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The discovery of a highly diastereoselevtive addition of 4-bromophenyllithium to imine derived form commercially available (S)-leucinol allowed the rapid development of a scaleable synthesis of a potent and selective cathepsin K inhibitor. The molecules capable of selectively inhibiting cathepsin K might serve as useful therapeutic agents against disease such as osteoporosis and other bone disorders involving excessive bone loss.

The air-stable compounds such as [Cu(SePy)]4, [Cu(3-Me3Si-2-SeNC5H4)]4, In(2-SeNC5H4) and In(3-Me3Si-2-SeNC5H3)3 were synthesized by the reaction of (2-Se-NNC5H4) with (SePy) and 3-(trimethylsilyl)pyridineselenolate ligands. Copper compounds such as [Cu(SePy)]4 and [Cu(3-Me3Si-2-SeNC5H4)]4 exhibited lower solubility in pyridine and other organic solvents compared to In(2-SeNC5H4) and In(3-Me3Si-2-SeNC5H3)3. Furthermore, the Cu complexes are composed of similar tetrahedral Cu(I) ions and Cu-Cu bonds that are bridged by selenolate ligands.

An all-atom force field-aided molecular dynamic stimulation of a reverse-Hoogsteen antiparallel d(CG.G)7 model of DNA triple helix in 1M saltwater solution enables a study of the structure, dynamics and energetics of the triple helix. The strand-II possesses A-form conformation, while the strands I and II have A, B and other forms also, as revealed by analyzing backbone conformations, sugar pseudorotation and helical parameters. The stimulations do not induce significant variations in the helix structure.

Synthetic methodology for angiotensin II (AII) receptor antagonist losartan involves a combination of the directed ortho-metalation and Suzuki coupling technique. This approach is an efficient and convergent method for constructing the biphenyltetrazole structure of the AII antagonists. The yield of losartan using this methodology is higher than that from previous methods.

Thermodynamics parameters such as log K, delta-H, and T-delta-S were evaluated for interactions of Na+, K+, Cu2+ and Ca2+ with a series of N, N'-dipivot lariat ethers to elucidate the complexation of cations with lariat ethers and the influence of several pendant arm substituents and their length on cation binding. Introduction of oxygen and nitrogen atom containing pendant arms into the parent macromolecule increased the stability.

The synthesis of symmetrical but chiral dibenzyl- and diphenyl-substituted pyridino-18-crown-6 ligands leads to a study of their recognition response to (R)- and (S)-alpha-(1-naphthyl)ethylammonium perchlorate. The nine ligands are differentiated into two diamides, one N-methylamide, two thionoamides, one N-methylthionoamide, two amines and one N-methylamine. Two monoazapyridino-18-crown-6 ligands are also prepared for usein enantiomeric separation. The study presents the efficiency of their enantiorecognition, their X-ray structures and conformational behaviors.

The development of intelligent multifunctional nanopesticides featuring enhanced foliage affinity and hierarchical target release is increasingly pivotal in modern agriculture. In this study, a novel cationic amphiphilic comb-shaped polymer, termed PEI-TA, was prepared via a one-step Michael addition between low-molecular-weight biodegradable polyethylenimine (PEI) and tetradecyl acrylate (TA), followed by neutralization with acetic acid. Using the emulsifier PEI-TA, a positively charged avermectin (AVM) nanoemulsion was prepared via a phase inversion emulsification process. Under optimal formulation, the obtained AVM nanoemulsion (defined as AVM@PEI-TA) demonstrated exceptional properties, including small size (as low as 67.6 nm), high encapsulation efficiency (up to 87.96%), and high stability toward shearing, storage, dilution, and UV irradiation. The emulsifier endowed AVM@PEI-TA with a pronounced thixotropy, so that the droplets exhibited no splash and bounce when they were sprayed on the cabbage leaf. Owing to the electrostatic attraction between the emulsifier and the leaf, AVM@PEI-TA showed improved leaf adhesion, better deposition, and higher washing resistance in contrast to both its negatively charged counterpart and AVM emulsifiable concentrate (AVM-EC). Compared to the large-sized particles, the small-sized particles of the AVM nanoemulsion more effectively traveled long distances through the vascular system of veins after entering the leaf apoplast. Moreover, the nanoparticles lost stability when exposed to multidimensional stimuli, including pH, temperature, esterase, and ursolic acid individually or simultaneously, thereby promoting the release of AVM. The release mechanisms were discussed for understanding the important role of the emulsifier in nanopesticides.

eEF2K, an atypical alpha-kinase, is responsible for regulating protein synthesis and energy homeostasis. Aberrant eEF2K function has been linked to various human cancers, including triple-negative breast cancer (TNBC). However, limited cellular activity of current eEF2K modulators impedes their clinical application. Based on the 2-phenyl-1,2,4-triazine-3,5(2 H ,4 H )-dione scaffold of our hits I4 and C1 , structure-activity relationship analysis led to the discovery of several more active derivatives (e.g., 19 , 34 , and 36 ) in inhibiting the viability of TNBC cell line MDA-MB-231. Moreover, the most potent compound 36 significantly suppresses the viability, proliferation, and migration of both MDA-MB-231 and HCC1806 cell lines. Mechanistically, compound 36 has a high binding affinity for the eEF2K protein and effectively induces its degradation. Additionally, 36 exerts a comparable tumor-suppressive effect to paclitaxel in an MDA-MB-231 cell xenograft mouse model with no obvious toxicity, demonstrating that compound 36 could be developed as a potential novel therapeutic for TNBC treatment.

We report a novel visible-light-driven photoredox-catalyzed cascade reaction involving Conia-ene-type cyclization and Smiles rearrangement initiated from alkyne-tethered α-sulfonyl esters. This methodology not only facilitates the rapid synthesis of a broad spectrum of highly substituted methylenecarbocycles but also introduces a new mechanistic pathway with aryl group migration, surpassing the conventional 1,5-hydrogen shift typically observed in Conia-ene reactions.

Conductive hydrogels exhibit tremendous potential for wearable bioelectronics, biosensing, and health monitoring applications, yet concurrently enhancing their biocompatibility and antimicrobial properties remains a long-standing challenge. Herein, we report an all-natural conductive supramolecular hydrogel (GT 5 -DACD 2 -B) prepared via the Schiff base reaction between the biofriendly dialdehyde cyclodextrin and gelatin. The potent antibacterial agent fusidic acid (FA) is incorporated through host-guest inclusion, enabling 100% inhibition of Staphylococcus aureus proliferation. The biocompatibility of our hydrogel is bolstered with tannic acid (TA) facilitating antibacterial effects through interactions with gelatin, while borax augments conductivity. This supramolecular hydrogel not only exhibits stable conductivity and rapid response characteristics but also functions as a flexible sensor for monitoring human movement, facial expressions, and speech recognition. Innovatively integrating biocompatibility, antimicrobial activity, and conductivity into a single system, our work pioneers a paradigm for developing multifunctional biosensors with integrated antibacterial functionalities, paving the way for advanced wearable bioelectronics with enhanced safety and multifunctionality.

The FLT3-ITD (internal tandem duplication) mutant has been a promising target for acute myeloid leukemia (AML) drug discovery but is now facing the challenge of resistance due to point mutations. Herein, we have discovered a type II FLT3 inhibitor, SILA-123 . This inhibitor has shown highly potent inhibitory effects against FLT3-WT (IC 50 = 2.1 nM) and FLT3-ITD (IC 50 = 1.0 nM), tumor cells with the FLT3-ITD mutant such as MOLM-13 (IC 50 = 0.98 nM) and MV4-11 (IC 50 = 0.19 nM), as well as BaF3 cells associated with the FLT3-ITD mutant and point mutations like BaF3-FLT3-ITD-G697R (IC 50 = 3.0 nM). Moreover, SILA-123 exhibited promising kinome selectivity against 310 kinases (S score (10) = 0.06). In in vivo studies, SILA-123 significantly suppressed the tumor growth in MV4-11 (50 mg/kg/d, TGI = 87.3%) and BaF3-FLT3-ITD-G697R (50 mg/kg/d, TGI = 60.0%) cell-inoculated allograft models. Our data suggested that SILA-123 might be a promising drug candidate for FLT3-ITD-positive AML.

Graphene chemical vapor deposition (CVD) growth directly on target using substrates presents a significant route toward graphene applications. However, the substrates are usually catalytic-inert and special-shaped; thus, large-scale, high-uniformity, and high-quality graphene growth is challenging. Herein, graphene-skinned glass fiber fabric (GGFF) was developed through graphene CVD growth on glass fiber fabric, a Widely used engineering material. A fluid dynamics rectification strategy was first proposed to synergistically regulate the distribution of carbon species in 3D space and their collisions with hierarchical-structured substrates, through which highly uniform deposition of high-quality graphene on fibers in large-scale 3D-woven fabric was realized. This strategy is universal and applicable to CVD systems using various carbon precursors. GGFF exhibits high electrical conductivity and photothermal conversion capability, based on which a natural energy harvester was first developed. It can harvest both solar and raindrop energy through solar heating and droplet-based electricity generating, presenting promising potentials to alleviate energy burdens.

The construction of heterogeneous microstructure and the selection of multicomponents have turned into a research hotspot in developing ultralight, multifunctional, high-efficiency electromagnetic wave absorbing (EMA) materials. Although aerogels are promising materials to fulfill the above requirements, the increase in functional fillers inevitably leads to the deterioration of intrinsic properties. Tuning the electromagnetic properties from the structural design point of view remains a difficult challenge. Herein, we design customized pore creation strategies via introducing sacrificial templates to optimize the conductive path and construct the discontinuous dielectric medium, increasing dielectric loss and achieving efficient microwave absorption properties. A 3D porous composite (MEM) was crafted, which encapsulated an EVA/FeCoNi (EVA/MNPs) framework with Ti 3 C 2 T x MXene coating by employing a direct heated cross-linking and immersion method. Controllable adjustment of the conductive network inside the porous structure and regulation of the dielectric character are achieved by porosity variation. Eventually, the MEM-5 with a porosity of 66.67% realizes RL min of -39.2 dB (2.2 mm) and can cover the entire X band. Moreover, through off-axis electronic holography and the calculation of conduction loss and polarization loss, the dielectric property is deeply investigated, and the inner mechanism of optimization is pointed out. Thanks to the inherent characteristic of EVA and the porous structure, MEM-5 showed excellent thermal insulating and superior compressibility, which can maintain 60 °C on a 90-100 °C continuous heating stage and reached a maximum compressive strength of 60.12 kPa at 50% strain. Conceivably, this work provides a facile method for the fabrication of highly efficient microwave absorbers applied under complex conditions.

There is a resurgence of research interest in inherently chiral calixarenes and heteracalixaromatics. However, the examples of macrocyclic ring-expanded homocalixarenes and heterocalixaromatics of inherent chirality are not known. Here we report an efficient method to construct inherently chiral N 2 ,O 2 -linked homo-heteracalixaromatics from reductive amination reactions between bis-aldehydes and aliphatic diamines. Examples of post-macrocyclization derivatization were also demonstrated. Enantiomers were obtained from resolution and did not undergo racemization at an elevated temperature. This study provides a new strategy to design novel and functional inherently chiral macrocycles that have potential applications in supramolecular chemistry.

Aerosol acidity (or pH) is one central parameter in determining the health, climate, and ecological effects of aerosols. While it is traditionally assumed that the long-term aerosol pH levels are determined by the relative abundances of atmospheric alkaline to acidic substances (referred to as R C/A hereinafter), we observed contrasting pH─ R C/A trends at different sites globally, i.e., rising alkali-to-acid ratios in the atmosphere may unexpectedly lead to increased aerosol acidity. Here, we examined this apparently counterintuitive phenomenon using the multiphase buffer theory. We show that the aerosol water content (AWC) set a pH "baseline" as the peak buffer pH, while the R C/A and particle-phase chemical compositions determine the deviation of pH from this baseline within the buffer ranges. Therefore, contrasting long-term pH trends may emerge when R C/A increases while the AWC or nitrate fraction decreases, or vice versa. Our results provided a theoretical framework for a quantitative understanding of the response of aerosol pH to variations in SO 2 , NO x versus NH 3 , and dust emissions, offering broad applications in studies on aerosol pH and the associated environmental and health effects.

To forge ahead with the next generation of power batteries boasting superior energy density, nickel-rich layered oxides are regarded as some of the most promising cathode materials. However, challenges such as microcracks, which are attributed to the elevated nickel content of the materials, have posed impediments to their further development and application. Consequently, this article focuses on the understanding of the materials in the deep delithiation state, dissecting their degradation mechanisms through a dual lens of electrochemical and mechanical properties. The comprehensive analysis reveals that microcracks within the particles exhibit a degree of reversibility. However, with repeated Li + de-/intercalation, these microcracks progressively propagate and permeate the entire particle, ultimately leading to particle fragmentation. Therefore, this study employs Dy 2 O 3 as an inducer to facilitate the growth of primary crystal grains, reducing the internal porosity of the particles. This effectively enhances the conductivity and lithium-ion diffusion kinetics in deep lithium-ion deintercalation states of nickel-rich cathode materials. The modified material exhibits significant suppression of microcrack formation and growth during cycling, leading to notable improvements in its chemical-mechanical properties. These degradation mechanisms and modification strategies of Ni-rich cathodes offer valuable insights into the development of Ni-rich cathode materials tailored for electric vehicles.

With the rapid development of mobile communication technology, the POI (piezoelectric on insulator) structure has gained recognition in the field of RF filtering. However, transverse modes remain in the passband of corresponding surface acoustic wave (SAW) devices, which impedes their application in crowded spectra. This article introduces a groove configuration to suppress transverse modes for POI SAW resonators employing a 50°YX-LiTaO 3 /SiO 2 /Si multilayered structure. First, the response of conventional POI SAW resonators was calculated by the 3D periodic FEM method, and the results indicate that transverse modes caused by energy leakage to busbar regions are serious in POI SAW resonators. Then, the groove configuration was adopted to confine energy within the aperture region by reducing the velocity at the end of IDT electrodes, and the groove dimension was optimized to achieve a nearly spurious-free response in the passband. Finally, experimental results of fabricated one-port SAW resonators with optimal groove configuration were provided to validate the suppression of transverse modes and the enhancement of the Q factor in the POI SAW resonator.

In recent years, there has been considerable push toward the biomedical applications with active particles, which have great potential to revolutionize disease diagnostics and therapy. The direct penetration of active particles through the cell membrane leads to more efficient intracellular delivery than previously considered endocytosis processes but may cause membrane disruption. Understanding fundamental behaviors of cell membranes in response to such extreme impacts by active particles is crucial to develop active particle-based biomedical technologies and manage health and safety issues in this emerging field. Unfortunately, the physical principles underlying the nonequilibrium behaviors from endocytosis to direct penetration remain elusive, and experiments are challenging. Here, we present a computed dynamic phase diagram for transmembrane transport of active particles and identify four characteristic dynamic phases in endocytosis and direct penetration according to the particle activity and membrane tension. The boundaries dividing these phases are analytically obtained with theoretical models, elucidating the nonequilibrium physics and criteria for the transition between different phases. Furthermore, we numerically and experimentally show three distinct dynamic regimes related to the interplay between necking and wrapping during the endocytosis process of active particles, which strikingly contrast the regimes for passive particles. Overall, these findings could be useful for sharpening the understanding of basic principles underlying biological issues related to the safe and efficient biomedical applications of such emerging matters.

Instant and strong adhesion to underwater adherends is a big challenge due to the continuous interference of water. Mussel foot protein-bioinspired catechol-based adhesives have garnered great interest in addressing this issue. Herein, a novel self-made catecholic compound with a long aliphatic chain was utilized to prepare thin (∼0.07 mm) and optically transparent (>80%) wet/underwater adhesive tapes by UV-initiated polymerization. Its adhesion activity was water-triggered, fast (<1 min), and strong (adhesion strength to porcine skin: ∼1.99 MPa; interfacial toughness: ∼610 J/m 2 , burst pressure: ∼1950 mmHg). The effect of the catechol/phenol group and positively charged moiety on the wet/underwater adhesion to abiotic/biotic substrates was investigated. On the wet/underwater adherends, the tape with catechol groups presented much higher interfacial toughness, adhesion strength, and burst pressure than the analogous tape with phenol groups. The tape with both the catechol group and cationic polyelectrolyte chitosan had a more impressive improvement in its adhesion to wet/underwater biological tissues than to abiotic substrates. Therefore, catechol and a positive moiety in the tape would synergistically enhance its wet/underwater adhesion to various substrates, especially to biological tissues. The instant, strong, and noncytotoxic tape may provide applications in underwater adhesion for sealing and wound closure.

Small secreted peptides (SSPs) are essential for defense mechanisms in plant-microbe interactions, acting as danger-associated molecular patterns (DAMPs). Despite the first discovery of SSPs over three decades ago, only a limited number of SSP families, particularly within Solanaceae plants, have been identified due to inefficient approaches. This study employed comparative genomics screens with Solanaceae proteomes (tomato, tobacco, and pepper) to discover a novel SSP family, SolP. Bioinformatics analysis suggests that SolP may serve as an endogenous signal initiating the plant PTI response. Interestingly, SolP family members from tomato, tobacco, and pepper share an identical sequence (VTSNALALVNRFAD), named SlSolP12 (also referred to as NtSolP15 or CaSolP1). Biochemical and phenotypic analyses revealed that synthetic SlSolP12 peptide triggers multiple defense responses: ROS burst, MAPK activation, callose deposition, stomatal closure, and expression of immune defense genes. Furthermore, SlSolP12 enhances systemic resistance against Botrytis cinerea infection in tomato plants and interferes with classical peptides, flg22 and Systemin, which modulate the immune response. Remarkably, SolP12 activates ROS in diverse plant species, such as Arabidopsis thaliana , soybean, and rice, showing a broad spectrum of biological activities. This study provides valuable approaches for identifying endogenous SSPs and highlights SlSolP12 as a novel DAMP that could serve as a useful target for crop protection.

To satisfy the demands of the food industry, innovative flavor enhancers need to be developed urgently to increase the food flavor. In our work, N-lauroyl phenylalanine (LP) was prepared from phenylalanine (l-Phe) and lauric acid (Lau) in water through the use of commercial enzymes (Promatex, Sumizyme FP-G, and Trypsin), and its flavor-presenting properties and mechanism were investigated. The highest LP yields obtained under one-factor optimized conditions were 61.28, 63.43, and 77.58%, respectively. Sensory assessment and an e-tongue test revealed that 1 mg/L LP enhanced the kokumi, saltiness, and umami of the simulated chicken broth solution and attenuated the bitterness of the l-isoleucine solution. The molecular simulation results suggested that the mechanisms of LP enhancement of kokumi and umami were related to hCaSR and hT1R1-hT1R3, and that hydrophobic forces and hydrogen bonds were involved in the binding of LP to taste receptors. The results implied that LP is a potential flavor enhancer for food applications.

The iontronic tactile sensing modality has garnered significant attention due to its exceptional sensitivity, immunity to noise, and versatility in materials. Recently, various formats of iontronic tactile sensors have been developed, including droplets, polymer films, paper, ionic gels, and fabrics. However, the stretchability of the current iontronic pressure sensing fabric is inadequate, hindered by the limited stretchiness of the ionic functional fabric. Incorporating a stretchable tactile sensing implement could enhance the wear comfortability by preventing relative movement and ensuring intimate contact between the sensor and the skin. The research focuses on the development of a stretchable iontronic pressure sensing (SIPS) fabric for monitoring diverse aspects of body health and movement in wearable applications. The tactile sensing structure is generated at the iontronic interface between highly stretchable ionic and conductive fabrics. In particular, the ionic fabric is prepared by coating a layer of polyurethane/ionic liquid gel onto a Spandex fabric. To showcase its remarkable sensitivity, stretchability, and ability to detect diverse body information, several application scenarios have been demonstrated including an elastic wristband for precise pulse wave detection, a flexible belt with multitactile sensing channels for respiration and motion tracking purposes, and a stretchable fabric cuff equipped with a high-resolution sensing array comprising 32 × 32 units for accurate gesture recognition.

Aqueous zinc-ion batteries (AZIBs) are poised to play a pivotal part in meeting the growing demands for energy storage and powering portable electronics for their superior security, affordability, and environmentally friendly characteristics. However, the detrimental side reactions occurring at the zinc anode and the dendrite caused by uneven zinc plating/stripping have greatly compromised the cycling life of AZIBs, thereby impeding their practical prospects. In this study, the interfacial comodulation strategy was employed by combining the "electrostatic shielding" effect of cations with the characteristic adsorption of anions. Two molar ZnSO 4 served as the matrix, and sodium hydroxyethyl sulfonate (SHES) was selected as a low-cost, nontoxic additive. Experimental results confirm that SHES and zinc anode exhibit robust interactions that lead to the formation of an electrostatic shield and a dynamic adsorption layer at the interface, thereby suppressing hydrogen evolution and corrosion. The combined "electrostatic shielding" effect of sodium ions and the robust characteristic adsorption of hydroxyethyl sulfonate anions serve to guide the directed three-dimensional (3D) diffusion of Zn 2+ , facilitating rapid, stable, and uniform deposition of zinc. Due to these effects, incorporating 0.2 M SHES as an additive extends the cycle life beyond 3600 h and enables a highly reversible process of deposition and stripping in symmetric cells. Additionally, the Zn-Cu half-cell exhibits reliable cycling for over 1400 cycles, achieving an average Coulombic efficiency of 99.6%. Moreover, the introduction of this additive substantially enhances the performance of Zn-MnO 2 and Zn-NH 4 V 4 O 10 full cells. This study demonstrates the practical feasibility of achieving anodes with high reversibility in AZIBs through the implementation of a strategy that involves anion adsorption at the interface, which holds paramount significance for the practical application of AZIBs.

Conventional lateral flow immunoassay (LFIA) usually suffers from poor antimatrix interference, unsatisfactory sensitivity, and lack of quantitative ability for target analyte detection in food matrices. In response to these limits, here, multifunctional nanomaterial ZnFe 2 O 4 nanoparticles (ZFOs) were developed and integrated into LFIA for powerful magnetic separation/enrichment and colorimetric/photothermal target sensing. Under optimum conditions, the detection for clenbuterol (CL) with magnetic enrichment achieves 9-fold higher sensitivity compared to that without enrichment and 162-fold higher sensitivity compared to that based on traditional colloidal golds. Attributing the improved performances of ZFOs, CL can be detected at ultralow levels in pork and milk with 10 min of immunoreaction time. The vLODs were 0.01 μg kg -1 for two modes, and the cutoff values of CL were about 5 and 3 μg kg -1 , respectively. More importantly, the enrichment ZFO-mediated LFIA (ZE-LFIA) exhibits a similar limit of detection (LOD) in both buffer solution and food matrix, demonstrating a universal resistance to the food matrix. The multitudinous performance merits of this ZE-LFIA with high sensitivity, matrix tolerance, accuracy, and specificity have ensured a broad application potential for target detection of clenbuterol and can serve as an experience for other veterinary drug residues' detection.

Porous solids can accommodate and release molecular hydrogen readily, making them attractive for minimizing the energy requirements for hydrogen storage relative to physical storage systems. However, H 2 adsorption enthalpies in such materials are generally weak (-3 to -7 kJ/mol), lowering capacities at ambient temperature. Metal-organic frameworks with well-defined structures and synthetic modularity could allow for tuning adsorbent-H 2 interactions for ambient-temperature storage. Recently, Cu 2.2 Zn 2.8 Cl 1.8 (btdd) 3 (H 2 btdd = bis(1 H -1,2,3-triazolo-[4,5- b ],[4',5'- i ])dibenzo[1,4]dioxin; Cu I -MFU-4 l ) was reported to show a large H 2 adsorption enthalpy of -32 kJ/mol owing to π-backbonding from Cu I to H 2 , exceeding the optimal binding strength for ambient-temperature storage (-15 to -25 kJ/mol). Toward realizing optimal H 2 binding, we sought to modulate the π-backbonding interactions by tuning the pyramidal geometry of the trigonal Cu I sites. A series of isostructural frameworks, Cu 2.7 M 2.3 X 1.3 (btdd) 3 (M = Mn, Cd; X = Cl, I; Cu I M-MFU-4 l ), was synthesized through postsynthetic modification of the corresponding materials M 5 X 4 (btdd) 3 (M = Mn, Cd; X = CH 3 CO 2 , I). This strategy adjusts the H 2 adsorption enthalpy at the Cu I sites according to the ionic radius of the central metal ion of the pentanuclear cluster node, leading to -33 kJ/mol for M = Zn II (0.74 Å), -27 kJ/mol for M = Mn II (0.83 Å), and -23 kJ/mol for M = Cd II (0.95 Å). Thus, Cu I Cd-MFU-4 l provides a second, more stable example of optimal H 2 binding energy for ambient-temperature storage among reported metal-organic frameworks. Structural, computational, and spectroscopic studies indicate that a larger central metal planarizes trigonal Cu I sites, weakening the π-backbonding to H 2 .

The surface of food processing equipment is easily affected by biofilm-forming bacteria, leading to cross-contamination and food safety hazards. The critical issue is how to endow the surface of contact materials with antibacterial and antibiofilm abilities. A sustainable, stable, and antibiofilm coating was prepared by phase transition of glutenin. The disulfide bonds in glutenin were reduced by tris(2-carboxyethyl)phosphine, triggering the phase transition of glutenin. Hydrophobic interactions and intermolecular disulfide bonds may be the primary forces. Furthermore, the phase-transited products formed a nanoscale coating on the surface of stainless steel and glass under their own adhesion force and gravity. The coating exhibited good stability in harsh environments. More importantly, after 3 h of direct contact, the colony of Escherichia coli and Staphylococcus aureus decreased by one logarithm. The amount of biofilm was observed to be significantly decreased through optical microscopy and scanning electron microscopy. This article provides a foundational module for developing novel coatings.

Excessive production of waste polyethylene terephthalate (PET) poses an ecological challenge, which necessitates developing technologies to extract the values from end-of-life PET. Upcycling has proven effective in addressing the low profitability of current recycling strategies, yet existing upcycling technologies operate under energy-intensive conditions. Here we report a cascade strategy to steer the transformation of PET waste into glycolate in an overall yield of 92.6% under ambient conditions. The cascade approach involves setting up a robust hydrolase with 95.6% PET depolymerization into ethylene glycol (EG) monomer within 12 h, followed by an electrochemical process initiated by a CO-tolerant Pd/Ni(OH) 2 catalyst to convert the EG intermediate into glycolate with high Faradaic efficiency of 97.5%. Techno-economic analysis and life cycle assessment indicate that, compared with the widely adopted electrochemical technology that heavily relies on alkaline pretreatment for PET depolymerization, our designed enzymatic-electrochemical approach offers a cost-effective and low-carbon pathway to upgrade PET.

Flexible sensors are promising for intelligent packaging and artificial intelligence, but the required multistimulus response is still a challenge in external environments. A candidate material for such multistimulus response is VO 2 due to its unique semiconducting properties. Herein, W-doped VO 2 (M) with a tunable phase transition temperature was prepared by the hydrothermal method, and then, VO 2 (M)-based flexible sensors were fabricated employing a direct-write strategy, where conductive inks with VO 2 (M) powders were patterned onto various substrates. These sensors achieve dual responses to temperature and strain and exhibit high stability (over 2000 stretch-release cycles) to accurately monitor various statuses (opening and closing, temperature changes, etc.) of intelligent packaging. The spatial pressure distribution of different objects was discerned by the prepared VO 2 (M)/poly(dimethylsiloxane) (PDMS) sponge flexible pressure sensor arrays, and the information was successfully edited using the Morse code. The sensing signals from the intelligent packaging were collected and remotely transmitted to intelligent terminals via a wireless local-area network to achieve real-time monitoring of the packaged contents. Therefore, in this work, we not only designed new flexible sensors with multiple stimulus responses but also demonstrated the potential applications of W-doped VO 2 (M)-based flexible sensors in intelligent packaging.

Spinel oxides have emerged as a promising candidate in the realm of nanozymes with variable oxidation states, while their limited active sites and low conductivity hinder further application. In this work, we synthesize a series of metal-doped NiCo 2 O 4 nanospheres decorated with Pd, which are deployed as highly efficient nanozymes for the detection of cancer biomarkers. Through meticulous modulation of the molar ratio between NiCo 2 O 4 and Pd, we orchestrated precise control over the oxygen vacancies and electronic structure within the nanozymes, a key factor in amplifying the catalytic prowess. Leveraging the superior H 2 O 2 reduction catalytic properties of Fe-NiCo 2 O 4 @Pd, we have successfully implemented its application in the electrochemical detection of biomarkers, achieving unparalleled analytical performance, much higher than that of Pd/C and other reported nanozymes. This research paves the way for innovative electron modification strategies in the design of high-performance nanozymes, presenting a formidable tool for clinical diagnostic analyses.

The stimulus-responsive regulation of enzyme catalytic activity and selectivity provides a new opportunity to extend the functionality and efficiency of immobilized enzymes. This work aims to design and synthesize a thermo-switchable enzyme@MOF for size-selective biocatalysis and biosensing through the immobilization of Candida rugosa lipase (CRL) within ZIF-8 functionalized with thermally responsive polymer, poly( N -isopropylacrylamide) (PNIPAM) (CRL@ZIF-8-PNIPAM). Unlike free CRL, which does not demonstrate substrate selectivity, we can reversibly tune the pore size of the ZIF-8-PNIPAM nanostructures (open pores or blocked pores) through temperature stimulus and subsequently modulate the substrate selectivity of CRL@ZIF-8-PNIPAM. CRL@ZIF-8-PNIPAM had the highest hydrolytic activity for small molecules (12 mM p -nitrophenol/mg protein/min, 4-nitrophenyl butyrate ( p -NP Be)) and the lowest hydrolytic activity for large molecules (0.16 mM p-nitrophenol/mg protein/min, 4-nitrophenyl palmitate ( p -NP P)). In addition, CRL@ZIF-8-PNIPAM demonstrated thermo-switchable behavior for large molecules ( p -NP P). The p -NP P hydrolytic activity of CRL@ZIF-8-PNIPAM was significantly lower at 40 °C (blocked pores) than at 27 °C (open pores). However, the transition of blocked pores and open pores is a gradual process that resulted in a delay in the "thermo-switchable" catalytic behavior of CRL@ZIF-8-PNIPAM during thermal cycling. CRL@ZIF-8-PNIPAM was also successfully used for the fabrication of electrochemical biosensors for the selective biosensing of pesticides with different molecular sizes.

Exploring emerging two-dimensional (2D) van der Waals (vdW) semiconducting materials and precisely tuning their electronic properties at the atomic level have long been recognized as crucial issues for developing their high-end electronic and optoelectronic applications. As a III-VI semiconductor, ultrathin layered hexagonal GaTe ( h -GaTe) remains unexplored in terms of its intrinsic electronic properties and band engineering strategies. Herein, we report the successful synthesis of ultrathin h -GaTe layers on a selected graphene/SiC(0001) substrate, via molecular beam epitaxy (MBE). The widely tunable quasiparticle band gaps (∼2.60-1.55 eV), as well as the vdW quantum well states (QWSs) that can be strictly counted by the layer numbers, are well characterized by onsite scanning tunneling microscopy/spectroscopy (STM/STS), and their origins are clearly addressed by density functional theory (DFT) calculations. More intriguingly, distinctive 8|8E and 4|4P (Ga) mirror twin boundaries (MTBs) are identified in the ultrathin h -GaTe flakes, which can induce decreased band gaps and prominent p-doping effects. This work should deepen our understanding on the electronic tunability of 2D III-VI semiconductors by thickness control and line defect engineering, which may hold promise for fabricating atomic-scale vertical and lateral homojunctions toward ultrascaled electronics and optoelectronics.

The micropore structure of tight sandstone affects the efficiency of CO 2 displacement of crude oil. As the pressure changes, the oil displacement efficiency ( E d ) in segments with different pore radii changes, and the asphaltene precipitation in the pores causes alterations in the pore structure and wettability, which constrain E d . Ten samples of tight sandstone from the Yanchang Formation in the Ordos Basin were selected for this study. A variety of methods, including X-ray diffraction (XRD), casting thin sections (CTS), scanning electron microscopy (SEM), high-pressure mercury intrusion (HPMI), CT scanning, and nuclear magnetic resonance (NMR) combined with CO 2 displacement, were used to study the efficiency of crude oil utilization and the amount of asphaltene deposited at different pore-throat radii, and then the impacts of pressure, pore structure, and wettability changes on E d were discussed. The findings indicate that samples have three types: macropore-fine throats (MF), medium pore-tiny throats (MT), and small pore-microthroats (SM). The MT exhibits a favorable configuration. The pore-throat radius of each sample can be divided into two segments, namely, large pore segments (P L ) and small pore segments (P S ), and the P L has a significant E d . The E d of the MF-type P S is constrained by pressure. The E d of P L is significantly affected by the pressure sensitivity for the MT, while the E d of P L for the SM structure is more affected by pressure. Changes in wettability and the precipitation of asphaltene are the results of the reaction between crude oil and CO 2 . In the MF, asphaltene precipitates from the P L , while in the MT and SM, asphaltene precipitates both from the P L and P S . The amount of asphaltene precipitation strongly affects the E d in P S . The oil wettability increases more obviously with better pore-throat configurations. This study offers a reference and foundational understanding for evaluating CO 2 displacement in tight sandstone reservoirs., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Cancer immunotherapy suffers from inefficient antigen presentation owing to the limited endocytosis of antigen by dendritic cells (DCs) and dysfunction of DCs in the immunosuppressive tumor microenvironment (ITME). Here, we revealed that cinnamaldehyde-grafted polyethylenimine (PC) held the potential to serve as a neoadjuvant to modulate the above processes and thus potentiate immune responses. The PC neoadjuvant could capture the tumor antigen generated during chemotherapy to enhance the crosstalk between the antigen and DCs. Then, it depleted the intracellular glutathione by the in situ Michael addition reaction, which not only activated the NOD-, LRR-, and pyrin domain-containing 3 (NLRP3) pathway to promote DCs maturation but also triggered the antigen release. As a result, it significantly augmented antigen presentation with a 46% ratio of DCs maturation and a 53% ratio of CD8 + T cell infiltration in low immunogenic murine breast cancer.

Antibody-drug conjugates (ADCs) comprise antibodies, cytotoxic payloads, and linkers, which can integrate the advantages of antibodies and small molecule drugs to achieve targeted cancer treatment. However, ADCs also have some shortcomings, such as non-negligible drug resistance, a low therapeutic index, and payload-related toxicity. Many studies have focused on changing the composition of ADCs, and some have even further extended the concept and types of targeted conjugated drugs by replacing the targeted antibodies in ADCs with peptides, revolutionarily introducing peptide-drug conjugates (PDCs). This Perspective summarizes the current research status of ADCs and PDCs and highlights the structural innovations of ADC components. In particular, PDCs are regarded as the next generation of potential targeted drugs after ADCs, and the current challenges of PDCs are analyzed. Our aim is to offer fresh insights for the efficient design and expedited development of innovative targeted conjugated drugs.

Abrus cantoniensis Hance is a vegetative food and can be used as a folk beverage or soup to clear liver toxins and prevent liver damage. However, the components and effects of A. cantoniensis Hance in alcohol-induced liver injury were unknown. This study aimed to obtain abundant phytochemicals from A. cantoniensis Hance and identify the potency of the isolates in preventing alcohol-induced liver injury. Alcohol-stimulated AML12 cells and Lieber-DeCarli diet-fed mice were used to establish in vitro and in vivo models, respectively. Our findings indicated that flavonoid glycosides, especially AH-15 , could significantly alleviate alcohol-induced liver injury by inhibiting oxidative stress. Furthermore, we demonstrated that AH-15 inhibited ferroptosis induced by lipid peroxidation. Mechanically, we found that AH-15 regulated nuclear factor erythroid 2-related factor 2 (NRF2) expression via activation of AMP-activated protein kinase (AMPK) signaling. These results indicate that A. cantoniensis Hance is a great potential functional food for alleviating alcohol-induced liver injury.

Anaerobic biodegradation rates (half-lives) of organic chemicals are pivotal for environmental risk assessment and remediation. Traditional experimental evaluation, constrained by prolonged, oxygen-free conditions, struggles to keep pace with emerging contaminants. Data-driven machine learning (ML) models serve as promising complements. However, reported quantitative structure-biodegradation relationships or ML models on anaerobic biodegradation are mostly based on small data sets (<100 records) and neglect experimental conditions, usually achieving compromised predictions. This work aimed to develop ML models for predicting the biodegradation half-lives of organic pollutants in anaerobic environments (i.e., sediment/soil and sludge). Focusing on important features of both chemicals and experimental conditions, we first curated two data sets, one for sediment/soil (SED) and the other for sludge (SLD), covering 978 records for 206 chemicals from the literature, and then conducted a meta-analysis. Next, we built a binary classification (half-life of 30 days as the cutoff) model with an accuracy of 81% and a regression model with R 2 of 0.56 for SED based on LightGBM (80% and 0.31 for SLD based on Extra tree, respectively). The model interpretations underscored the significance of experimental conditions (e.g., temperature and inoculum dosage), as evidenced by their high feature importance, and the models were found to correctly capture the effects of chemical substructures, for example, branched structures and aromatic rings prolonged half-lives while methyl group and ortho-substitution on rings shortened half-lives. The applicability domains of the models were also defined, resulting in reasonable prediction for the half-lives of 41% (SED) or 67% (SLD) of over 4000 persistent, bioaccumulative, and toxic chemicals. Overall, this study pioneers ML models for predicting the anaerobic degradation half-lives, offering valuable support for future evaluation and implementation of chemical anaerobic biodegradation.

The development of liquid biopsy methods for the accurate and reliable detection of miRNAs in whole blood is critical for the early diagnosis and monitoring of diseases. However, accurate quantification of miRNA expression levels remains challenging due to the complex matrix and low abundance of miRNAs in blood samples. Herein, we report a contactless signal output strategy with low background interference that ensures "zero-contact" between the reaction system and the colorimetry system. The designed target-induced magnetic ZnS/ZIF-90/ZnS network can serve as a unique signal amplifier and transducer. It releases hydrogen sulfide (H 2 S) gas in an acidic solution which can be concentrated in a droplet of only a few microliters in volume, etching the silver layer of Au@Ag nanostars (NSTs) in the droplet. This will lead to changes in the localized surface plasmon resonance signals of the NSTs. Finally, quantitative detection of let-7a is realized by measuring the offset value of the UV-vis absorption peak. Therefore, by virtue of the synergistic action of quadruple signal amplification methods, including catalytic hairpin assembly, ZnS/ZIF-90/ZnS, magnetic separation, and microextraction, the "All-in-Tube" ultrasensitive detection of low-abundance let-7a in whole blood is achieved with a detection limit as low as the aM level. In addition, the "zero-contact" signal output mode effectively solves the problem of complex matrix interference, demonstrating the great potential of this method for miRNA quantification in complex samples, such as whole blood.

The surface of Titan, Saturn's icy moon, is believed to be composed of various molecular minerals with a great diversity in structure and composition. Under the surface conditions, 93 K and 1.45 atm, most small molecules solidify and form minerals, including acetylene and ammonia. These two compounds can not only form single-component solids but also a 1:1 binary cocrystal that exhibits intriguing rotor phase behavior. This cocrystal is a putative mineral on Titan and other planetary bodies such as comets. In addition, the structure of the cocrystal is relevant to fundamental science as it can help better understand the emergence of rotor phases. Here, we present a detailed vibrational neutron spectroscopic study supported by a neutron powder diffraction study on the cocrystal and the single-phase solids. The experimentally observed spectral bands were assigned based on theoretical calculations. The established spectra-properties correlations for the cocrystal corroborate the observed properties. To the best of our knowledge, this study presents the first example of the application of neutron vibrational spectroscopy in studying Titan-relevant organic minerals.

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging the synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated the synthesis of a series of chiral functionalized cyclopropanes with high yield, enantioselectivity, and diastereoselectivity (44 examples, up to 93% yield and >99% ee). A possible reaction mechanism involving cyclopropene desymmetrization by Co-H species and imine addition by Co-alkyl species was proposed. This study provides a novel route to important chiral cyclopropanes and extends the frontier of asymmetric metallaphotoredox catalysis.

In recent years, flexible strain sensors have gradually come into our lives due to their superiority in the field of biomonitoring. However, these sensors still suffer from poor durability, high hysteresis, and difficulty in calibration, resulting in great hindrance of practical application. Herein, starting with interfacial interaction regulation and structure-induced cracking, flexible strain sensors with high performance are successfully fabricated. In this strategy, dopamine treatment is used to enhance the bonding between flexible substrates and carbon nanotubes (CNT). The combination within the conductive networks is then controlled by substituting the CNT type. Braid-like fibers are employed to achieve controllable expansion of the conductive layer cracks. Finally, we obtain strain sensors that possess high linearity ( R 2 = 0.997) with low hysteresis (5%), high sensitivity (GF = 60) and wide sensing range (0-50%), short response time (62 ms), outstanding stability, and repeatability (>10,000 cycles). Flexible strain sensors with all performances good are rarely reported. Static and dynamic respiration and pulse signal monitoring by the fiber sensor are demonstrated. Moreover, a knee joint monitoring system is constructed for the monitoring of various walking stances, which is of great value to the diagnosis and rehabilitation of many diseases.