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Inthis article, the decoupling proportional–integral–derivative(PID) controller is designed for multi-input multi-output (MIMO) processeswith time delays. Three basic issues on the decoupling control arerestudied here: the computation of the decoupler, the selection ofthe decoupled matrix, and the design of the controller. Consideringthe difficulty of computing the inverse-based dynamic decoupler, especiallyfor nonsquare processes, here, we introduce a new concept of nyquistset to describe the dynamic of the decoupler. Then, based on the nyquistset, the decoupler is approximated as a low order transfer functionmatrix though the complex-curve fitting technique. In addition, somerules are proposed to reselect the decoupled matrix if it cannot producea feasible decoupler. With the proposed decoupler, a model reductiontechnique and a new robust internal model control (IMC) principleare employed to design the decentralized PI controller. The decouplerand the decentralized PI controller are implemented by a centralizedPID controller, which is the desired decoupling controller. Simulationstudies demonstrate the effectiveness and merits of the presentedmethodology. [ABSTRACT FROM AUTHOR]

A study aimed to investigate the signaling pathway of zearalenone (ZEA) leading to the apoptosis of ovarian granulosa cells (GCs) and explore the potential of vitamin E (VE) in alleviating ZEA-induced apoptosis of GCs. We constructed an apoptosis model for GCs based on exposure to the environmental toxin ZEA. Transcriptome analysis revealed that ZEA induced endoplasmic reticulum stress by activating the ATF4-Chop pathway. The addition of inhibitors targeting the estrogen receptor (ER) demonstrated that ZEA activates the ATF4-Chop pathway through ER-beta. As a strong antioxidant, VE is thought to mitigate ZEA-induced toxicity. Interestingly, molecular docking analysis at the PERK active site of the endoplasmic reticulum stress revealed a high binding capacity of VE. VE supplementation reduced apoptosis in GCs and decreased the expression of p-eIF-2α, ATF4, and Chop. Mouse tests also demonstrated that VE supplementation effectively mitigated ovarian dysfunction induced by ZEA, as evidenced by increased body weight gain, reduced oxidative stress, and decreased cell death. In summary, the present study demonstrates that ZEA activates the PERK-eIF-2α-ATF4-Chop pathway through ERβ, leading to endoplasmic reticulum stress and apoptosis of GCs. Conversely, VE inhibits the PERK/eIF-2α/ATF4/Chop signaling pathways, mitigating endoplasmic reticulum stress and improving ZEA-induced reproductive toxicity.

Cyclin-dependent kinase 7 (CDK7) is a key regulator of the cell cycle and transcription, making it a promising target for cancer therapy. Although current CDK7 inhibitors have improved in their selectivity and druglike properties, CDK7 inhibitors have failed to progress through clinical development due to severe gastrointestinal and hematotoxic side effects. To mitigate these limitations, we have developed novel, macrocyclic, noncovalent CDK7 hit compounds 2 and 3 using a macrocyclization platform that has optimized these compounds from SY-5609, a leading clinical asset. We conducted extensive structure-activity relationship (SAR) studies to improve their potency, enhance oral bioavailability, and reduce intestinal distribution, which resulted in compound 13 . Compound 13 exhibits potent in vitro activity, good ADME properties, and robust in vivo antitumor activity in xenograft models as a monotherapy. Notably, compound 13 with lower basicity demonstrated improved Caco-2 permeability, reduced blood/plasma ratio, and reduced intestinal distribution in rats, thus mitigating gastrointestinal and hematotoxic side effects.

The selective oxidation of methylbenzene to value-added products is of indisputable importance in organic synthesis. Although photocatalytic oxidation reactions of toluene have achieved great success for the preparation of its oxidative products, such as carboxylic acids, benzaldehyde, and benzoate, there remains a lack of a unified photocatalytic system for the selective preparation of these oxidation products. Herein, we report a metal- and additive-free photocatalytic protocol enabled by aryl halides using O 2 as a green oxidant for the selective synthesis of the above-mentioned three oxidation products by adjusting the reaction solvent. This strategy features many advantages, including environmentally friendly and mild reaction conditions, broad substrate applicability and functional group tolerance, and potential practical application for the synthesis of aromatic carboxylic drugs and polymer materials and degradation of polystyrene waste. The continuous-flow system was utilized for the oxidation of toluene, which resulted in a reduced reaction time and increased production efficiency. Detailed mechanistic investigation revealed that the hydrogen atom transfer process was facilitated by the bromine radical from aryl halides for further oxidation, and an electron donor-acceptor complex of methylbenzene and aryl halides may exist.

Reactive oxygen species (ROS)-mediated photocatalytic antibacterial materials are emerging as promising alternatives for the antibiotic-free therapy of drug-resistant bacterial infections. However, the overall efficiency of photocatalytic sterilization is restricted by the rapid recombination of the charge carriers. Herein, we design an in-plane π-conjugated donor-acceptor (D-A) system (g-C 3 N 4 -Zn-NC), comprising graphitic carbon nitride (g-C 3 N 4 ) as the donor and Zn single-atom anchored nitrogen-doped carbon (Zn-NC) as the acceptor. Experimental and theoretical results reveal that the introduction of Zn-NC induces the formation of an intermediate band in g-C 3 N 4 -Zn-NC, extending the spectral absorption range and facilitating charge carrier transfer and separation. Additionally, the synergistic effects of the dual sites, the N═C-N sites of the g-C 3 N 4 "donor" and the atomic Zn-N 4 sites of the Zn-NC "acceptor", boost ROS production. Consequently, the biocompatible g-C 3 N 4 -Zn-NC effectively kills methicillin-resistant Staphylococcus aureus (MRSA) under visible-light irradiation and promotes the healing of MRSA-infected wounds on mouse skin.

Atmospheric fine particulate matter (PM 2.5 ) poses threats to the cardiovascular system. Red blood cells (RBCs) are the most abundant cells in blood, which are actively involved in multiple hematological diseases, such as blood clot formation and thrombosis. Exploring how PM 2.5 with spatiotemporal heterogeneity influences the hematological system by targeting RBCs would help gain insights into the deleterious effects of PM 2.5 and provide clues for finding the causative components therein. Herein, the PM 2.5 samples collected from 3 urban sites in Beijing (i.e., Chaoyang, Shunyi, and Yanqing districts) during 4 seasons of 2022 were studied for their toxicities to mouse RBCs, and the main contributing components were further explored through chemical analysis and correlation measure. The results showed that exposure to PM 2.5 samples decreased adenosine triphosphate (ATP) levels and increased phosphatidylserine (PS) externalization of RBCs, causing cell morphological deformity. The Pearson correlation analysis showed that the aromaticity of the dissolved organic matter (DOM) in PM 2.5 samples was positively correlated with PS exposure of RBCs, showing that the lignin-like compounds were the potential contributors. The negative correlation of zeta potentials of PM 2.5 samples with PS exposure of RBCs showed the particle-derived bioactivities of this airborne pollutant. The simulative test based on artificial nanomaterials of carbon black (CB) and oxidized CB (OCB) confirmed the crucial role of particulate carbon in PM 2.5 -induced effects on RBCs, and soot with a certain oxidation degree was, thus, recognized as another contributor, given its ubiquitous existence in PM 2.5 samples. This study, for the first time, revealed PM 2.5 -induced PS exposure of RBCs, and the causative components of DOM and soot were unraveled. Considering the inevitable contact of airborne PM 2.5 with RBCs in the blood circulatory system, the findings obtained herein would help bridge the gap between PM 2.5 exposure and the risk of cardiovascular diseases, like thrombogenesis.

Catalytic methanolysis of ammonia borane (NH 3 BH 3 ) is a prospective technology in the field of hydrogen energy in which hydrogen production and hydrogen storage can be integrated together. The splitting of the O-H bond is identified as the rate-determining step (RDS) in this reaction. Thus, a deep understanding of the relationship between the electronic structure of the catalyst, especially the localized electron density of active sites, and the breaking behaviors of the O-H bond is of extreme importance for the rational design of robust catalysts for the reaction. In this work, sea urchin-like tricobalt tetroxide/copper oxide (Co 3 O 4 /CuO) nanostructures with rich oxygen vacancies (O v ) were fabricated by a simple synthetic route. In NH 3 BH 3 methanolysis, the optimal Co 3 O 4 /CuO sample exhibited ultrahigh catalytic activity with a turnover frequency (TOF) of 87.5 min -1 . Interestingly, when NH 3 BH 3 methanolysis was carried out under visible-light illumination, the TOF further increased to 116.4 min -1 , which is the highest TOF value among those of the noble-metal-free catalysts ever documented in the literature. Theoretical calculation results evidenced that the Cu site in the Co 3 O 4 /CuO sample was in charge of the adsorption and activation of methanol molecules. Both the O v and visible-light illumination can help electrons on the Cu site flow to the adsorbed methanol molecule, thus leading to localized electron redistribution of the methanol molecule and the extension of the O-H bond. The cooperation of O v and visible light makes splitting of the O-H bond easier, which is favorable for fast hydrogen release from NH 3 BH 3 methanolysis. This study helps us to gain an insight into the influence of localized electron redistribution of methanol molecules on the RDS, which conduces to the rational design of highly effective nanocatalysts. Moreover, the coinduction strategy for localized electron redistribution with oxygen vacancy engineering and visible-light illumination opens up a route to boost catalytic activity in NH 3 BH 3 methanolysis.

To address the challenge of chiral recognition in terms of efficiency and generality, we propose a novel fluorescence sensing approach by rationally designing metal-ion-responsive chiral molecular tweezers. The flexible and adaptable molecular tweezers enable facile recognition of 31 structurally varied chiral primary amine compounds, including amino acids, amino acid esters, and chiral amines. Notably, upon stimulation by zinc ions, the chiral molecular tweezers demonstrate a higher enantioselective fluorescence response. Combined density functional theory calculations reveal that the chiral sensing mechanism relies on differential reaction rates and potential hydrogen-bonding interactions between the two enantiomers and the chiral receptor, which results in one of the enantiomers forming a more abundant, stable, and structurally rigid complex with the receptor, resulting in a significant increase in the fluorescence intensity and enantioselectivity. The stimuli-responsive molecular tweezers approach provides a novel strategy for precise stereocontrol and universality of chiral recognition, offering a promising tool for applications in various fields.

There is increasing evidence that particulate matter (PM) pollution may adversely impact cognition. Considering that sleep is critical for cognitive health and occupies about one-third of human life, understanding the cognitive effects of indoor PM exposure during sleep and the potential cognitive benefits of reducing such exposure is crucial, yet currently unknown. This randomized, double-blind crossover intervention trial was conducted among 80 college students with real and sham PM filtration in their dormitories. Real-time indoor PM levels and nocturnal sleep parameters were monitored, followed by quantification of serum neurotransmitter metabolites and cognitive assessments in the mornings. We found that PM exposure during sleep, particularly PM 1 and PM 2.5 , affected immediate and delayed memory, executive function, and global cognition. Reducing PM exposure during sleep resulted in improvements in multiple cognitive domains, with a 0.21 (95% CI: 0.05, 0.36) increase in global cognitive z-score, in which increased sleep oxygen saturation (SpO 2 ) and alterations in dopamine metabolism and histidine metabolism played important roles. Notably, even when indoor PM 2.5 levels were below the WHO air quality guidelines, further reducing PM exposure could still improve sleep SpO 2 and neurotransmitter metabolism. This study provides a promising strategy to mitigate indoor PM-induced cognitive impairment.

Photovoltaic power is a rapidly growing component of the renewable energy sector. Photovoltaic power stations (PVPSs) on coastal tidal flats offer benefits, but the lack of information on the effects of PVPSs on benthic ecosystems and sediment carbon storage can hamper the development of eco-friendly renewable energy. We sampled the macrobenthos and sediment cores at a PVPS on a coastal tidal flat in eastern China. The biodiversity indicators and benthic ecological quality based on macrobenthos were mostly higher under the photovoltaic panels than elsewhere. These variations were primarily driven by pH, sediment grain size, and chlorophyll- a content. However, the PVPS had exerted a considerable influence on the macrobenthic community structure. Furthermore, the carbon stocks in the sediment cores from under the photovoltaic panels were similar to those in the reference sites. These results suggest that this PVPS has not had discernible short-term adverse effects on the benthic ecosystems or sediment carbon storage of the tidal flat. Nevertheless, the potentially long-term and cascading risks throughout the ecosystem warrant caution. Therefore, we recommend that policymakers adopt a cautious development strategy and implement long-term, high-frequency monitoring to ensure the sustainability of renewable energy production on coastal tidal flats.

The dissociation rate constant ( k off ) significantly impacts the drug potency and dosing frequency. This work proposes a powerful optimization-based framework for de novo drug design guided by k off . First, a comprehensive database containing 2,773 unique k off values is created. Based on the database, a novel generic dissociation kinetic model is developed with a mixture-of-experts architecture, enabling high-throughput predictions of k off with high accuracy. The developed model is then integrated with an optimization-based mathematical programming approach to design drug candidates with low k off . Finally, the τ-RAMD method is utilized to rigorously verify the designed potential drug candidates. In a case study, the framework successfully identified numerous new potential HSP90 inhibitor candidates, achieving a maximum 45.7% improvement in residence time (τ = 1/ k off ) compared to that of a known exceptional HSP90 inhibitor. These findings demonstrate the feasibility and effectiveness of the kinetics-guided optimization-based de novo drug design framework in designing drug candidates with prolonged τ.

A method for the efficient synthesis of chiral cycloallylalcohols has been developed, achieving excellent yields and enantioselectivities (>99% conversion, turnover number of ≤50 000, and >99% ee). This approach accommodates a variety of cycloalkenones with different aryl substituents and is tolerant of a broad range of functional groups. The synthetic utility of this method has been demonstrated through gram-scale synthesis and subsequent transformations into diverse enantioenriched oxygen-containing compounds.

l-Tryptophan decarboxylase (TDC) and l-3,4-dihydroxyphenylalanine decarboxylase (DDC) catalyze the decarboxylation of l-tryptophan, 5-hydroxytryptophan, and l-3,4-dihydroxyphenylalanine. In this study, we analyzed the amino acid compositions of the substrate-binding pockets of TDC from Catharanthus roseus ( Cr TDC) and DDC from Sus scrofa ( Ss DDC), explored the specificity of key amino acids within these pockets, and elucidated mechanisms influencing substrate selectivity and catalytic activity in both enzymes, using whole-cell catalysis to screen mutants and determine enzymatic kinetic parameters. The results demonstrated that residues Ala-103 and Val-122 in Cr TDC, along with their corresponding sites Thr-82 and Ile-101 in Ss DDC, significantly influence substrate selectivity and catalytic efficiency. Molecular dynamics simulations revealed that substrate selectivity and catalytic efficiency depends on the nucleophilic attack distance between the substrate's amino group and the C4' of pyridoxal 5'-phosphate. This study elucidates the catalytic mechanisms and structural bases of TDC and DDC, guiding enhancements in the related aromatic monoamine biosynthesis.

Dye sensitization enhances the luminescence of lanthanide nanoparticles by improving light-harvesting. Typically, Yb 3+ serves as an energy bridge but absorbs at a single transition, limiting dyes' options (λ ex > 700 nm) due to the spectral overlap requirement. In contrast, the emitter Er 3+ spans energy levels from UV to NIR, making it ideal for multicolor excitation. We developed a strategy to directly sensitize Er 3+ upconversion (UCL) and downconversion luminescence (DCL) by using cyanine dyes. Cy5 demonstrated the greatest enhancement, achieving a 1942-fold UCL and 70-fold DCL increase compared to nanoparticles alone (Er-NPs) under 980 nm excitation. Smaller Er-NPs exhibited brighter dye-sensitized luminescence due to enhanced interfacial energy transfer. A 2 nm inert shell produced the brightest UCL, while thicker shells improved DCL. Dye-sensitized Er 3+ emissions at 2 H 11/2 (525 nm) and 2 P 3/2 (408 nm) enabled temperature monitoring with a maximum sensitivity ( S a ) of 3.69%/K. This approach holds significant potential for optical temperature sensing and medical imaging.

High-throughput single-cell heterogeneity imaging and analysis is essential for understanding complex biological systems and for advancing personalized precision disease diagnosis and treatment. Here, we present a miniaturized lensless chemiluminescence chip for high-throughput single-cell functional imaging with subcellular resolution. With the sensitive chemiluminescence sensing and wide field of view of contact lensless imaging, we demonstrated the chemiluminescent imaging of over 1000 single cells, and their membrane glycoprotein and the high-throughput single-cell heterogeneity of membrane protein imaging were examined for precision analysis. Furthermore, the functional adhesion and heterogeneity of single live cells were imaged and explored. This miniaturized lensless on-chip CL-CMOS imaging platform enables high-throughput single-cell imaging and analysis with high sensitivity and subcellular resolution, providing new techniques for the cellular study of biological heterogeneity and has potential application in precision disease diagnosis and treatment at the point-of-care settings.

During the high-temperature oxygen evolution reaction for CO 2 electrolysis in solid oxide electrolysis cells (SOECs), the key elementary process of O 2- transfer is restricted by the high anodic oxygen pressure thermodynamically, thus requiring a high external voltage [open-circuit voltage (OCV)] to drive the electrolysis reaction. Herein, electrochemical CH 4 reforming is introduced to the SOEC anode, which remarkably lowers the anodic oxygen pressure and OCV, finally reducing the energy demand from 3.12 to 0.11 kW h per cubic meter of CO. Meanwhile, atomically dispersed Ru species is anchored on the anode surface due to the strong metal-support interaction, which exhibits superior CH 4 reforming activity (90% of CO selectivity) and stability (300 h) to the infiltrated Ru nanoparticles and doped Ru species in the bulk lattice at 600 °C. This work proposes an efficient strategy to boost the SOEC performance thermodynamically and produce value-added chemicals at both the cathode and anode of SOEC simultaneously.

Extending the depth-of-charge (DoC) of the layered oxide cathode presents an essential route to improve the competitiveness of the Na-ion battery versus the commercialized LiFePO 4 -based Li-ion battery (0.8 CNY/Wh). However, the DoC-dependent boundary between detrimental/irreversible structural distortion and neutral/reversible structure interconversion cannot be clearly distinguished, which is attributed to the ambiguous recognition of correlation among the complex phase transition, local covalent environment evolution, and charge compensation. Herein, to bridge the above gap, we employed O3-NaNi 1/3 Fe 1/3 Mn 1/3 O 2 as the prototype cathode and extended the target DoC from typical Na0.4 (∼125 mAh/g, 4.0 V cutoff) to Na0.2 (∼180 mAh/g, 4.3 V cutoff). Regarding phase transition and charge compensation, the O3-to-P3 phase transition occurs before moderate Na 0.4 -DoC (Fe/Mn redox silence, Ni oxidation dominated), while further desodiation (start from Na 0.4 ) induces a P-to-O slab transition, resulting in the coexistence of P3 and OP2 phases and subsequent OP2/O3 intergrowth phases at higher DoC (Na 0.2 ), upon which the Fe 3+ -to-Fe 4+ oxidation is activated for capacity contribution. The local covalent environment presents severer deviation at high DoC (merely 0.2 mol desodiation from Na 0.4 to Na 0.2 ), which can be attributed not only to the slab gliding induced by the P-to-O slab transition but also to the further aggravation caused by the Jahn-Teller distortion of the FeO 6 octahedron. Such irreversible distortion of the local covalent environment would be accumulated and evolved/deteriorated into structural degradation during long-term cycling. Furthermore, the rate-dependent artificial regulation of redox process has been demonstrated and the doping strategy toward structural stabilization has been proposed.

Photothermal therapy (PTT) is an efficient way to combat bacterial infections and circumvent multidrug resistance. However, balancing efficacious bacterial killing and minimizing damage to the surrounding normal tissues remain a great challenge. Herein, a highly cooperative Prussian blue/kaolinite (PB/Kaol) hybrid nanosystem is constructed for antibacterial therapy to accelerate the healing of infected wounds. After hybridization with Kaol, the prepared PB/Kaol forms interfacial Al-O-Fe bonds, a fast charge transfer channel from Kaol to PB, which contributes to the enhanced photothermal effect of PB/Kaol. Additionally, the hydroxyl and Lewis acid-base sites of the Kaol surface could promote the adhesion of PB/Kaol to bacteria, thereby ensuring that as much hyperthermia as possible is focused on the bacteria and minimizing damage to the surrounding healthy tissues. Furthermore, PB/Kaol inherits the anti-inflammatory and hemostasis functions of PB and Kaol, resulting in the rapid healing of infected wounds.

The cleavage of the benzene-oxygen (C aryl -O(C)) bond of the lignin β-O-4 linkage is expected to relieve condensation of the degradation product and improve the product value. Nevertheless, the electrochemical breaking of the C aryl -O(C) bond has not been achieved yet due to the high dissociation energy (∼409 kJ mol -1 ) and the easy over-reduction of aromatic compounds. Here, we report an aqueous electrochemical reduction strategy for breaking C aryl -O(C) bonds via the regulation of molecular adsorption. The density functional theory (DFT) calculations and quartz crystal microbalance (QCM) measurements reveal that the residual Cu(I) in the CuO electrocatalyst enhances the adsorption of the 2-phenoxy-1-phenylethyl alcohol (PPE) by the C aryl -O(C) bond and lowers the energy barrier of the protons attacking the oxygen atom in the β-O-4 linkage. Thus, compared to the Cu electrocatalyst (with a hydroquinone yield of 47.4% and a benzyl alcohol yield of 24.8%), the CuO nanorod exhibits a much higher yield of hydroquinone (95.3%) and benzyl alcohol (88.6%) at a potential of -0.4 V vs reversible hydrogen electrode (RHE) in an undivided cell. Moreover, the reaction pathway and the cleavage of the C aryl -O(C) bond are identified through a combination of in situ synchrotron-radiation Fourier transformed infrared spectroscopy (SR-FTIR) and DFT calculations. This effective method is utilized for poplar lignin electrolysis, yielding 10.9 wt % of guaiacylglycerol, with an outstanding selectivity of >63.0%. This work provides an efficient and mild method of cleavage of C aryl -O(C) bonds in lignin valorization.

Lysine cyclodeaminase (LCD)-mediated synthesis of l-pipecolic acid (l-PA) from l-lysine (l-Lys) is a promising approach. However, only one LCD has been reported, and its inadequate activity limits industrial applications. To address this problem, a substrate analogue-guided enzyme mining strategy was employed. A novel ornithine cyclodeaminase (OCD) from Rhizobium leguminosarum ( Rl OCD) was identified in combination with directed macrogenomic approaches. Rl OCD displayed a conversion rate of 28% at a substrate loading as high as 1000 mM. A multiregion synergy strategy consisting of pocket reshaping, dynamical cross-correlation matrix-guided coevolutionary design, and surface modification was used to design Rl OCD from the inside-out. A quadruple mutant (V93C/L119C/I170T/R90L) designated Mu4 with significantly increased activity was obtained, which showed a 28.46-fold increase in the catalytic efficiency. The conversion of Mu4 was 91% within 10 h at 1000 mM (146.19 g L -1 ) loading. The space-time yield of 282.1 g L -1 d -1 is the highest level ever reported. Molecular dynamics simulations and interaction analyses revealed that efficient pocket expansion and unique conformational rearrangements increased the affinity for the substrate, resulting in a more catalytically active conformation. This study expands the toolbox for the production of l-PA and demonstrates the effectiveness and potential of Mu4 for its production.

The preparation of high-quality highly oriented metal-organic framework (MOF) thin films is desirable for developing advanced functional devices. However, the pathways for controlling the oriented growth of MOFs are largely unknown, and determining their microcosmic evolution at the complex solid-liquid interface remains a challenge. Herein, we investigate the critical early growth stage of typical HKUST-1 on the COOH-functionalized Au substrate utilizing a combination of in situ surface-enhanced infrared spectroscopy, X-ray photoelectron spectroscopy, and photoinduced force microscopy. Detailed molecular level information indicates that it is not only the COOH-terminated SAM itself but also the distinct interfacial structures of the first metal coordinate layer and second ligand coordinate layer, which can be regulated in aprotic and protic solvents, that dominate the initial growth behavior of MOF and thus lead to the [111], [100], and polycrystal facet-oriented growth of HKUST-1. Moreover, the prepared HKUST-1 films exhibit a crystal facet-dependent catalytic rate in the chemical fixation of CO 2 into cyclic carbonate. Our observations provide a reasonable guide for designing MOF-based anisotropic functional equipment.

Smart fibers capable of integrating the multifunctionality of actuation and self-sensation into a single proprioceptive device have significant applications in soft robots and biomedicine. Especially, the achievement of self-sensing the movement patterns of different actuating segments in one fiber is still a great challenge. Herein, in this study, a fiber with the controllable Janus architecture is successfully proposed via an artful centrifugation-driven hierarchical gradient self-assembly strategy, which couples two functional components of piezoresistive carbon nanotubes and magnetic NdFeB nanoparticles into the upper and lower layers of this flexible fibrous framework with the porous sponge structure partially, respectively. As predicted, the final product exhibits the as-anticipated bionic proprioceptive behaviors of programmable actuating deformation and highly selective response to bending, stretching, and pressure with high washable stability and mechanical performances. More importantly, assisted by the different three-dimensional printing molds, the superlong Janus fibers with various controllable lengths of the reversed but sequential multistage segments can be fabricated, offering the hybrid magnetic actuation and proprioceptive sensation existing at arbitrary nodes. Therefore, several kinds of soft organism-inspired Janus fiber-derived soft robots with the arbitrarily controlled segmental characters were assembled as the proof-of-concept, which can not only realize a snake or inchworm-inspired successive contracting-stretching deformation and a sperm-inspired self-rotating crawling motion but also self-sense the signals of each segment themselves in real time and then be used to navigate an object to target position in a liquid-filled confined tube. It is believed that this work promotes the further development of proprioceptive soft robots.

Peroxynitrite (ONOO - ) is a short-term reactive biological oxidant and plays an important role in cellular signal transduction and homeostatic regulation. However, excess ONOO - is associated with neurodegenerative and cardiovascular diseases. Therefore, rapid, sensitive, and accurate assays for ONOO - detection are essential for exploring its physiological and pathological function. In this work, a wavelength-shifted and ratiometric fluorescent sensing platform for ONOO - is constructed by splitting green fluorescent carbon dots (G-CDs) and aggregating orange fluorescent carbon dots (O-CDs). The mixed G-CDs and O-CDs (M-CDs) show a fast and precise response to ONOO - in the range of 0-250 μM, with a detection limit of 10 nM. In the linearity range within 3 μM ONOO - , an obvious wavelength shift of G-CDs from 495 to 475 nm is observed owing to the oxidation and nitration of ONOO - to the surface-state fluorescence of G-CDs, accompanied by the splitting of G-CDs. In the linearity range of 3-250 μM ONOO - , the fluorescence of G-CDs remains constant, while the molecular-state fluorescence of O-CDs gradually quenches by the oxidation and nitration of ONOO - through the fluorescence static process and induces their aggregation. Additionally, M-CDs show favorable intracellular imaging of endogenous and exogenous ONOO - . This study not only presents a new fluorescence wavelength shift mechanism for ONOO - sensing but also provides insights into CDs' fluorescence mechanism by exploring their morphology and structure via reacting with reactive oxygen species (ROS).

Microbial electrochemical systems (MESs), as a green and sustainable technology, can decompose organics in wastewater to recover bioelectricity. Electroactive biofilms, a microbial community structure encased in a self-produced matrix, play a decisive role in determining the efficiency of MESs. However, as an essential component of the biofilm matrix, the role of exopolysaccharides in electroactive biofilm formation and their influence on extracellular electron transfer (EET) have been rarely studied. Herein, to explore the effects of exopolysaccharides on biofilm formation and EET rate, we first inhibited the key genes responsible for exopolysaccharide biosynthesis (namely, so_3171 , so_3172 , so_3177 , and so_3178 ) by using antisense RNA in Shewanella oneidensis MR-1. Then, to explore the underlying mechanisms why inhibition of exopolysaccharide synthesis could enhance biofilm formation and promote the EET rate, we characterized cell physiology and electrophysiology. The results showed inhibition of exopolysaccharide biosynthesis not only altered cell surface hydrophobicity and promoted intercellular adhesion and aggregation, but also increased biosynthesis of c -type cytochromes and decreased interfacial resistance, thus promoting electroactive biofilm formation and improving the EET rate of S. oneidensis . Lastly, to evaluate and intensify the capability of exopolysaccharide-reduced strains in harvesting electrical energy from actual liquor wastewater, engineered strain Δ3171-as3177 was further constructed to treat an actual thin stillage. The results showed that the output power density reached 380.98 mW m -2 , 11.1-fold higher than that of WT strain, which exhibited excellent capability of harvesting electricity from actual liquor wastewater. This study sheds light on the underlying mechanism of how inhibition of exopolysaccharides impacts electroactive biofilm formation and EET rate, which suggested that regulating exopolysaccharide biosynthesis is a promising avenue for increasing the EET rate.

Herein, a new fluorooxoborate α-KB 3 O 4 F 2 is synthesized successfully in a closed system. It crystallizes in the P 2 1 / n space group and features the rare one-dimensional (1D) zigzag [B 6 O 8 F 4 ] ∞ chains built by fundamental building blocks (FBBs) [B 6 O 9 F 4 ]. To the best of our knowledge, KB 3 O 4 F 2 is a unique example of inorganic anhydrous borate whose two polymorphs show 1D B-O/F chains constructed by different FBBs but the same symmetry operation. Different from β- KB 3 O 4 F 2 , the inconsistent arrangement of π-conjugated [B 2 O 5 ] units in α- KB 3 O 4 F 2 makes it exhibit a small birefringence (0.011@546 nm). Further, α- KB 3 O 4 F 2 owns a deep-ultraviolet (DUV) cutoff edge (<200 nm), suggesting that it has a potential application as the zero-order waveplate material in the DUV region.

Purpose: To investigate the effects of hepatic enzyme activity variations and CYP2B6 gene polymorphisms on the in vivo and in vitro metabolism of efavirenz., Main Methods: In vitro enzyme systems using rat and human liver microsomes (RLM/HLM) were established, with in vivo studies conducted on Sprague-Dawley rats. Metabolite detection was performed via LC-MS/MS. Human recombinant CYP2B6 microsomes were prepared using a baculovirus-insect cell system and ultracentrifugation, with efavirenz serving as the substrate to study enzyme kinetics., Results: Isavuconazole exhibited an IC 50 of 21.14 ± 0.57 μM in RLM, indicating a mixed competitive and noncompetitive mechanism, and an IC 50 of 40.44 ± 4.23 μM in HLM, suggesting an anticompetitive mechanism. In rats, coadministration of efavirenz and isavuconazole significantly increased the AUC, T max , and C max of efavirenz. Co-administration of efavirenz and rifampicin significantly elevated the AUC, T max , and C max of 8-OH-efavirenz. The activity of CYP2B6.4, 6, and 7 increased significantly compared to CYP2B6.1, with relative clearance ranging from 158.34% to 212.72%. Conversely, the activity of CYP2B6.3, 8, 10, 11, 13-15, 18-21, 23-27, 31-33, and 37 was markedly reduced, ranging from 4.30% to 79.89%., Conclusion: Variations in liver enzyme activity and CYP2B6 genetic polymorphisms can significantly alter the metabolism of efavirenz. It provides laboratory-based data for the precise application of efavirenz and other CYP2B6 substrate drugs.

The Bi 2 Se 3 family can exhibit many intriguing topological insulator properties, including a narrow bandgap and strong surface states, which show excellent nonlinear optical properties. Thinning bulk Bi 2 Se 3 family materials to create a low-cost photoelectric modulation device and explaining the mechanisms of nonlinear optical differences in different types of materials remain challenges. Based on liquid-phase exfoliation technology and tapered fiber, this work prepared optoelectronic modulation devices for various samples within the Bi 2 Se 3 family, quantitatively compared their nonlinear optical properties, and analyzed the sources of differentiation using the occupied and unoccupied multiband structure theory. The results correspond well to the phenomena observed in the ultrafast laser, which will provide strong support for the design of higher performance photoelectric devices based on topological insulators.

Photocatalytic hydrogen peroxide (H 2 O 2 ) production encounters a major impediment in its low solar-to-chemical conversion (SCC) efficiency due to undesired H 2 O 2 product decomposition. Herein, an isolated nickel (Ni) atom modification strategy is developed to adjust the thermodynamic process of H 2 O 2 production to address the challenge. Sacrificial experiments and in situ characterization reveal that H 2 O 2 generation occurs via a highly selective indirect two-electron oxygen reduction reaction. The optimized photocatalyst exhibits a remarkable H 2 O 2 production rate of 338.9 μmol g cat -1 h -1 in pure water, representing a 48-fold enhancement. Notably, it attains an impressive SCC efficiency of 1.05%, surpassing that of current state-of-the-art catalysts. Theoretical insights reveal the downshifted d-band center facilitates moderate O 2 adsorption and barrier-free *OOH conversion, favoring H 2 O 2 release and preventing *H 2 O 2 decomposition. This work showcases efficient H 2 O 2 photosynthesis via d-band manipulation, presenting a fresh perspective for advancing high-efficiency SCC systems.

With the rapid advancement of electronic integration technology, the requirements for the working environment and stability of the heat dissipation equipment have become increasingly stringent. Consequently, studying a high-efficiency gas-liquid two-phase heat transfer surface holds significant importance. Aiming at the limited liquid transport performance caused by the temperature gradient in the heat transfer process, this paper combines the wetting gradient with the shape gradient and proposes a gradient-wettable multiwedge patterned surface, where droplets can be transported over long distances and at high velocities. In this paper, the effect of the average wetting gradient on droplet transport performance is investigated by designing a multiwedge hydrophilic pattern and adjusting the wetting properties of the hydrophobic region. The study focuses on the temperature gradient resistance of gradient-wettable, multiwedge patterned surfaces, providing a mechanistic explanation of the surface's ability to resist temperature gradients through theoretical analysis. It is shown that the gradient wettability multiwedge patterned surface has better resistance to the temperature gradient that hinders the droplet movement, and the droplets can still achieve transport of ∼38 mm at an average speed of ∼158 mm/s under the temperature gradient of 0.59 °C/mm. The research in this paper provides some insights into the application of temperature gradient resistance on heat transfer surfaces and contributes to heat dissipation methods for electronic integrated environments.

High-temperature or heat stress (HS) represents a significant environmental challenge that adversely affects crop growth and poses a substantial threat to agricultural production. Pleurotus ostreatus , recognized as the second most widely cultivated edible fungus worldwide, is particularly susceptible to the detrimental effects of HS. Enhancing the HS resistance of P. ostreatus is crucial for increasing its yield. In a prior investigation, we discovered that salicylic acid (SA) enhanced the resistance of P. ostreatus mycelia to HS through a metabolic rearrangement. The present study further investigated the effects of SA on P. ostreatus under HS. Cultivation experiments revealed that exogenous SA improved the mycelium recovery growth rate, yield, and fruiting body quality after HS. Further experiments revealed that exogenous SA mitigated the damage to the MAPK-Slt2 signal produced by HS while maintaining cell wall integrity. Furthermore, we hypothesized that the phenylalanine ammonia-lyase pathway might serve as a source for SA. In this context, we identified two salicylic hydroxylases, Po1102164 and Po1104438. Both HS and exogenous SA were found to elevate intracellular SA levels, thereby enhancing the resistance of P. ostreatus to HS.

We report the design and synthesis of the first aliphatic covalent organic framework (COF), NUS-119, and its subsequent conversion to NUS-120, marking the first fully saturated COF. NUS-119 is built by imine-linkages exhibiting high crystallinity and porosity, achieved by using a Lewis acid as a reaction modulator to circumvent compatibility issues between the Brønsted acid and the strong basic monomer. The structure was successfully solved using 3D microelectron diffraction (microED) techniques. NUS-119 and NUS-120 demonstrated remarkable catalytic performance in base-catalyzed Knoevenagel condensation reactions, exhibiting high conversion rates, excellent size selectivity, and good recyclability. This work advances the understanding of COF materials and paves the way for future research and applications.

A nonthermal pretreatment using dielectric barrier discharge cold plasma (DBD-CP) was developed to improve the stress resistance of paddy rice during postharvest storage. The physicochemical properties, bioactive characteristics, and secondary metabolites of paddy rice were assessed after applying an optimized DBD-CP procedure, with enzyme activities and gene expression monitored over a 60 day storage period at 35 °C. A 17.06% reduction in the total color change index was noted in the DBD-CP group. Bioactive compounds, particularly gallic acid, were significantly increased, enhancing the defense mechanisms against high-temperature stress. Nontargeted metabolomics analysis indicated an upregulation of phenylpropanoid metabolism in DBD-CP-treated rice compared to controls, with notable increases in secondary metabolites such as coumaric acid, caffeic acid, and sinapic acid, suggesting potential biomarkers for stress resistance. Further verification showed significant enhancements in key enzymes of phenylpropanoid metabolism, including phenylalanine ammonia lyase (PAL), cinnamic acid-4-hydroxylase (C4H), plant coumaric acid-3-hydroxylase (C3H), and cinnamyl alcohol dehydrogenase (CAD), with increases ranging from 1.71 to 2.28 times. Gene expression levels of OsPAL7 , OsC4H4 , and OsCAD2 aligned with these enzymatic changes post-DBD-CP treatment. In conclusion, DBD-CP treatment can modulate phenylpropanoid metabolism in paddy rice, thereby enhancing bioactive compound levels to reduce stress damage during high-temperature storage.

Optical metasurfaces have revolutionized analog computing and image processing at subwavelength scales with faster speed and lower power consumption. They typically involve spatial differentiation with an engineered angular dispersion. Quasi-bound states in the continuum (quasi-BICs) have emerged as powerful tools for customizing optical resonances. While quasi-BICs have been widely used with high Q -factors and enhanced field confinement, their potential in image processing remains unexplored. Here, we demonstrate edge detection imaging by leveraging quasi-BIC in an all-dielectric metasurface. This metasurface, composed of four nanodisks per unit cell, supports a polarization-independent quasi-BIC through structural perturbations, allowing simultaneously engineering Q -factor and angular dispersion. It can perform isotropic two-dimensional spatial differentiation, which is crucial for edge detection. We fabricate the metasurfaces and validate their efficient, high-quality edge detection under different polarizations. Our findings illuminate the mechanisms of edge detection with quasi-BIC metasurfaces, opening new avenues for ultracompact, low-power optical computing devices.

The liquid-liquid interface offers a confined space to control the growth of nanomaterials. In this study, Fe(II) (water phase) induced Meso-tetra (4-carboxyphenyl) porphyrin (H 2 TCPP) (CHCl 3 , organic phase) into nanoaggregates (Fe-TCPP) in the liquid-liquid interface. By tuning the ratio of DMF in organic solvents, Fe(II) induced H 2 TCPP into two nanoaggregates (Fe-TCPP-1 and Fe-TCPP-2) with different morphologies via coordination interaction occurring at the water-CHCl 3 interface. Interestingly, the Fe-TCPP nanoaggregates possess dual enzyme-like activity (peroxidase-like and oxidase-like activity). In particular, both Fe-TCPP-1 and Fe-TCPP-2 demonstrate a peroxidase-/oxidase-like activity under visible light irradiation that is higher than that in the dark. Comparatively, Fe-TCPP-2 exhibits enhanced peroxide-like (POD) activity together with oxidase-like (OXD) activity compared with that of Fe-TCPP-1 under the corresponding similar conditions. The excellent enzyme mimic activity of Fe-TCPP nanozymes is ascribed to the generated hydroxyl radicals (·OH) and superoxide anions (O 2 •- ). Remarkably, the catalytic activity of Fe-TCPP-2 remains more than 90% even in the higher temperature range of 35-40 °C, which is significant for biological detection under physiological conditions. Based on the outstanding dual enzyme-like activity of Fe-TCPP-2, a colorimetric sensing platform for methimazole (an antithyroid medicine) has been developed, demonstrating a linear detection range of 10-100 μM and a detection limit of 4.44 μM.

Excited-state interactions within the organic layer play a critical role in sensitized phosphorescence of two-dimensional (2D) perovskites. Herein, we regulate excited-state interactions utilizing isomeric organic ligands 1-naphthylmethylamine (1-NMA) and 1-(2-naphthyl)-methanamine (2-NMA). Transient absorption and first-principles calculations are employed to elucidate the mechanisms of triplet energy transfer (TET) and triplet excimer formation. The results indicate that wave function hybridization and tunneling effect at the inorganic/organic interface contribute to rapid (∼20 ps) and highly efficient (>98%) TET, with the triplet excimer being generated in (1-NMA) 2 PbBr 4 at picosecond time-scale. However, triplet excimer is barely observed in (2-NMA) 2 PbBr 4 due to varying ligand stacking modes. Despite rapid TET, the efficiency of sensitized phosphorescence is low (<0.5%), which is ascribed to pronounced nonradiative decay. By mixing isomeric ligands and optimizing respective ratio, a maximum phosphorescence enhancement of 7.6 folds is achieved. This work provides a detailed mechanistic understanding of triplet excimer sensitization and regulation of sensitized phosphorescence.

Enhanced production stability and efficiency along with a decrease in production costs are required to build efficient microbial cell factories. Target genes can be integrated into the genome to enhance genetic stability, reduce reliance on antibiotics, and alleviate the metabolic burden. However, selecting the optimal insertion site for the desired gene expression levels remains challenging. Therefore, 18 commonly used Escherichia coli integration sites were systematically characterized in this study. Promoters of different strengths were combined with integration sites, yielding a differential intensity range of up to 93-fold. This indicated the versatility and precision of this approach for controlling gene expression levels. Referring to the library, pathway genes were strategically integrated into the E. coli genome based on their respective expression levels. Genetically stable and highly efficient engineered strains that could biosynthesize arbutin and p -aminobenzoic acid were constructed.

Wearable electronic devices with multifunctions such as flexible, integrated, and self-powered play a crucial role in the fields of health monitoring, motion monitoring, and human-computer interaction. However, their core basic components, flexible pressure sensors, face challenges including poor long-term stability and insufficient real-time sensing accuracy. In order to solve the challenges of long-term, stable, and accurate sensing of the sensor, this paper prepares polydimethylsiloxane (SHPDMS) with intrinsic self-healing property and designs a high-sensitivity self-healing capacitive flexible pressure sensor with dual microstructures (grating microstructured electrodes and microporous dielectric layer) as the substrate based on SHPDMS. Specifically speaking, the self-healing of the sensor under mild conditions was realized by introducing reversible imine bonds with low bonding energy into the polydimethylsiloxane (PDMS) flexible substrate, which solved the problem of the material's long-term service durability. A grating-like microstructure was introduced into the flexible electrode by using a spotted bamboo taro leaf as a template, and a dual microstructure sensor was constructed by combining it with a microporous dielectric layer doped with single-walled carbon nanotubes. This way reduces the elastic modulus of the dielectric layer, improves the dielectric constant of the sensor under loading, and thus significantly improves the sensor's sensitivity and extends the measurement accuracy in a low-stress range. The prepared self-healing flexible sensor achieves a sensitivity of 3.6 kPa -1 , a minimum detection limit of 5 Pa, a response recovery time of less than 80 ms, and stability over 5000 cycles, which exceeds most previously reported silicone rubber-based capacitive flexible sensors.

Characterization of arsenic (As)-responsive genes is fundamental to solving the issue of As contamination in rice. Herein, we establish the involvement of an RAV transcription factor OsAAT1 ( Arsenic Accumulation and Tolerance 1 ) in regulating As response in rice. The expression of OsAAT1 is significantly higher in roots and stems of rice seedlings and is clearly upregulated by higher concentrations of arsenite [As(III)]. Compared with wild-type (WT) plants, OsAAT1 -overexpressed transgenic lines (OE- OsAAT1 ) exhibit tolerance, while OsAAT1 -knockout mutants ( Osaat1 ) are sensitive to As(III) stress. Notably, the application of exogenous 1-naphthylacetic acid (NAA) greatly enhances the As tolerance of WT and transgenic lines, with stronger effects on OE- OsAAT1 . The change in OsAAT1 expression leads to the alteration of As and auxin accumulation in transgenic plants by regulating the expression of OsLsi1 , OsLsi2 , OsCRL4 , and OsAUX1 genes. Moreover, overexpression of OsAAT1 accelerates ROS scavenging and phytochelatins (PCs) synthesis, especially with the addition of exogenous NAA. OsAAT1 localizes in the nucleus and works as a transcriptional suppressor. OsGH3-12, belonging to the auxin-responsive GH3 gene family, is the downstream target gene of OsAAT1, whose expression is extensively downregulated by As(III). These findings provide new insights into As response via auxin signaling pathway in rice.

Acute kidney injury (AKI) represents a prevalent and complex clinical event, characterized by irreversible damage to renal tubular epithelial cells and high intensive care unit (ICU) admission rates and mortality. The kidneys are highly susceptible to oxidative stress, inflammation, pyroptosis, and programmed cell death. Pyroptosis poses a significant risk, exacerbating the damage and inflammation of renal tubular cells. Disulfiram (DSF), an FDA-approved medication for alcohol cessation, inhibits the pyroptotic pore-forming protein Gasdermin-D (GSDMD), positioning it as a potential solution for emergency relief against an inflammatory response. However, current obstacles include poor water solubility, rapid metabolism, and off-target effects. Inspired by this discovery, bovine serum albumin (BSA), which has already entered clinical application, has been utilized to produce safe and long-lasting nanoparticles (BSA@DSF NPs), addressing the challenges posed by DSF's physicochemical properties. By targeting the GSDMD protein, the potent pro-inflammatory effects of pyroptosis were mitigated, leading to the alleviation of AKI induced by ischemia-reperfusion injury. This research offers a straightforward and efficient concept for treating AKI, potentially enhancing the transition to clinical practice.