress the leakage current of GMA-modified PP thanks to the charge-trapping effect. The quasi-hydrogen bond originating from the interaction between the high-polar GMA group and flexible PP chain raises the thermostability while averaging the electron distribution between hydrogen and acceptor oxygen, which is conducive to lessening electric weak points, suppressing charge transport, and finally enhancing the electrical breakdown strength. This work provides new thinking on polymer dielectric design and charge transport regulation utilizing electron structure and weak interaction at the molecular scale.

Molecular property prediction (MPP) techniques are pivotal in reducing drug development costs by preemptively predicting bioactivity and ADMET properties. Despite the application of numerous deep learning approaches, enhancing the representational capacity of these models remains a significant challenge. This paper presents a novel knowledge-based Transformer framework, KnoMol, designed to improve the understanding of molecular structures. KnoMol integrates expert chemical knowledge into the Transformer, emulating the analytical methods of medicinal chemists. Additionally, the multiperspective attention mechanism provides a more precise way to represent ring systems. In the evaluation experiments, KnoMol achieved state-of-the-art performance on both MoleculeNet and small-scale data sets, surpassing existing models in terms of accuracy and generalization. Further research indicated that the incorporation of knowledge significantly reduces KnoMol's reliance on data volumes, offering a solution to the challenge of data scarcity. Moreover, KnoMol identified several new inhibitors of HER2 in a case study, demonstrating its value in real-world applications. Overall, this research not only provides a powerful tool for MPP but also serves as a successful precedent for embedding knowledge into Transformers, with positive implications for computer-aided drug discovery and the development of MPP algorithms.

Poly(ADP-ribose) polymerase 1 (PARP1) inhibitors have revolutionized the treatment of many cancers with DNA-repairing deficiencies via synthetic lethality. Advocated by the polypharmacology concept, recent evidence discovered that a significantly synergistic effect in increasing the death of cancer cells was observed by simultaneously perturbating the enzymatic activities of bromodomain-containing protein 4 (BRD4) and PARP1. Here, we developed a novel cheminformatics approach combined with a structure-based method aiming to facilitate the design of dual PARP1-BRD4 inhibitors. Instead of linking pharmacophores, the developed approach first identified merged pharmacophores (a pool of amide-containing ring systems), from which phenanthridin-6(5 H )-one was further prioritized. Based on this starting point, several small molecules were rationally designed, among which HF4 exhibited low micromolar inhibitory activity against BRD4 and PARP1, particularly exhibiting strong inhibition of BRD4 BD1 with an IC 50 value of 204 nM. Furthermore, it demonstrated potent antiproliferative effects against breast cancer gene-deficient and proficient breast cancer cell lines by arresting cell cycle progression and impeding DNA damage repair. Collectively, our systematic efforts to design lead-like molecules have the potential to open doors for the exploration of dual PARP1-BRD4 inhibitors as a promising avenue for breast cancer treatment. Furthermore, the developed approach can be extended to systematically design inhibitors targeting PARP1 and other related targets.

The development of intelligent reversible reconfigurable metamaterials has great significance in constructing three-dimensional metamaterials and introducing reversible tunability into metamaterials. Here, we introduce an intelligent metamaterial consisting of a two-way shape memory polymer (2W-SMP) ethylene vinyl acetate copolymer (EVA) actuator substrate and a patterned flexible-rigid film. Mechanical buckling of the 2W-SMP substrate was controlled by thermal stimulation. This makes it possible to afford an ability to initiate 3D structure formation or shape reconfiguration remotely in an on-demand fashion. In addition, the shape of the 2W-SMP substrate is temperature-dependent, allowing repeatable reversible deformation through temperature control after a single programming. Therefore, the electromagnetic properties of metamaterials can also be repeatedly and reversibly tuned between 9.15 and 10.82 GHz. Experimental demonstrations include the deformation and tunable electromagnetic properties of intelligent reversible reconfigurable metamaterial cells. The results create many opportunities for advanced programmable three-dimensional metamaterials.

The integration of solar steam generation and the hydrovoltaic effect is a promising strategy for simultaneously solving water scarcity and energy crises. However, it is still a challenge to attain a high water evaporation rate and a strong output of electricity in a single device. Here, we report a three-dimensional (3D) hierarchical Cu 2- x O@Cu foam for solar-driven harvesting of freshwater and electricity efficiently. The 3D Cu 2- x O@Cu foam synthesized by chemical etching shows a rough surface and porous structure, making it have a hydrophilic surface, high light absorption performance, and excellent photothermal effect. For deionized water, the evaporation rate is as high as 3.03 kg m -2 h -1 ; meanwhile, the output voltage is 0.37 V under 1 solar irradiation. For real seawater, the evaporation rate decreases to about 2.48 kg m -2 h -1 , the output voltage increases to 0.41 V, and the maximum output power density is 9.47 μW cm -2 . Both the water evaporation and power generation performance are very competitive. Outdoor experiments demonstrate that the 3D hierarchical Cu 2- x O@Cu foam can desalinate seawater, while generating electricity continuously.

Neuroblastoma (NB) is a rare and malignant pediatric solid tumor. Due to its heterogeneity, it poses significant challenges for treatment, resulting in a high mortality rate. This study aimed to identify new therapeutic drugs by modeling the TrkB receptor from PDB 4AT5 and conducting virtual screening of compounds from the YaTCM database (containing 47,696 compounds derived from 6220 Traditional Chinese Medicines). The screening utilized the E-pharmacophore approach to select compounds with potential binding affinity to TrkB. The binding abilities of these compounds were tested through molecular dynamics simulations, stretch dynamics simulations, and US simulations. Among the top 11 optimized hit compounds, DHPA and 3″-demethylhexahydrocurcumin are prominent. Further simulations reveal that they form stable receptor-ligand binary complexes with TrkB. In subsequent in vitro cell experiments, 3″-demethylhexahydrocurcumin is eliminated due to its high IC 50 for killing NB cells. Low concentrations of DHPA can significantly kill NB cells. Additionally, DHPA can inhibit the expression of TrkB, the activation of TrkB's downstream signaling pathways, and affect the thermal stability of TrkB protein and its response to streptase protease degradation. DHPA may be a potential TrkB inhibitor., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

We report a novel cobalt-catalyzed intramolecular 1,4-hydrofunctionalization of dienes. The reaction proceeds under mild conditions and is amenable to N- and O-nucleophiles. The protocol exhibits exclusive regioselectivity, yielding a number of different alkenyl heterocycles, including but not limited to dihydroisobenzofurans, isochromanes, tetrahydrofurans, morpholines, lactones, and isoindolines. Experimental studies were performed to offer some insight into the different mechanistic pathways and to rationalize the regio- and stereoselectivities of the reaction.

Quantitative estimates of reaction barriers and solvent effects are essential for developing kinetic mechanisms and predicting reaction outcomes. Here, we create a new data set of 5,600 unique elementary radical reactions calculated using the M06-2X/def2-QZVP//B3LYP-D3(BJ)/def2-TZVP level of theory. A conformer search is done for each species using TPSS/def2-TZVP. Gibbs free energies of activation and of reaction for these radical reactions in 40 common solvents are obtained using COSMO-RS for solvation effects. These balanced reactions involve the elements H, C, N, O, and S, contain up to 19 heavy atoms, and have atom-mapped SMILES. All transition states are verified by an intrinsic reaction coordinate calculation. We next train a deep graph network to directly estimate the Gibbs free energy of activation and of reaction in both gas and solution phases using only the atom-mapped SMILES of the reactant and product and the SMILES of the solvent. This simple input representation avoids computationally expensive optimizations for the reactant, transition state, and product structures during inference, making our model well-suited for high-throughput predictive chemistry and quickly providing information for (retro-)synthesis planning tools. To properly measure model performance, we report results on both interpolative and extrapolative data splits and also compare to several baseline models. During training and testing, the data set is augmented by including the reverse direction of each reaction and variants with different resonance structures. After data augmentation, we have around 2 million entries to train the model, which achieves a testing set mean absolute error of 1.16 kcal mol -1 for the Gibbs free energy of activation in solution. We anticipate this model will accelerate predictions for high-throughput screening to quickly identify relevant reactions in solution, and our data set will serve as a benchmark for future studies.

Maize chlorotic mottle virus (MCMV) is one of the main viruses causing significant losses in maize. N 6 -methyladenosine (m 6 A) RNA modification has been proven to play important regulatory roles in plant development and stress response. In this study, we found that MCMV infection significantly up-regulated the m 6 A level in maize, and methylated RNA immunoprecipitation sequencing (MeRIP-seq) and RNA sequencing (RNA-seq) were performed to investigate the distribution of m 6 A modified peaks and gene expression patterns in MCMV-infected maize plants. The results showed that 1325 differentially methylated genes (DMGs) and 47 differentially methylated and expressed genes (DMEGs) were identified and analyzed. Moreover, the results of virus-induced gene silencing (VIGS) assays showed that ZmECT18 and ZmGST31 were required for MCMV infection, while silencing of ZmMTC , ZmSCI1 or ZmTIP1 significantly promoted MCMV infection in maize. Our findings provided novel insights into the regulatory roles of m 6 A modification in maize response to MCMV infection.

Artificial ionic sensory systems, bridging the divide between biological systems and electronics, mimic human skin functions but face critical challenges with biocompatibility, comfort, signal stability, and simplifying packaging. Here, we present a simple and permeable skin-interfaced iontronic mechanosensing (SIIM) architecture that integrates human skin as natural ionic material and hierarchically porous MXene-fiber composite membranes as sensing electrodes. The SIIM system eliminates complex ionic material design and multilayer matrix, exhibiting ultrahigh pressure sensitivities (5.4 kPa -1 , <75 Pa), a low detection limit (6 Pa), excellent output stability along with high permeability to minimize the impact of sweating on sensing. The noncytotoxic nature of SIIM electrodes ensures excellent biocompatibility (>97% cell coincubational viability), facilitating long-term wearability and high biosafety. Furthermore, the scalable SIIM configuration integrated with matrix smart gloves, effectively monitors human physical movements. This SIIM-based sensor with marked sensing capabilities, structural simplicity, and scalability, holds promising potential in diverse wearable applications.

Fog collection is a promising solution for mitigating the urgent water shortage around the world. Despite the delicate design of various bionic fog harvesting surfaces with prowess to enable fast fog capture and programmed water transport, achieving sustainable and efficient fog collection by regulating the macroscale surface refreshment efficacy remains rarely concerned yet is effective. Here, we proposed a bioinspired structural design to achieve significant improvement on the surface refreshment efficacy to 46.47%, nearly 5 times larger than that of conventional design. Specifically, we constructed superhydrophilic vein-like microchannels on a superhydrophobic brass surface by using laser texture technology and hydrothermal treatment. Our microchannel design acts as a "highway" for synergically transporting and converging the collected fog droplets, as well as rapidly refreshing large surface area for the subsequent fog collection, reminiscent of the leaf veins responsible for the persistent mass transport between plant tissues. The practical implementation also convinced our design of a maximum water collection efficiency of up to 506.67 mg cm -2 h -1 and a long-term performance stability within a 10 h test. Our design is generic to most of the fog harvesting materials, showing great application potential for efficient atmospheric fog collection.

Owing to its multiple fascinating properties of renewability, biodegradability, biocompatibility, and antibacterial activity, chitin is expected to become a green cornerstone of next-generation functional materials. Chitin nanofibers, as building blocks, form multiscale hierarchical structures spanning nano- and macrolevels in living organisms, which pave the way for sophisticated functions. Therefore, from a biomimetic perspective, exploiting chitin nanofibers for use in multifunctional, high-performance materials is a promising approach. Here, we first summarize the latest advances in the multiscale hierarchical structure assembly mode of chitin and its derivative nanofibers, including top-down exfoliation and bottom-up synthesis. Subsequently, we emphasize the environmental impacts of these methods, which are crucial for whether chitin nanofibers can truly contribute to a more eco-friendly era. Furthermore, the latest progress of chitin nanofibers in environmental and medical applications is also discussed. Finally, the potential challenges and tailored solutions of chitin nanofibers are further proposed, covering raw material, structure, function, manufacturing, policies, etc.

Interfacial contact electrification can catalyze redox reactions through a process called contact-electro-catalysis (CEC). The two main reaction paths for producing reactive oxygen species via CEC are the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR). Herein, we designed a polymer/metal Janus composite catalyst that regulated the reaction rates of the WOR and ORR based on the catalyst composition. The ORR was preferentially enhanced when the polymer was negatively charged during contact electrification, while the WOR was preferentially enhanced when the polymer was positively charged. This phenomenon was observed for various conductive materials. The increase in the enhancement of the reaction rates depended on the conductivity and work function of the metal. We expect that this efficient CEC method can form a universal strategy for improving the performance of existing catalysts, as contact electrification is common in nature.

Organic-inorganic hybrid resists offer a solution to the issue of low sensitivity in organic photoresists like poly(methyl methacrylate) (PMMA). In this study, an organic-inorganic hybrid resist (PMMA-Al 2 O 3 ) with high sensitivity and resolution was prepared by depositing metal oxides into PMMA using sequential infiltration synthesis (SIS). PMMA-Al 2 O 3 was prepared by precisely controlling the number of SIS cycles (<23) in various atomic layer deposition (ALD) processes to facilitate the growth of metal oxides within PMMA pores. The impact of different metal oxide contents and distributions on the sensitivity and resolution of electron beam exposure was investigated. Numerical simulations of the deposit formation within the PMMA pores were performed by solving the pore-scale ALD governing equations fed by the reactor-scale boundary conditions. The gradual pore constriction with SIS cycles was predicted and validated by the experimental charaterizations. The results demonstrated that PMMA-Al 2 O 3 was prepared using 20 SIS cycles, which corresponds to the numerically predicted occurrence of the pore blockage at the upper region of the PMMA layer, exhibiting optimal electron beam (e-beam) resolution while enabling line exposure with a width of 50 nm. While the corresponding sensitivity was lower than those of the samples prepared using 5 and 10 SIS cycles, the degradation of the PMMA structure was affected under exposure. The pattern transfer results showed that the line width was well retained for 20 cycles of deposition because of the high etching resistance of Al 2 O 3 . This research is expected to provide an effective approach to developing next-generation high-performance photoresists.

Staphylococcus aureus ( S. aureus ) is one of the most common foodborne pathogens worldwide, which poses a great threat to public health. It is of utmost importance to develop rapid, simple, and sensitive methods for the determination of S. aureus . A signal-on photoelectrochemical (PEC) aptasensor is constructed herein based on titanium carbide (Ti 3 C 2 T x )-Au nanobipyramids (NBPs)/ZnO nanoarrays (NRs). The reliability and capability of the PEC aptasensor make it suitable for the sensitive and selective determination of S. aureus . First, the electrostatically self-assembled Ti 3 C 2 T x -Au NBP nanomaterial was coated on the ZnO NR surface by a spin-coating method. On the one hand, Ti 3 C 2 T x -Au NBPs can broaden the spectral absorption of ZnO NRs, resulting in Ti 3 C 2 T x -Au NBPs/ZnO NR composites that exhibit a wide range of absorption from the ultraviolet to the infrared region. On the other hand, Ti 3 C 2 T x can reduce the agglomeration of nanoparticles, while Au NBPs can effectively fix the aptamer through the Au-S bond. Specifically, the experimental results show that when S. aureus is present, the Au NBPs-aptamer- S. aureus complex is shed from the electrode surface, altering the interfacial electron transfer model and reducing the steric hindrance. Consequently, an amplified photocurrent signal for the quantitative determination of S. aureus is obtained. Under optimal experimental conditions, a linear correlation is observed between the current response of the aptasensor and the logarithm of the S. aureus concentration (ranging from 1.0 to 1.0 × 10 6 CFU/mL), with an impressive detection limit as low as 0.5 CFU/mL. Furthermore, the aptasensor has been successfully employed for the detection of S. aureus in milk, with the recovery of 93.0%-99.0%. Hence, this research offers a novel approach for the detection of foodborne pathogens and other noxious substances.

Constructing van der Waals (vdW) heterostructures is a prospective approach that is essential for developing a new generation of functional two-dimensional (2D) materials and designing new conceptual nanodevices. Using density-functional theory combined with a nonequilibrium Green's function approach allows for the theoretical and systematic exploration of the electronic structure, transport properties, and sensitivity of organic small molecules adsorbed on 2D C 3 B/graphene (Gra) and C 3 N/Gra vdW heterojunctions. Calculations show the metallic properties of C 3 B/Gra and C 3 N/Gra after the formation of heterojunctions. Interestingly, the heterojunctions C 3 B/Gra (C 3 N/Gra) for the adsorption of small organic molecules (C 2 H 2 , C 2 H 4 , CH 3 OH, CH 4 , and HCHO) at the C 3 B (C 3 N) side are sensitive to the chemisorption of C 2 H 2 and C 2 H 4 . Similarly, the Gra/C 3 B is chemisorbed for both C 2 H 2 and C 2 H 4 when adsorbed on Gra side, while it is only chemisorbed for C 2 H 2 in Gra/C 3 N. Interestingly, all heterojunctions on different sides are physisorbed for CH 3 OH, CH 4 , and HCHO. Furthermore, the calculated I-V curves demonstrate that the devices based on the adsorption of C 2 H 2 and C 2 H 4 at each side of the heterojunction have remarkable anisotropy, in with the current being considerably greater in the zigzag direction than in the armchair direction. More specifically, with C 2 H 2 adsorbed on the Gra side, the sensitivity along the armchair direction is up to 85.0% for Gra/C 3 B and close to 100% for Gra/C 3 N. This study reveals that C 3 B/Gra (C 3 N/Gra) heterojunctions with high selectivity, high anisotropy, and excellent sensitivity are highly prospective 2D materials for applications, which further contributes new insights into the development of future electronic nanodevices.

An amino functionalized paper-based material that utilized amino functionalized polymer particles as sensing probes and adsorption sites was fabricated via internal sizing technology for application in formaldehyde detection and adsorption. A large specific surface area and the porous structure of the paper fibers enable the application of the composite paper-based material as a sensor at low concentrations of primary amine groups. The material reacts with low levels of formaldehyde, resulting in a concentration-based change in the pH, which is rapidly expressed as a color change. After exposure to formaldehyde (0.02 mg/m 3 ) for 10 min, the color of the composite paper-based material changed from pink to brown, demonstrating the high sensitivity of the material, and this transition could be clearly observed using the naked eye. Additionally, the composite paper-based material acts as an adsorbent at a high content of amino groups, owing to a rapid addition reaction with formaldehyde, exhibiting a high adsorption capacity. Considering the high sensitivity, adsorption capacity, and adsorption speed for formaldehyde, the as-developed composite paper-based material exhibits promising application potential in the field of formaldehyde detection and adsorption.

As lithium-ion batteries (LIBs) become more widespread, the number of spent LIBs gradually increases. Until now, recycling of spent LIBs has mainly concentrated on high-value cathodes, but the anode graphite has not yet attracted wide attention. In this work, spent graphite from LIBs was oxidized to graphene oxide and then thermally reduced to reduced graphene oxide (RGO), which serves as the cathode of aqueous Zn dual-ion batteries (ZDIBs). The thermal reduction process enables RGO with a large layer spacing and porous structure, which increase the anion insertion sites and transfer kinetics. As a result, the corresponding battery exhibits a high specific capacity of 96.82 mAh g -1 at 1 A g -1 , superior rate capability, and a high capacity retention rate of 80% after 2000 cycles. Moreover, RGO gradually transforms into a long-range disordered structure during the cycling process, which provides more transport routes and active sites for anion insertion and thus leads to the increase of capacity. This work combines the recycling of spent graphite with aqueous ZDIBs, realizing the high-value use of spent graphite.

Conventional approaches for in situ remediation of mercury (Hg)-contaminated soils and sediments rely mostly on precipitation or adsorption. However, this can generate Hg-rich surfaces that facilitate microbial production of methylmercury (MeHg), a potent, bioaccumulative neurotoxin. Herein, we prove the concept that the risk of mercury methylation can be effectively minimized by adding sulfur-intercalated layered double hydroxide (S-LDH) to Hg-contaminated soils. Hg bound to S-LDH has minimal methylation potential when incubated with model methylating bacteria Pseudodesulfovibrio mercurii ND132 and Geobacter sulfurreducens PCA. With a combination of spectroscopic and microscopic evidence, as well as theoretical calculations, we confirm that dissolved Hg(II) tends to enter the interlayers of S-LDH to bind to the sulfur groups intercalated within, leading to the formation of nanoscale metacinnabar (β-HgS). This not only physically blocks the contact of methylating microorganisms but also inhibits secondary release of bound mercury in the presence of strong binding ligands in porewater. This study highlights the promising concept of in situ risk reduction of heavy metal contamination by inducing precipitation within (nano)confined domains, achieving a sustainable outcome of enhanced removal and reduced bioaccessibility for pollutants that may otherwise be bioavailable in the form of nanoprecipitates.

Cesium-based two-dimensional (2D) perovskites with attractive phase and environmental stability have broad application prospects in single-junction and tandem perovskite solar cells (PSCs). However, the severe nonradiative recombination and significant energy losses due to disordered phase orientations and phase distributions greatly hinder the carrier transport performance of cesium-based 2D PSCs and severely limit their photovoltaic performance. Here, we employ an asymmetric chiral spacer cation source, ( R )-α-phenylethylamine acrylate ( R -α-PEAAA), to prepare high-quality 2D cesium-based films with uniform phase distribution and high out-of-plane orientation by air processing, resulting in efficient carrier transport. More importantly, the asymmetric chiral spacer R -α-PEA has a stronger dipole moment than its isomer (PEA), which can regulate the dielectric properties of cesium-based 2D perovskites and promote charge dissociation. In addition, the chiral R -α-PEA can optimize the morphology and out-of-plane orientation of perovskite films, reduce trap density and nonradiative recombination loss, and optimize energy level alignment, thus enhancing carrier transport. As a result, cesium-based 2D PSCs ( R -α-PEA 2 Cs 4 Pb 5 I 16 , n = 5) achieved a record power conversion efficiency of 19.71% and the unencapsulated device maintained over 90% efficiency after 1500 h of continuous light exposure and ambient storage (35 ± 5% relative humidity). This study provides an idea for the development of chiral 2D perovskite with efficient charge carrier transport toward efficient and stable cesium-based 2D PSCs.

Peptidyl-prolyl cis-trans isomerase NIMA-interacting 1 (PIN1) has emerged as a promising therapeutic target for cancer treatment. However, the current PIN1 inhibitors have shown limited efficacy in animal models, leaving the question of whether PIN1 is a proper oncologic target still unanswered. By screening a 1 trillion DNA-encoded library (DEL), we identified novel nonacidic compounds. Among resynthesized DEL compounds, DEL1067 - 56 - 469 ( A0 ) is the most potent one (KD = 430 nM, IC 50 = 420 nM). Further optimization of A0 resulted in compound C10 with much improved potency (KD = 25 nM, IC 50 = 150 nM). As an alternative approach, C10 was then converted into proteolysis targeting chimeras (PROTACs) in order to achieve deeper downregulation of the PIN1 protein in cancer cell lines. Unfortunately, neither PIN1 inhibitors nor PIN1 PROTACs demonstrated meaningful antiproliferation activity. In addition, siRNA knock-down experiments provided unfavorable evidence of PIN1 as an oncologic target. Our findings highlight the complexity of targeting PIN1 for cancer therapy.

It is important to attain red hot exciton materials applicable in highly efficient organic light-emitting diodes with low-efficiency roll-off, but their development is restricted by the energy gap law. Herein, the sulfur atom was replaced by a heavier selenium atom based on benzothiadiazole to obtain a new benzoselenadiazole acceptor with a heavy atom effect and stronger electron-withdrawing ability. Two novel red hot exciton materials named BSe-DtBuTPA and BSe-2PhCz-d 24 were designed and synthesized based on the benzoselenadiazole unit. Benefiting from the heavy-atom effect of selenium and the small Δ E S 1 T 2 , both emitters exhibited ultrafast high-lying reverse intersystem crossing rate constants (7.00 × 10 7 and 1.17 × 10 7 s -1 ). The devices based on BSe-DtBuTPA and BSe-2PhCz-d 24 demonstrated maximum external quantum efficiencies of 4.81 and 7.15% with emission peaks at 653 and 596 nm, respectively. The device based on deep-red BSe-DtBuTPA exhibited negligible efficiency roll-off of 18.5% at 10000 cd/m 2 .

In this work, various novel pyridinyl- and pyridinium-modified Aza-BODIPY PSs were designed and constructed based on monoiodo Aza-BODIPY PSs ( BDP-4 and BDP-15 ) in an attempt to construct "structure-inherent organelles-targeted" PSs to endow potential organelle-targeting ability. Pyridinyl PSs displayed potent photodynamic efficacy, and monorigidified PSs were very effective. The monorigidified PS 20 with meta -pyridinyl moiety displayed the most potent photoactivity and negligible dark toxicity with a favorable dark/phototoxicity ratio (>4800). To our surprise, monorigidified PS with meta -pyridinyl moiety (e.g., 20 ) was lipid droplet-targeted. 20 showed good cellular uptake and intracellular ROS generation compared with BDP-15 . The preliminary cell death process exploration indicated that 20 resulted in lipid peroxidation and induced cell death through an iron-independent ferroptosis-like cell death pathway. In vivo antitumor efficacy experiments manifested that 20 significantly inhibited tumor growth and outperformed BDP-15 and Ce6 even under a single low-dose light irradiation (30 J/cm 2 ).

Ovalbumin (OVA) is a high-quality protein for humans. Modifying microorganisms to produce proteins offers a solution to potential food protein shortages. In this study, OVA was expressed in Saccharomyces cerevisiae . Initially, screening signal peptides led to extracellular OVA reaching 3.4 mg/L using the INU1 signal peptide. Coexpressing Kar2 and PDI increased OVA production to 5.1 mg/L. Optimizing the expression levels of regulators OPI1, INO2, and INO4 expanded the endoplasmic reticulum membrane, raising yield to 5.5 mg/L. Combining both strategies increased OVA production to 6.2 mg/L, 82% higher than control. This strategy also enhanced secretion of other proteins. Finally, fed-batch fermentation in a 3-L bioreactor significantly boosted OVA production to 116.3 mg/L. This study provides insights for the heterologous synthesis of other high-quality proteins for future food applications.

Electronic waste is an emerging source of per- and polyfluoroalkyl substance (PFAS) emissions to the environment, yet the contribution from hazardous recycling practices in the South Asian region remains unclear. This study detected 41 PFAS in soil samples from e-waste recycling sites in Pakistan and the total concentrations were 7.43-367 ng/g dry weight (dw) (median: 37.7 ng/g dw). Trifluoroacetic acid (TFA) and 6:2 fluorotelomer sulfonic acid emerged as the dominant PFAS, constituting 49% and 13% of the total PFAS concentrations, respectively. Notably, nine CF 3 -containing emerging PFAS were identified by the high-resolution mass spectrometry (HRMS)-based screening. Specifically, hexafluoroisopropanol and bistriflimide (NTf2) were consistently identified across all the samples, with quantified concentrations reaching up to 854 and 90 ng/g dw, respectively. This suggests their potential association with electronic manufacturing and recycling processes. Furthermore, except for NTf2, all the identified emerging PFAS were confirmed as precursors of TFA with molar yields of 8.87-40.0% by the TOP assay validation in Milli-Q water. Overall, this study reveals significant emission of PFAS from hazardous e-waste recycling practices and emphasizes the identification of emerging sources of TFA from precursor transformation, which are essential for PFAS risk assessment.

Transfer printing is a technology widely used in the production of flexible electronics and vertically stacked devices, which involves the transfer of predefined electronic components from a rigid donor substrate to a receiver substrate with a stamp, potentially avoiding the limitations associated with lithographic processes. However, the stamps typically used in transfer printing have several limitations related to unwanted organic solvents, substantial loading, film damage, and inadequate adhesion switching ratios. This study introduces a thermally responsive phase-change stamp for efficient and damage-free transfer printing inspired by the adhesion properties observed during water freezing and ice melting. The stamp employs phase-change composites and simple fabrication protocols, providing robust initial adhesion strength and switchability. The underlying mechanism of switchable adhesion is investigated through experimental and numerical studies. Notably, the stamp eliminates the need for extra preload by spontaneously interlocking with the ink through in situ melting and crystallization. This minimizes ink damage and wrinkle formation during pickup while maintaining strong initial adhesion. During printing, the stamp exhibits a sufficiently weak adhesion state for reliable and consistent release, enabling multiscale, conformal, and damage-free transfer printing, ranging from nano- to wafer-scale. The fabrication of nanoscale short-channel transistors, epidermal electrodes, and human-machine interfaces highlights the potential of this technique in various emerging applications of nanoelectronics, nano optoelectronics, and soft bioelectronics.

Benefiting from easy visualization and simultaneous detection of multiple targets, fluorescence microbeads are commonly used as fluorescence-sensing elements to detect pollutants in the environment. However, the application of fluorescence microbead-based sensor arrays is still limited because fluorescence dyes always suffer from self-quenching, photobleaching, and spectral overlap. Herein, three kinds of gold nanoclusters (Au NCs) were assembled with polystyrene microspheres (PS NPs) by electrostatic interaction to prepare fluorescence microbeads (PS-Au NCs), developing a sensor array for the simultaneous analysis of multiple metal ions. In this work, different PS-Au NCs showed an enhancing or quenching fluorescence response to various metal ions, owing to distinct binding capacities. Combined with the recognition algorithm from linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA), this sensor assay could realize single-component and multicomponent qualitative detection for 8 kinds of heavy metal ions (HMIs) including Cu 2+ , Co 2+ , Pb 2+ , Hg 2+ , and Ce 3+ . Particularly, the large surface area of PS NPs could provide a direct reaction microenvironment to improve the efficiency of the detection process. Meanwhile, the fluorescence property of Au NCs could also be enhanced by a partially effective aggregation-induced emission (AIE) effect to give better fluorescence signal output. Under optimal conditions, 8 kinds of heavy metals and their multicomponent mixtures could be identified at concentrations as low as 0.62 μM. Meanwhile, the analytical performance of this sensor assay in water samples was also verified, meeting the requirement of actual analysis. This study provides a great potential and practical example of single-batch, multicomponent identification for HMIs.

Developing brain-inspired neuromorphic paradigms is imperative to breaking through the von Neumann bottleneck. The emulation of synaptic functionality has motivated the exploration of optoelectronic memristive devices as high-performance artificial synapses, yet the realization of such a modulatory terminal capable of full light-modulation, especially near-infrared stimuli, remains a challenge. Here, a fully light-modulated synaptic memristor is reported on a P-MoSe 2 /P x O y heterostructure formed by a facile one-step selenization process. The results demonstrate successful achievement of multiwavelength (visible 470 nm to near-infrared 808 nm) modulated switching operations (reset in 0.21-0.97 V) and diverse synaptic behaviors, including postsynaptic current, paired-pulse facilitation, short- and long-term memory (STM and LTM), and learning-forgetting. Notably, the device can exhibit a 3.42 μA PSC increase under six identical 655 nm stimuli, a 11.90-46.24 μA PSC modulation by changing 808 nm light intensity from 6 to 14 mW/cm 2 , and a transition from STM to LTM lasting between 2.47 and 4.27 s by a prolonged 808 nm pulse from 1 to 30 s. A novel possible light-induced switching mechanism in such a heterostructure is proposed. Furthermore, brain-like light-stimulated memory behavior and Pavlov's classical conditioning demonstrate the device's capacity for processing complex inputs. The study presents a design toward a multiwavelength modulated artificial visual system for color recognition.

Emerging optoelectronic memristive devices with high parallelism and low-power consumption have made neuromorphic computing hardware a tangible reality. The coordination of conductivity regulation through both electrical and light signals is pivotal for advancing the development of synaptic memristors with brainlike functionalities. Here, an artificial visual synapse is presented with the Ti 3 C 2 MXene memristor which demonstrates not only the nonvolatile memory effect (Set/Reset: 0.58/-0.55 V; Retention: >10 3 s) and sustained multistage conductivity, but also facile modulation of both electrical- and light-stimulated synaptic behaviors. By adjusting the stimulus parameters, the Ti 3 C 2 MXene enables the realization of biosynaptic excitatory postsynaptic current, sustained conductivity, stable long-term facilitation/depression, paired pulse facilitation, spiking-timing-dependent plasticity, and experiential learning. Particularly, benefiting from the distinguishable photoconductive and memory effects of multiple near-infrared intensities (7-13 mW/cm 2 ), potential applications in visual nociceptive perception ("threshold", "noadaption", "relaxation") and imaging (e.g., "Superman" cartoon character) in infrared environments are well achieved in such Ti 3 C 2 MXene memristors. These results hold significant implications for the future advancement of integrated optoelectronic sensing, memory, nociception, and imaging systems.

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.

An electrochemically mediated enzyme process for nicotinamide adenine dinucleotide (NADH) oxidation and biosensing has been developed in which the oxygen-dependent activities of wild-type NADH oxidase are replaced by electrochemical regeneration of the flavin adenine dinucleotide (FAD) cofactor in the active site. Consequently, the present bioelectrocatalysis does not rely on a continuous oxygen supply through bubbling air or pure oxygen in biosynthetic applications, which reduces enzyme stability. The coupled electrochemical and enzymatic catalysis is achieved through a combination of enzyme immobilization on the electrode and electrochemical oxidation of FADH 2 in the active site mediated by the electron transfer mediator ferrocene carboxylic acid (FcCA). Furthermore, to minimize the effect of dissolved oxygen when the electrocatalytic process is exposed to air, we successfully designed mutations at the Leu40 and Cys42 sites of Leuconostoc mesenteroides ( Lm NOx) to block the oxygen passage into the active site and to eliminate the native FAD cofactor regeneration half-reaction. The engineered enzymes, whose activities are significantly reduced or inactive in solution, are electrocatalytically active toward conversion of NADH to NAD + , demonstrating successful FAD cofactor regeneration in the active site via electrochemistry. Finally, we developed two highly responsive electrochemical biosensors for NADH detection which has a superior substrate specific to standard detectors using metal electrodes, and comparable detection range and detection limit (1-3 μM)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Digital light processing (DLP) bioprinting, known for its high resolution and speed, enables the precise spatial arrangement of biomaterials and has become integral to advancing tissue engineering and regenerative medicine. Nevertheless, inherent light scattering presents significant challenges to the fidelity of the manufactured structures. Herein, we introduce a photoinhibition strategy based on Rutin nanoparticles (Rnps), attenuating the scattering effect through concurrent photoabsorption and free radical reaction. Compared to the widely utilized biocompatible photoabsorber tartrazine (Tar), Rnps-infused bioink enhanced printing speed (1.9×), interlayer homogeneity (58% less overexposure), resolution (38.3% improvement), and print tolerance (3× high-precision range) to minimize trial-and-error. The biocompatible and antioxidative Rnps significantly improved cytocompatibility and exhibited resistance to oxidative stress-induced damage in printed constructs, as demonstrated with human induced pluripotent stem cell-derived endothelial cells (hiPSC-ECs). The related properties of Rnps facilitate the facile fabrication of multimaterial, heterogeneous, and cell-laden biomimetic constructs with intricate structures. The developed photoinhibitor, with its profound adaptability, promises wide biomedical applications tailored to specific biological requirements.