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Industrial fermentation applications typically require enzymes that exhibit high stability and activity at high temperatures. However, efforts to simultaneously improve these properties are usually limited by a trade-off between stability and activity. This report describes a computational strategy to enhance both activity and thermal stability of the mesophilic organophosphate-degrading enzyme, methyl parathion hydrolase (MPH). To predict hotspot mutation sites, we assembled a library of features associated with the target properties for each residue and then prioritized candidate sites by hierarchical clustering. Subsequent in silico screening with multiple algorithms to simulate selective pressures yielded a subset of 23 candidate mutations. Iterative parallel screening of mutations that improved thermal stability and activity yielded, MPHase-m5b, which exhibited 13.3 °C higher T m and 4.2 times higher catalytic activity than wild-type (WT) MPH over a wide temperature range. Systematic analysis of crystal structures, molecular dynamics (MD) simulations, and quantum mechanics/molecular mechanics (QM/MM) calculations revealed a wider entrance to the active site that increased substrate access with an extensive network of interactions outside the active site that reinforced αβ/βα sandwich architecture to improve thermal stability. This study thus provides an advanced, rational design framework to improve efficiency in engineering highly active, thermostable biocatalysts for industrial applications., (© 2024 Wiley-VCH GmbH.)

1,3-Dioxolane (DOL), with its broad liquid phase temperature window and low Li + -solvent binding energy, stands out as an ideal solvent candidate for the wide-temperature and high-rate electrolytes. Unfortunately, DOL is susceptible to undergo ring-opening polymerization under common lithium salts, which markedly retards the reaction kinetics. This work introduces the organic basic additive 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) to effectively suppress the polymerization, thus achieving compatibility between LiFSI, LiDFOB lithium salts, and DOL. Furthermore, density functional theory (DFT) calculations are utilized to elucidate the underlying mechanisms of DOL polymerization and to clarify how DBU inhibits its polymerization. The resulting electrolyte, devoid of polymer chain formation, forms a weak solvation structure rich in anions, which demonstrates rapid ion transport kinetics in the bulk electrolyte and excellent electrochemical stability at the electrolyte-electrode interfaces (EEIs) simultaneously. When applied to the LiFePO 4 ||graphite full cell, it exhibits exceptional wide-temperature and high-rate performance, with specific capacities reaching 101.2 mAh g -1 at room temperature (20 C), 36.9 mAh g -1 at -40 °C (0.5 C), and 118.0 mAh g -1 at 60 °C (20 C). This study significantly guides the development of wide-temperature, high-rate electrolytes., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

In this study, the VO 2 @5%Cu-VMOF/graphite felt (GF) is prepared as an electro-Fenton cathode via hydrothermal process and low-temperature carbonization for efficient antibiotics degradation. The VO 2 @5%Cu-VMOF/GF cathode exhibit great ciprofloxacin (CIP) degradation performance over the pH range of 2.1-7.2, and CIP removal reached 98.1% within 60 min at a pH of 3.4, with corresponding total organic carbon (TOC) removal of 68.7%. The cathode also showed desired catalytic performance toward various antibiotics decomposition. The great catalytic activity of the VO 2 @5%Cu-VMOF/GF cathode is attributed to lattice strain induced by Cu doping, and the elimination of the overpotential difference between the optimal oxygen reduction potential (OP ORR) and optimal metal reduction potential (OP MRR). Density Function Theory (DFT) calculations showed that Cu doping facilitated electrons accumulation around V atoms, and thus increased the content of low-valence metals in the cathode material. Four possible degradation pathways for CIP are proposed and intermediate toxicity is evaluated. This work advances the design and application of MOF derivatives as electro-Fenton cathodic materials for emerging contaminants degradation., (© 2024 Wiley‐VCH GmbH.)

Although multiplexed DNA fluorescence in situ hybridization (FISH) enables tracking the spatial localization of thousands of genomic loci using probes within individual cells, the high rates of undetected probes impede the depiction of 3D chromosome structures. Current data imputation methods neither utilize single-cell Hi-C data, which elucidate 3D genome architectures using sequencing nor leverage multimodal RNA FISH data that reflect cell-type information, limiting the effectiveness of these methods in complex tissues such as the mouse brain. To this end, a novel multiplexed DNA FISH imputation method named ImputeHiFI is proposed, which fully utilizes the complementary structural information from single-cell Hi-C data and the cell type signature from RNA FISH data to obtain a high-fidelity and complete spatial location of chromatin loci. ImputeHiFI enhances cell clustering, compartment identification, and cell subtype detection at the single-cell level in the mouse brain. ImputeHiFI improves the recognition of cell-type-specific loops in three high-resolution datasets. In short, ImputeHiFI is a powerful tool capable of imputing multiplexed DNA FISH data from various resolutions and imaging protocols, facilitating studies of 3D genome structures and functions., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Rechargeable lithium metal batteries (LMBs) are promising next-generation energy storage systems due to their high theoretical energy density. However, their practical applications are hindered by lithium dendrite growth and various intricate issues associated with the cathodes. These challenges can be mitigated by using organosulfur-based mediators (OSMs), which offer the advantages of abundance, tailorable structures, and unique functional adaptability. These features enable the rational design of targeted functionalities, enhance the interfacial stability of the lithium anode and cathode, and accelerate the redox kinetics of electrodes via alternative reaction pathways, thereby effectively improving the performance of LMBs. Unlike the extensively explored field of organosulfur cathode materials, OSMs have garnered little attention. This review systematically summarizes recent advancements in OSMs for various LMB systems, including lithium-sulfur, lithium-selenium, lithium-oxygen, lithium-intercalation cathode batteries, and other LMB systems. It briefly elucidates the operating principles of these LMB systems, the regulatory mechanisms of the corresponding OSMs, and the fundamentals of OSMs activity. Ultimately, strategic optimizations are proposed for designing novel OSMs, advanced mechanism investigation, expanded applications, and the development of safe battery systems, thereby providing directions to narrow the gap between rational modulation of organosulfur compounds and their practical implementation in batteries., (© 2024 Wiley‐VCH GmbH.)

All-solid-state lithium metal batteries (ASSLMBs) are renowned for their high energy density and safety, positioning them as leading candidates for next-generation energy storage solutions. In this study, pure polymer solid-state electrolytes are developed using the solution casting method, optimized for room temperature operation. The base material, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), is enhanced with succinonitrile (SN) and polyacrylonitrile (PAN) to improve its electrochemical performance at room temperature. The optimized electrolyte, PSP-0.05, demonstrated superior characteristics, including an ionic conductivity (σ) of 3.2 × 10 -4  S cm -1 and a wide voltage window of up to 5 V. When integrated into full batteries, PSP-0.05 exhibited exceptional performance in multiplicative cycling tests at room temperature, achieving discharge specific capacities of 132 and 113 mAh g -1 at 3 and 5 C rates, respectively. Additionally, long-term cycling at 1 C rate resulted in an initial discharge-specific capacity of 145.2 mAh g -1 with over 94.9% capacity retention after 1000 cycles. Given the simplicity of the preparation process and its impressive electrochemical properties, the PSP-0.05 electrolyte holds significant potential for practical applications in safer ASSLMBs., (© 2024 Wiley‐VCH GmbH.)

Silk fibroin (SF) with good biocompatibility can enable an efficient and safe implementation of neural interfaces. However, it has been difficult to achieve a robust integration of patterned conducting materials (multichannel electrodes) on flexible SF film substrates due to the absence of some enduring interactions. In this study, a thermo-assisted pattern-transfer technique is demonstrated that can facilely transfer a layer of pre-set poly(3,4-ethylenedioxythiophene) (PEDOT) onto the flexible SF substrate through an interpenetrating network of 2 polymer chains, achieving a desired substrate/conductor intertwined interface with good flexibility (≈33 MPa), conductivity (386 S cm -1 ) and stability in liquid state over 4 months simultaneously. Importantly, this technique can be combined with ink-jet printing to prepare a multichannel SF-based neural interface for the electrocorticogram (ECoG) recording and inflammation remission in rat models. The SF-based neural interface with satisfied tissue conformability, biocompatibility, and bioelectric conductivity is a promising ECoG acquisition tool, where the demonstrated approach can also be useful to develop other SF-based flexible bioelectronics., (© 2024 Wiley‐VCH GmbH.)

There is an urgent need to fully understand the biology of third generation EGFR-tyrosine kinase inhibitors (EGFR-TKIs), particularly osimertinib, and to develop mechanism-driven strategies to manage their acquired resistance. Transient receptor potential melastatin-2 (TRPM2) functions as an important regulator of Ca 2+ influx, but its role in mediating therapeutic efficacies of EGFR-TKIs and acquired resistance to EGFR-TKIs has been rarely studied. This study has demonstrated a previously undiscovered role of suppression of TRPM2 and subsequent inhibition of Ca 2+ influx and induction of ROS and DNA damage in mediating apoptosis induction and the therapeutic efficacy of osimertinib against EGFR mutant NSCLC. The rebound elevation represents a key mechanism accounting for the emergence of acquired resistance to osimertinib and other third generation EGFR-TKIs. Accordingly, targeting TRPM2 is a potentially promising strategy for overcoming and preventing acquired resistance to osimertinib, warranting further study in this direction including the development of cancer therapy-optimized TRPM2 inhibitors., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Biomass assumes an increasingly vital role in the realm of renewable energy and sustainable development due to its abundant availability, renewability, and minimal environmental impact. Within this context, 5-hydroxymethylfurfural (HMF), derived from sugar dehydration, stands out as a critical bio-derived product. It serves as a pivotal multifunctional platform compound, integral in synthesizing various vital chemicals, including furan-based polymers, fine chemicals, and biofuels. The high reactivity of HMF, attributed to its highly active aldehyde, hydroxyl, and furan ring, underscores the challenge of selectively regulating its conversion to obtain the desired products. This review highlights the research progress on efficient catalytic systems for HMF synthesis, oxidation, reduction, and etherification. Additionally, it outlines the techno-economic analysis (TEA) and prospective research directions for the production of furan-based chemicals. Despite significant progress in catalysis research, and certain process routes demonstrating substantial economics, with key indicators surpassing petroleum-based products, a gap persists between fundamental research and large-scale industrialization. This is due to the lack of comprehensive engineering research on bio-based chemicals, making the commercialization process a distant goal. These findings provide valuable insights for further development of this field., (© 2024 Wiley‐VCH GmbH.)

Lithium-ion batteries (LIBs) are paramount in energy storage in consumer electronics and electric vehicles. However, a narrow operating temperature range severely constrains their evolution. In this study, a wide-temperature operating LIB system is constructed utilizing carbon nanotube (CNT)-based electrodes and a "constructive alliance" electrolyte. The unique microstructure of the CNT current collector, with high electrical and thermal conductivity, accelerates the reaction kinetics of active materials at subzero temperatures and optimizes the thermal management of the entire electrode at elevated temperatures. Furthermore, a strategy employing the "constructive alliance" electrolyte is proposed, demonstrating that a simple combination of commercially available electrolytes can enhance resilience to harsh thermal conditions. Molecular dynamics simulations and density functional theory calculations reveal that the hybrid electrolyte predominantly adopts aggregate solvation structures and possesses low Li + desolvation barriers regardless of thermal variations. Consequently, the assembled Li 4 Ti 5 O 12 //LiCoO 2 full cell, with a negative/positive electrode material ratio of 1.2, exhibits outstanding electrochemical performance in the wide temperature range of -40 and 60 °C. This innovative strategy overcomes challenges in wide-temperature electrolyte research and offers promise for next-generation wide-temperature LIBs., (© 2024 Wiley‐VCH GmbH.)

Bismuth-based materials have been recognized as the appealing anodes for potassium-ion batteries (PIBs) due to their high theoretical capacity. However, the kinetics sluggishness and capacity decline induced by the structure distortion predominately retard their further development. Here, a heterostructure of polyaniline intercalated Bi 2 O 2 CO 3 /MXene (BOC-PA/MXene) hybrids is reported via simple self-assembly strategy. The ingenious design of heterointerface-rich architecture motivates significantly the interior self-built-in electric field (IEF) and high-density electron flow, thus accelerating the charge transfer and boosting ion diffusion. As a result, the hybrids realize a high reversible specific capacity, satisfying rate capability as well as long-term cycling stability. The in/ex situ characterizations further elucidate the stepwise intercalation-conversion-alloying reaction mechanism of BOC-PA/MXene. More encouragingly, the full cell investigation further highlights its competitive merits for practical application in further PIBs. The present work not only opens the way to the design of other electrodes with an appropriate working mechanism but also offers inspiration for built-in electric-field engineering toward high-performance energy storage devices., (© 2024 Wiley‐VCH GmbH.)

Lithium-ion batteries play an integral role in various aspects of daily life, yet there is a pressing need to enhance their safety and cycling stability. In this study, we have successfully developed a highly secure and flexible solid-state polymer electrolyte (SPE) through the in situ polymerization of allyl acetoacetate (AAA) monomers. This SPE constructed an efficient Li + transport channel inside and effectively improved the solid-solid interface contact of solid-state batteries to reduce interfacial impedance. Furthermore, it exhibited excellent thermal stability, an ionic conductivity of 3.82×10 -4  S cm -1 at room temperature (RT), and a Li + transport number (t Li+ ) of 0.66. The numerous oxygen vacancies on layered inorganic SiO 2 created an excellent environment for TFSI - immobilization. Free Li + migrated rapidly at the C=O equivalence site with the poly(allyl acetoacetate) (PAAA) matrix. Consequently, when cycled at 0.5C and RT, it displayed an initial discharge specific capacity of 140.6 mAh g -1 with a discharge specific capacity retention rate of 70 % even after 500 cycles. Similarly, when cycled at a higher rate of 5C, it demonstrated an initial discharge specific capacity of 132.3 mAh g -1 while maintaining excellent cycling stability., (© 2024 Wiley-VCH GmbH.)

Surface defects on photocatalysts could promote carrier separation and generate unsaturated sites for chemisorption and reactant activation. Nevertheless, the inactivation of oxygen vacancies (OVs) would deteriorate catalytic activity and limit the durability of defective materials. Herein, bagasse-derived carbon quantum dots (CQDs) are loaded on the Sn-doped Bi 2 O 2 CO 3 (BOC) via hydrothermal procedure to create Bi─O─C chemical bonding at the interface, which not only provides efficient atomic-level interfacial electron channels for accelerating carriers transfer, but also enhances durability. The optimized Sn-BOC/CQDs-2 achieves the highest photocatalytic removal efficiencies for levofloxacin (LEV) (88.7%) and Cr (VI) (99.3%). The elimination efficiency for LEV and Cr (VI) from the Sn-BOC/CQDs-2 is maintained at 55.1% and 77.0% while the Sn-BOC is completely deactivated after four cycle tests. Furthermore, the key role of CQDs in stabilization of OVs is to replace OVs as the active center of H 2 O and O 2 adsorption and activation, thereby preventing reactant molecules from occupying OVs. Based on theoretical calculations of the Fukui index and intermediates identification, three possible degradation pathways of LEV are inferred. This work provides new insight into improving the stability of defective photocatalysts., (© 2024 Wiley‐VCH GmbH.)

Developing efficient and stable halide perovskite-based photocatalysts for highly selectivity reduction CO 2 to valuable fuels remains a significant challenge due to their intrinsic instability. Herein, a novel heterostructure featuring 2D Cs 3 Sb 2 I 9 nanosheets on a 3D flower-like mesoporous NiTiO 3 framework using a top-down stepwise membrane fabrication technique is constructed. The unique bilayer heterostructure formed on the 3D mesoporous framework endowed NiTiO 3 /Cs 3 Sb 2 I 9 with sufficient and close interface contact, minimizing charge transport distance, and effectively promoting the charge transfer at the interface, thus improving the reaction efficiency of the catalyst surface. As revealed by characterization and calculation, the coupling of Cs 3 Sb 2 I 9 with NiTiO 3 facilitates the hydrogenation process during catalytic, directing reaction intermediates toward highly selective CH 4 production. Furthermore, the van der Waals forces inherent in the 3D/2D heterostructure with face-to-face contact provide superior stability, ensuring the efficient realization of photocatalytic CO 2 reduction to CH 4 . Consequently, the optimized 3D/2D NiTiO 3 /Cs 3 Sb 2 I 9 heterostructure demonstrates an impressive CH 4 yield of 43.4 µmol g -1  h -1 with a selectivity of up to 88.6%, surpassing most reported perovskite-based photocatalysts to date. This investigation contributes to overcoming the challenges of commercializing perovskite-based photocatalysts and paves the way for the development of sustainable and efficient CO 2 conversion technologies., (© 2024 Wiley‐VCH GmbH.)

Quantitative analysis of optical attenuation based on optical coherence tomography images will offer an effective method to enhance diagnostic capabilities. In this paper, the optical attenuation in demineralized caries specimens was calculated to distinguish between normal teeth and carious teeth and further to differentiate the severity of caries, and thus come to the half-automated diagnosis of dental caries. Results show that the attenuation coefficient in carious regions is approximately 4.97 mm - 1 ± 0.206 , while that of normal teeth is about 3.69 mm - 1 ± 0.231 . Attenuation coefficient of carious regions is 35% higher than that of normal teeth. Moreover, five classes of caries were qualified and classified based on the optical attenuation coefficient. Compared with the healthy teeth, there is a noticeable disparity in the attenuation coefficients of carious teeth, both on the surface and at the dentinoenamel junction. This study provides a method for accurate caries diagnosis, particularly in detection of early lesions and subtle structural changes., (© 2024 Wiley‐VCH GmbH.)

The interplay between bacteria and their host influences the homeostasis of the human immune microenvironment, and this reciprocal interaction also affects the process of tissue damage repair. A variety of immunomodulatory commensal bacteria reside in the body, capable of delivering membrane vesicles (MVs) to host cells to regulate the local immune microenvironment. This research revealed, for the initial time, the significant enhancement of mucosal and cutaneous wound healing by MVs secreted by the human commensal Lactobacillus reuteri (RMVs) through modulation of the inflammatory environment in wound tissue. Local administration of RMVs reduces the proportion of pro-inflammatory macrophages in inflamed tissues and mitigates the level of local inflammation, thereby facilitating the healing of oral mucosa and cutaneous wounds. The elevated oxidative stress levels in activated pro-inflammatory macrophages can be modulated by RMVs, resulting in phenotypic transformation of macrophages. Furthermore, 3-hydroxypropionaldehyde present in RMVs can decrease the mitochondrial permeability of macrophages and stabilize the mitochondrial membrane potential, thereby promoting the conversion of macrophages to an anti-inflammatory phenotype. This study pioneers the significance of commensal bacterial MVs in tissue injury repair and presents a novel concept for the repair of tissue damage., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Triple-negative breast cancer (TNBC), due to its high malignant degree and strong invasion ability, leads to poor prognosis and easy recurrence, so effectively curbing the invasion of TNBC is the key to obtaining the ideal therapeutic effect. Herein, a therapeutic strategy is developed that curbs high invasions of TNBC by inhibiting cell physiological activity and disrupting tumor cell structural function to achieve the time and space dual-blockade. The time blockade is caused by the breakthrough of the tumor-reducing blockade based on the ferroptosis process and the oxidation-toxic free radicals generated by enhanced sonodynamic therapy (SDT). Meanwhile, alkyl radicals from 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (AIPH) and 1 O 2 attacked the organelles of tumor cells under ultrasound (US), reducing the physiological activity of the cells. The attack of free radicals on the cytoskeleton, especially on the proteins of F-actin and its assembly pathway, achieves precise space blockade of TNBC. The damage to the cytoskeleton and the suppression of the repair process leads to a significant decline in the ability of tumor cells to metastasize and invade other organs. In summary, the FTM@AM nanoplatforms have a highly effective killing and invasion inhibition effect on invasive TNBC mediated by ultrasound, showcasing promising clinical transformation potential., (© 2024 Wiley‐VCH GmbH.)

The discovery of the topological transition in twisted bilayer (tBL) materials has attracted considerable attention in nano-optics. In the analogue of acoustics, however, no such topological transition has been found due to the inherent nondirectional scalar property of acoustic pressure. In this work, by using a theory-based nonlocal anisotropic design, the in-plane acoustic pressure is transformed into a spatially distributed vector field using twisted multilayer metasurfaces. So-called "acoustic magic angle"-related acoustic phenomena occur, such as nonlocal polariton hybridization and the topological Lifshitz transition. The dispersion becomes flat at the acoustic magic angle, enabling polarized excitations to propagate in a single direction. Moreover, the acoustic topological transition (from hyperbolic to elliptic dispersion) is experimentally observed for the first time as the twist angle continuously changes. This unique characteristic facilitates low-loss tunable polariton hybridization at the subwavelength scale. A twisted trilayer acoustic metasurface is also experimentally demonstrated, and more possibilities for manipulating acoustic waves are found. These discoveries not only enrich the concepts of moiré physics and topological acoustics but also provide a complete framework of theory and methodologies for explaining the phenomena that are observed., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

In South and Southeast Asia, the habit of chewing betel nuts is prevalent, which leads to oral submucous fibrosis (OSF). OSF is a well-established precancerous lesion, and a portion of OSF cases eventually progress to oral squamous cell carcinoma (OSCC). However, the specific molecular mechanisms underlying the malignant transformation of OSCC from OSF are poorly understood. In this study, the leading-edge techniques of Spatial Transcriptomics (ST) and Spatial Metabolomics (SM) are integrated to obtain spatial location information of cancer cells, fibroblasts, and immune cells, as well as the transcriptomic and metabolomic landscapes in OSF-derived OSCC tissues. This work reveals for the first time that some OSF-derived OSCC cells undergo partial epithelial-mesenchymal transition (pEMT) within the in situ carcinoma (ISC) region, eventually acquiring fibroblast-like phenotypes and participating in collagen deposition. Complex interactions among epithelial cells, fibroblasts, and immune cells in the tumor microenvironment are demonstrated. Most importantly, significant metabolic reprogramming in OSF-derived OSCC, including abnormal polyamine metabolism, potentially playing a pivotal role in promoting tumorigenesis and immune evasion is discovered. The ST and SM data in this study shed new light on deciphering the mechanisms of OSF-derived OSCC. The work also offers invaluable clues for the prevention and treatment of OSCC., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

We reported the synthesis of a series of structurally diverse CPL-active molecules, in which pyrene units were installed to chiral pm/po-[2,2]PCP scaffolds either with or without a triple bond spacer for pm/po-PCP-P1 and pm/po-PCP-P2, respectively. The X-ray crystallographic analyses revealed that these pyrene-based [2,2]PCP derivatives exhibited diverse structures and crystal packings in the solid phases. The pyrene-based [2,2]PCP derivatives exhibit various (chir)optical properties in organic solutions, depending on their respective structures. In a mixture of dioxane and water, pm/po-PCP-P1 emit green excimer fluorescence, whereas pm/po-PCP-P2 emit blue one. The chiroptical investigation demonstrated that Rp-pm-PCP-P1 and Rp-pm-PCP-P2 exhibited completely opposite CD and CPL signals even they possess the same chiral Rp-[2,2]PCP core. The same argument also holds for other chiral pyrene-based [2,2]PCP derivatives. The theoretical calculation revealed that these unusual phenomena were attributed to different orientation between transition electric dipole moments and the magnetic dipole moments originating from the presence or absence of a triple bond spacer. These pyrene-based [2,2]PCP derivatives display various colours and fluorescence emissions in the solid state and PMMA films, possibly due to the different packings as observed in the crystal structure. Moreover, these compounds also can interact with perylene diimide through π-π interactions, leading to near-white fluorescence., (© 2023 Wiley-VCH GmbH.)

Strong, lightweight, and shape-memory cellulose aerogels have great potential in multifunctional applications. However, achieving the integration of these features into a cellulose aerogel without harsh chemical modifications and the addition of mechanical enhancers remains challenging. In this study, a strong, lightweight, and water-stimulated shape-memory all-cellulose aerogel (ACA) is created using a combination strategy of partial dissolution and unidirectional freezing from bamboo. Benefiting from the firm architecture of cellulose microfibers bridging cellulose nanofibers /regenerated cellulose aggregated layers and the bonding of different cellulose crystal components (cellulose Iβ and cellulose II), the ACA, with low density (60.74 mg cm -3 ), possesses high compressive modulus (radial section: 1.2 MPa, axial section: 0.96 MPa). Additionally, when stimulated with water, the ACA exhibits excellent shape-memory features, including highly reversible compression-resilience and instantaneous fold-expansion behaviors. As a versatile scaffold, ACA can be integrated with hydroxyapatite, carboxyl carbon nanotubes, and LiCl, respectively, via a simple impregnation method to yield functionalized cellulose composites for applications in thermal insulation, electromagnetic interference shielding, and piezoresistive sensors. This study provides inspiration and a reliable strategy for the elaborately structural design of functional cellulose aerogels endows application prospects in various multifunction opportunities., (© 2023 Wiley-VCH GmbH.)

Efficient storage and separation of holes and electrons pose significant challenges for catalytic reactions, particularly in the context of single-phase catalysis. Herein, V 2 C MXene, with its intrinsic polarized electric field, successfully overcomes this obstacle. To enhance hole storage, a multistep etching process is employed under reducing conditions to control the content of surface termination groups, thus exposing more defective active sites. The intrinsically polarized electric field confines holes to the surface of the layer and free electrons within the layer, leading to a lag in e - release compared to h + . The quantities of stored holes and electrons are measured to be 18.13 µmol g -1 and 106.37 µmol g -1 , respectively. Under dark, V 2 C demonstrates excellent and stable dark-catalytic performance, degrading 57.91% of tetracycline (TC 40 mg L -1 ) and removing 23% of total organic carbon (TOC) after 140 min. In simulated sunlight and near-infrared light, the corresponding degradation rates reach 72.24% and 79.54%, with corresponding TOC removal rates of 49% and 48%, respectively. The hole and electron induced localized surface plasmon resonance (LSPR) effects contribute to a long-lasting and enhanced broad-spectrum mineralization of V 2 C MXene. This study provides valuable insights into the research and application of all-weather MXene energy storage catalytic materials., (© 2023 Wiley-VCH GmbH.)

Developing stable silicon-based and lithium metal anodes still faces many challenges. Designing new highly practical silicon-based anodes with low-volume expansion and high electrical conductivity, and inhibiting lithium dendrite growth are avenues for developing silicon-based and lithium metal anodes, respectively. In this study, SiO x C y microtubes are synthesized using a chemical vapor deposition method. As Li-ion battery anodes, the as-prepared SiO x C y not only combines the advantages of nanomaterials and the practical properties of micromaterials, but also exhibits high initial Coulombic efficiency (80.3%), low volume fluctuations (20.4%), and high cyclability (98% capacity retention after 1000 cycles). Furthermore, SiO x C y , as a lithium deposition substrate, can effectively promote the uniform deposition of metallic lithium. As a result, low nucleation overpotential (only 6.0 mV) and high Coulombic efficiency (≈98.9% after 650 cycles, 1.0 mA cm -2 and 1.0 mAh cm -2 ) are obtained on half cells, as well as small voltage hysteresis (only 9.5 mV, at 1.0 mA cm -2 ) on symmetric cells based on SiO x C y . Full batteries based on both SiO x C y and SiO x C y @Li anodes demonstrate great practicality. This work provides a new perspective for the simultaneous development of practical SiO x C y and dendrite-free lithium metal anodes., (© 2023 Wiley-VCH GmbH.)

Lithium-sulfur (Li-S) batteries with high energy density and low cost are the most promising competitor in the next generation of new energy reserve devices. However, there are still many problems that hinder its commercialization, mainly including shuttle of soluble polysulfides, slow reaction kinetics, and growth of Li dendrites. In order to solve above issues, various explorations have been carried out for various configurations, such as electrodes, separators, and electrolytes. Among them, the separator in contact with both anode and cathode is in a particularly special position. Reasonable design-modified material of separator can solve above key problems. Heterostructure engineering as a promising modification method can combine characteristics of different materials to generate synergistic effect at heterogeneous interface that is conducive to Li-S electrochemical behavior. This review not only elaborates the role of heterostructure-modified separators in dealing with above problems, but also analyzes the improvement of wettability and thermal stability of separators by modification of heterostructure materials, systematically clarifies its advantages, and summarizes some related progress in recent years. Finally, future development direction of heterostructure-based separator in Li-S batteries is given., (© 2023 Wiley-VCH GmbH.)

Hematogenous metastasis is the main approach for colorectal cancer liver metastasis (CRCLM). However, as the gatekeepers in the tumor vessels, the role of TPCs in hematogenous metastasis remains largely unknown, which may be attributed to the lack of specific biomarkers for TPC isolation. Here, microdissection combined with a pericyte medium-based approach is developed to obtain TPCs from CRC patients. Proteomic analysis reveals that TRP channel-associated factor 2 (TCAF2), a partner protein of the transient receptor potential cation channel subfamily M member 8 (TRPM8), is overexpressed in TPCs from patients with CRCLM. TCAF2 in TPCs is correlated with liver metastasis, short overall survival, and disease-free survival in CRC patients. Gain- and loss-of-function experiments validate that TCAF2 in TPCs promotes tumor cell motility, epithelial-mesenchymal transition (EMT), and CRCLM, which is attenuated in pericyte-conditional Tcaf2-knockout mice. Mechanistically, TCAF2 inhibits the expression and activity of TRPM8, leading to Wnt5a secretion in TPCs, which facilitates EMT via the activation of the STAT3 signaling pathway in tumor cells. Menthol, a TRPM8 agonist, significantly suppresses Wnt5a secretion in TPCs and CRCLM. This study reveals the previously unidentified pro-metastatic effects of TPCs from the perspective of cold-sensory receptors, providing a promising diagnostic biomarker and therapeutic target for CRCLM., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Rechargeable sodium ion batteries (SIBs) have promising applications in large-scale energy storage systems. Iron-based Prussian blue analogs (PBAs) are considered as potential cathodes owing to their rigid open framework, low-cost, and simple synthesis. However, it is still a challenge to increase the sodium content in the structure of PBAs and thus suppress the generation of defects in the structure. Herein, a series of isostructural PBAs samples are synthesized and the isostructural evolution of PBAs from cubic to monoclinic after modifying the conditions is witnessed. Accompanied by, the increased sodium content and crystallinity are discovered in PBAs structure. The as-obtained sodium iron hexacyanoferrate (Na 1.75 Fe[Fe(CN) 6 ] 0.9743 ·2.76H 2 O) exhibits high charge capacity of 150 mAh g -1 at 0.1 C (17 mA g -1 ) and excellent rate performance (74 mAh g -1 at 50 C (8500 mA g -1 )). Moreover, their highly reversible Na + ions intercalation/de-intercalation mechanism is verified by in situ Raman and Powder X-ray diffraction (PXRD) techniques. More importantly, the Na 1.75 Fe[Fe(CN) 6 ] 0.9743 ·2.76H 2 O sample can be directly assembled in a full cell with hard carbon (HC) anode and shows excellent electrochemical performances. Finally, the relationship between PBAs structure and electrochemical performance is summarized and prospected., (© 2023 Wiley-VCH GmbH.)

Antigen delivery based on non-virus-like particle self-associating protein nanoscffolds, such as Aquifex aeolicus lumazine synthase (AaLS), is limited due to the immunotoxicity and/or premature clearance of antigen-scaffold complex resulted from triggering unregulated innate immune responses. Here, using rational immunoinformatics prediction and computational modeling, we screen the T epitope peptides from thermophilic nanoproteins with the same spatial structure as hyperthermophilic icosahedral AaLS, and reassemble them into a novel thermostable self-assembling nanoscaffold RP T that can specifically activate T cell-mediated immunity. Tumor model antigen ovalbumin T epitopes and the severe acute respiratory syndrome coronavirus 2 receptor-binding domain are loaded onto the scaffold surface through the SpyCather/SpyTag system to construct nanovaccines. Compared to AaLS, RP T -constructed nanovaccines elicit more potent cytotoxic T cell and CD4 + T helper 1 (Th1)-biased immune responses, and generate less anti-scaffold antibody. Moreover, RP T significantly upregulate the expression of transcription factors and cytokines related to the differentiation of type-1 conventional dendritic cells, promoting the cross-presentation of antigens to CD8 + T cells and Th1 polarization of CD4 + T cells. RP T confers antigens with increased stability against heating, freeze-thawing, and lyophilization with almost no antigenicity loss. This novel nanoscaffold offers a simple, safe, and robust strategy for boosting T-cell immunity-dependent vaccine development., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

As one of the most widely used drugs, acetaminophen, is the leading cause of acute liver injury. In addition, acetaminophen-induced liver injury (AILI) has a strong relationship with the overproduced reactive oxygen species, which can be effectively eliminated by nanozymes. To address these challenges, mesoporous PdPt@MnO 2 nanoprobes (PPM NPs) mimicking peroxide, catalase, and superoxide dismutase-like properties are synthesized. They demonstrate nontoxicity, high colloidal stability, and exceptional reactive oxygen species (ROS)-scavenging ability. By scavenging excessive ROS, decreasing inflammatory cytokines, and inhibiting the recruitment and activation of monocyte/macrophage cells and neutrophils, the pathology mechanism of PPM NPs in AILI is confirmed. Moreover, PPM NPs' therapeutic effect and good biocompatibility may facilitate the clinical treatment of AILI., (© 2023 Wiley-VCH GmbH.)

The development of high-performance electrode materials is crucial for the advancement of sodium ion batteries (SIBs), and NiCo 2 S 4 has been identified as a promising anode material due to its high theoretical capacity and abundant redox centers. However, its practical application in SIBs is hampered by issues such as severe volume variations and poor cycle stability. Herein, the Mn-doped NiCo 2 S 4 @graphene nanosheets (GNs) composite electrodes with hollow nanocages were designed using a structure engineering method to relieve the volume expansion and improve the transport kinetics and conductivity of the NiCo 2 S 4 electrode during cycling. Physical characterization and electrochemical tests, combined with density functional theory (DFT) calculations indicate that the resulting 3 % Mn-NCS@GNs electrode demonstrates excellent electrochemical performance (352.9 mAh g -1 at 200 mA g -1 after 200 cycles, and 315.3 mAh g -1 at 5000 mA g -1 ). This work provides a promising strategy for enhancing the sodium storage performance of metal sulfide electrodes., (© 2023 Wiley-VCH GmbH.)

Antibacterial photodynamic therapy (APDT) has received considerable attention owing to its superiority. ZIF-8 was used to address the poor stability of the photosensitizer Rose Bengal (RB) encapsulation to synthesize RB@ZIF-8 NPs, which were doped into a composite film with poly (ϵ-caprolactone) (PCL) and polyvinyl alcohol-quaternary ammonium chitosan (PVA-QCS) as substrates to form composite films (PQZ). The composite films exhibited excellent photodynamic sterilization and good resistance to bacterial adhesion. The tensile strength of the film increased to 43.4 MPa, which was approximately 1.8 times that of the PCL film. With the addition of SiO 2 and RB@ZIF-8 NPs, the film exhibited water repellency and UV-blocking properties. RAW264.7 cells were selected using the MTT method to confirm that the composite films had excellent biocompatibility and had no significant inhibitory effect on cell growth and reproduction. PQZ multifunctional composite films show potential as novel APDT antimicrobial materials for food packaging., (© 2023 Wiley-VCH GmbH.)

Nanoparticles (NPs) at high loadings are often used in mixed matrix membranes (MMMs) to improve gas separation properties, but they can lead to defects and poor processability that impede membrane fabrication. Herein, it is demonstrated that branched nanorods (NRs) with controlled aspect ratios can significantly reduce the required loading to achieve superior gas separation properties while maintaining excellent processability, as demonstrated by the dispersion of palladium (Pd) NRs in polybenzimidazole for H 2 /CO 2 separation. Increasing the aspect ratio from 1 for NPs to 40 for NRs decreases the percolation threshold volume fraction by a factor of 30, from 0.35 to 0.011. An MMM with percolated networks formed by Pd NRs at a volume fraction of 0.039 exhibits H 2 permeability of 110 Barrer and H 2 /CO 2 selectivity of 31 when challenged with simulated syngas at 200 °C, surpassing Robeson's upper bound. This work highlights the advantage of NRs over NPs and nanowires and shows that right-sizing nanofillers in MMMs is critical to construct highly sieving pathways at minimal loadings. This work paves the way for this general feature to be applied across materials systems for a variety of chemical separations., (© 2023 Wiley-VCH GmbH.)

NiCo 2 S 4 is an attractive anode for sodium-ion batteries (SIBs) due to its high capacity and excellent redox reversibility. Practical deployment of NiCo 2 S 4 electrode in SIBs, however, is still hindered by the inferior capacity and unsatisfactory cycling performance, which result from the mismatch between the electrolyte chemistry and electrode. Herein, a functional electrolyte containing 1.0 m NaCF 3 SO 3 in diethylene glycol dimethyl ether (DEGDME) (1.0 m NaCF 3 SO 3 -DEGDME) is developed, which can be readily used for NiCo 2 S 4 anode with high initial coulomb efficiency (96.2%), enhanced cycling performance, and boosted capacities (341.7 mA h g -1 after 250 continuous cycles at the current density of 200 mA g -1 ). The electrochemical tests and related phase characterization combined with density functional theory (DFT) calculation indicate the ether-based electrolyte is more suitable for the NiCo 2 S 4 anode in SIBs due to the formation of a stable electrode-electrolyte interface. Additionally, the importance of the voltage window is also demonstrated to further optimize the electrochemical performance of the NiCo 2 S 4 electrode. The formation of sulfide intermediates during charging and discharging is predicted by combining DFT and verified by in situ XRD and HRTEM. The findings indicate that electrolyte engineering would be an effective way of performance enhancement for sulfides in practical SIBs., (© 2023 Wiley-VCH GmbH.)

Scaling up the chemical vapor deposition (CVD) of monolayer transition metal dichalcogenides (TMDCs) is in high demand for practical applications. However, for CVD-grown TMDCs on a large scale, there are many existing factors that result in their poor uniformity. In particular, gas flow, which usually leads to inhomogeneous distributions of precursor concentrations, has yet to be well controlled. In this work, the growth of uniform monolayer MoS 2 on a large scale by the delicate control of gas flows of precursors, which is realized by vertically aligning a well-designed perforated carbon nanotube (p-CNT) film face-to-face with the substrate in a horizontal tube furnace, is achieved. The p-CNT film releases gaseous Mo precursor from the solid part and allows S vapor to pass through the hollow part, resulting in uniform distributions of both gas flow rate and precursor concentrations near the substrate. Simulation results further verify that the well-designed p-CNT film guarantees a steady gas flow and a uniform spatial distribution of precursors. Consequently, the as-grown monolayer MoS 2 shows quite good uniformity in geometry, density, structure, and electrical properties. This work provides a universal pathway for the synthesis of large-scale uniform monolayer TMDCs, and will advance their applications in high-performance electronic devices., (© 2023 Wiley-VCH GmbH.)

Background: Lipidomics and metabolomics are closely related to tumor phenotypes, and serum lipoprotein subclasses and small-molecule metabolites are considered as promising biomarkers for breast cancer (BC) diagnosis. This study aimed to explore potential biomarker models based on lipidomic and metabolomic analysis that could distinguish BC from healthy controls (HCs) and triple-negative BC (TNBC) from non-TNBC., Methods: Blood samples were collected from 114 patients with BC and 75 HCs. A total of 112 types of lipoprotein subclasses and 30 types of small-molecule metabolites in the serum were detected by 1 H-NMR. All lipoprotein subclasses and small-molecule metabolites were subjected to a three-step screening process in the order of significance (p < 0.05), univariate regression (p < 0.1), and lasso regression (nonzero coefficient). Discriminant models of BC versus HCs and TNBC versus non-TNBC were established using binary logistic regression., Results: We developed a valid discriminant model based on three-biomarker panel (formic acid, TPA2, and L6TG) that could distinguish patients with BC from HCs. The area under the receiver operating characteristic curve (AUC) was 0.999 (95% confidence interval [CI]: 0.995-1.000) and 0.990 (95% CI: 0.959-1.000) in the training and validation sets, respectively. Based on the panel (D-dimer, CA15-3, CEA, L5CH, glutamine, and ornithine), a discriminant model was established to differentiate between TNBC and non-TNBC, with AUC of 0.892 (95% CI: 0.778-0.967) and 0.905 (95% CI: 0.754-0.987) in the training and validation sets, respectively., Conclusion: This study revealed lipidomic and metabolomic differences between BC versus HCs and TNBC versus non-TNBC. Two validated discriminatory models established against lipidomic and metabolomic differences can accurately distinguish BC from HCs and TNBC from non-TNBC., Impact: Two validated discriminatory models can be used for early BC screening and help BC patients avoid time-consuming, expensive, and dangerous BC screening., (© 2022 Wiley-VCH GmbH.)

Fluorescence imaging uses changes in the fluorescence intensity and emission wavelength to analyze multiple targets simultaneously. To increase the number of targets that can be identified simultaneously, fluorescence blinking can be used as an additional parameter. To understand and eventually control blinking, we used DNA as a platform to elucidate the processes of electron transfer (ET) leading to blinking, down to the rate constants. With a fixed ET distance, various blinking patterns were observed depending on the DNA sequence between the donor and acceptor units of the DNA platform. The blinking pattern was successfully described with a combination of ET rate constants. Therefore, molecules with various blinking patterns can be developed by tuning ET. It is expected that the number of targets that can be analyzed simultaneously will increase by the power of the number of blinking patterns., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The polysulfide (PS) dissolution and low conductivity of lithium sulfides (Li 2 S) are generally considered the main reasons for limiting the reversible capacity of the lithium-sulfur (Li-S) system. However, as the inevitable intermediate between PSs and Li 2 S, lithium disulfide (Li 2 S 2 ) evolutions are always overlooked. Herein, Li 2 S 2 evolutions are monitored from the operando measurements on the pouch cell level. Results indicate that Li 2 S 2 undergoes slow electrochemical reduction and chemical disproportionation simultaneously during the discharging process, leading to further PS dissolution and Li 2 S generation without capacity contribution. Compared with the fully oxidized Li 2 S, Li 2 S 2 still residues at the end of the charging state. Therefore, instead of the considered Li 2 S and PSs, slow electrochemical conversions and side chemical reactions of Li 2 S 2 are the determining factors in limiting the sulfur utilization, corresponding to the poor reversible capacity of Li-S batteries., (© 2023 Wiley-VCH GmbH.)

Silicon is an excellent candidate for the next generation of ultra-high performance anode materials, with the rapid iteration of the lithium-ion battery industry. High-quality silicon sources are the cornerstone of the development of silicon anodes, and silicon cutting waste (SCW) is one of them while still faces the problems of poor performance and unclear structure-activity relationship. Herein, a simple, efficient, and inexpensive purification method is implemented to reduce impurities in SCW and expose the morphology of nanosheets therein. Furthermore, HF is used to modulate the abundant native O in SCW after thermodynamic and kinetic considerations, realizing the mechanical support for the internal Si in the form of an amorphous SiO 2 shell. Afterward, SCNS@SiO 2 -2.5 with a 1.0 nm thick SiO 2 shell exhibits a reversible capacity of 1583.3 mAh g -1 after 200 cycles at 0.8 A g -1 . Ultimately, the molecular dynamics simulations profoundly reveal that the amorphous SiO 2 shell is transformed into the extremely ductile Li x SiO y shell to ditch stress and relieve strain during the lithiation/delithiation process., (© 2022 Wiley-VCH GmbH.)

Triple-negative breast cancer (TNBC) has higher molecular heterogeneity and metastatic potential and the poorest prognosis. Because of limited therapeutics against TNBC, irradiation (IR) therapy is still a common treatment option for patients with lymph nodes or brain metastasis. Thus, it is urgent to develop strategies to enhance the sensitivity of TNBC tumors to low-dose IR. Here, the authors report that E3 ubiquitin ligase Ring finger protein 126 (RNF126) is important for IR-induced ATR-CHK1 pathway activation to enhance DNA damage repair (DDR). Mechanistically, RNF126 physically associates with the MRE11-RAD50-NBS1 (MRN) complex and ubiquitinates MRE11 at K339 and K480 to increase its DNA exonuclease activity, subsequent RPA binding, and ATR phosphorylation, promoting sustained DDR in a homologous recombination repair-prone manner. Accordingly, depletion of RNF126 leads to increased genomic instability and radiation sensitivity in both TNBC cells and mice. Furthermore, it is found that RNF126 expression is induced by IR activating the HER2-AKT-NF-κB pathway and targeting RNF126 expression with dihydroartemisinin significantly improves the sensitivity of TNBC tumors in the brain to IR treatment in vivo. Together, these results reveal that RNF126-mediated MRE11 ubiquitination is a critical regulator of the DDR, which provides a promising target for improving the sensitivity of TNBC to radiotherapy., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Human-interfaced electronic systems require strain-resilient circuits. However, present integrated stretchable electronics easily suffer from electrical deterioration and face challenges in forming robust multilayered soft-rigid hybrid configurations. Here, a bilayer liquid-solid conductor (b-LSC) with amphiphilic properties is introduced to reliably interface with both rigid electronics and elastomeric substrates. The top liquid metal can self-solder its interface with rigid electronics at a resistance 30% lower than the traditional tin-soldered rigid interface. The bottom polar composite comprising liquid metal particles and polymers can not only reliably interface with elastomers but also help the b-LSC heal after breakage. The b-LSC can be scalably fabricated by printing and subsequent peeling strategies, showing ultra-high strain-insensitive conductivity (maximum 22 532 S cm -1 ), extreme stretchability (2260%), and negligible resistance change under ultra-high strain (0.34 times increase under 1000% strain). It can act as stretchable vertical interconnect access for connecting multilayered layouts and can be scalably and universally fabricated on various substrates with a resolution of ≈200 µm. It is demonstrated that it can construct stretchable sensor arrays, multi-layered stretchable displays, highly integrated haptic user-interactive optoelectric E-skins, visualized heaters, robot touch sensing systems, and wireless powering for wearable electronics., (© 2022 Wiley-VCH GmbH.)

Metal-free polymer daytime radiative cooling coatings with hierarchical eye-like air pores are proposed and fabricated with a super-large-scale film-stretching method. The hierarchically porous film (HPF) can be further coated with polymethyl methacrylate (PMMA) micro-hemispheres, forming coated HPF (cHPF), which do not dramatically change the optical or thermal properties. The cHPF is slightly better with a lower solar absorptivity (2.4%) and a higher thermal emissivity over the atmospheric transparency window (90.1%). The low solar absorptivity is due to the strong scattering of the hierarchical eye-like air pores, while the molecular vibrations and the focusing effect of the PMMA micro-hemispheres contribute to the high emissivity. An average mid-day temperature reduction of 7.92 °C is achieved relative to the air temperature, and the average cooling power reaches 116.0 W m -2 , which are much better than the cooling performances of the commercial cooling cushion. During the day, the cHPF-covered simulated building is up to 6.47 and 4.84 °C cooler than the ambient and the white painted counterpart, respectively. The film is durable and resistant to chemical etching, and very promising to use globally, especially in warm and tropical regions., (© 2022 Wiley-VCH GmbH.)

Disulfide bond formation is a common mechanism for regulating conformational changes in proteins during oxidative folding. Despite extensive studies of the use of multiple disulfide bonds to constrain peptide conformation, few studies have explored their usage in developing self-assembling peptides. Herein, we report that a thiol-rich peptide could fold into an amphiphilic β-hairpin conformation through the formation of two hetero-disulfide bonds upon oxidation, subsequently self-assembling into a mechanically rigid hydrogel. Breaking disulfide bonds under reductive condition, the hydrogel exhibited a transition from hydrogel to solution. Molecular simulation revealed that intermolecular interaction between two tryptophan residues was indispensable for hydrogelation. This work is the first case of the use of multiple disulfide bonds to control conformational change and self-assembly, and provides a cell-compatible hydrogel material for potential biomedical application., (© 2022 Wiley-VCH GmbH.)

Extracellular vesicles (EVs) have attracted attention as delivery vehicles due to their structure, composition, and unique properties in regeneration and immunomodulation. However, difficulties during production and isolation processes of EVs limit their large-scale clinical applications. EV mimetics (EVMs), prepared via top-down strategies that improve the yield of nanoparticles while retaining biological properties similar to those of EVs have been used to address these limitations. Herein, the preparation of EVMs is reviewed and their characteristics in terms of structure, composition, targeting ability, cellular uptake mechanism, and immunogenicity, as well as their strengths, limitations, and future clinical application prospects as EV alternatives are summarized., (© 2022 Wiley-VCH GmbH.)

The mitochondria represent a potential target for the treatment of triple-negative breast cancer (TNBC) and shikonin (SK) has shown remarkable therapeutic effects on TNBC. Herein, it is found that SK possesses potent inhibitory effects on mitochondrial biogenesis via targeting polymerase gamma (POLG). However, its application is restricted by its poor aqueous solubility and stability, and therefore, a biomimetic micelle to aid with tumor lesion accumulation and mitochondria-targeted delivery of SK is designed. A folic acid (FA) conjugated polyethylene glycol derivative (FA-PEG-FA) is inserted onto the external membranes of red blood cells (FP-RBCm) to prepare a "right-side-out" RBCm-camouflaged cationic micelle (ThTM/SK@FP-RBCm). Both FP-RBCm coating and a triphenylphosphine (TPP) moiety on the periphery of micelles contribute to tumor lesion distribution, receptor-mediated cellular uptake, and electrostatic attraction-dependent mitochondrial targeting, thereby maximizing inhibitory effects on mitochondrial biosynthesis in TNBC cells. Intravenous administration of ThTM/SK@FP-RBCm leads to profound inhibition of tumor growth and lung metastasis in a TNBC mouse model with no obvious toxicity. This work highlights the mitochondria-targeted delivery of SK using a "right-side-out" membrane-camouflaged micelle for the inhibition of mitochondrial biogenesis and enhanced therapeutic effects on TNBC., (© 2022 Wiley-VCH GmbH.)

Miharamycins belong to a class of peptidyl nucleoside antibiotics with a unique nine-carbon pyranosyl amino acid core and a rare 2-aminopurine moiety. Herein, we report the de novo total synthesis of miharamycin B and its biosynthetic precursor from 3-bromofuran and Garner's aldehyde through a modified Achmatowicz reaction. Many challenges were resolved toward the de novo synthesis of miharamycin B, including the introduction of a dense array of functional groups, the stereoselective construction of consecutive stereocenters, dealing with the variability of the anomeric positions, and promoting site-selectivity in the cyclization to form the tetrahydrofuran ring. This de novo synthesis strategy enables efficient preparation of 3'-substituted saccharides, allowing the study of their structure-activity relationships and mode of action, and meets the growing demand for the development of novel antibiotics inspired by miharamycin natural products., (© 2022 Wiley-VCH GmbH.)

Diabetic wound is a significant challenge for clinical treatment with high morbidity and mortality. Plenty of hydrogels with good biocompatibility have been widely used in diabetic wound healing. However, most of them cannot be directly absorbed and utilized by the wounds, which prolongs the regeneration time. Here a new type of healing hydrogel is developed that is based on histidine, a natural dietary essential amino acid that is significant for tissue formation. The amino acid is cross-linked with zinc ions (Zn 2+ ) and sodium alginate (SA) via dynamic coordinate and hydrogen bonds, respectively, forming a histidine-SA-Zn 2+ (HSZH) hydrogel with good injectable, adhesive, biocompatible, and antibacterial properties. Application of this dual-dynamic-bond cross-linked HSZH hydrogel accelerates the migration and angiogenesis of skin-related cells in vitro. Furthermore, it significantly promotes the healing of infected diabetic wounds in vivo and uniquely allows a full repair of wounds within ≈13 days, while ≈27 days are required for the healing process of the control group. This work provides a new strategy for designing wound dressing materials, that weakly cross-linked material based on tissue-friendly micromolecules can heal the wounds more efficiently than highly cross-linked materials based on long-chain polymers., (© 2022 Wiley-VCH GmbH.)

In this work, electrocatalytic upgrade of n-valeraldehyde to octane with higher activity and selectivity is achieved over Au single-atom catalysts (SACs)-NiMn 2 O 4 spinel synergetic composites. Experiments combined with density functional theory calculation collaboratively demonstrate that Au single-atoms occupy surface Ni 2+ vacancies of NiMn 2 O 4 , which play a dominant role in n-valeraldehyde selective oxidation. A detailed investigation reveals that the initial n-valeraldehyde molecule preferentially adsorbs on the Mn tetrahedral site of NiMn 2 O 4 spinel synergetic structures, and the subsequent n-valeraldehyde molecule easily adsorbs on the Ni site. Specifically, Au single-atom surficial derivation over spinel lowers the adsorption energy (E ads ) of the initial n-valeraldehyde molecule, which will facilitate its adsorption on the Mn site of Au SACs-NiMn 2 O 4 . Furthermore, the single-atom Au surficial derivation not only alters the electronic structure of Au SACs-NiMn 2 O 4 but also lower the E ads of subsequent n-valeraldehyde molecule. Hence, the subsequent n-valeraldehyde molecules prefer adsorption on Au sites rather than Ni sites, and the process of two alkyl radicals originating from Mn-C 4 H 9 and Au-C 4 H 9 dimerization into an octane is accordingly accelerated. This work will provide an avenue for the rational design of SACs and supply a vital mechanism for understanding the electrocatalytic upgrade of n-valeraldehyde to octane., (© 2022 Wiley-VCH GmbH.)

Mixed matrix materials (MMMs) hold great potential for membrane gas separations by merging nanofillers with unique nanostructures and polymers with excellent processability. In situ growth of the nanofillers is adapted to mitigate interfacial incompatibility to avoid the selectivity loss. Surprisingly, functional polymers have not been exploited to co-grow the nanofillers for membrane applications. Herein, in situ synergistic growth of crystalline zeolite imidazole framework-8 (ZIF-8) in polybenzimidazole (PBI), creating highly porous structures with high gas permeability, is demonstrated. More importantly, PBI contains benzimidazole groups (similar to the precursor for ZIF-8, i.e., 2-methylimidazole) and induces the formation of amorphous ZIFs, enhancing interfacial compatibility and creating highly size-discriminating bottlenecks. For instance, the formation of 15 mass% ZIF-8 in PBI improves H 2 permeability and H 2 /CO 2 selectivity by ≈100% at 35 °C, breaking the permeability/selectivity tradeoff. This work unveils a new platform of MMMs comprising functional polymer-incorporated amorphous ZIFs with hierarchical nanostructures for various applications., (© 2022 Wiley-VCH GmbH.)

Amid the burgeoning environmental concerns, electrochemical energy storage is of great demand, inspiring the rapid development of electrolytes. Quasi-liquid solid electrolytes (QLSEs) demonstrate exciting properties that combine high ionic conductivity and safety. Herein, a QLSE system is constructed by confining ionic liquids (ILs) into 2D materials-based membranes, which creates a subtle platform for the investigation of the nanoconfined ion transport process. The highest ionic conductivity increment of 506% can be observed when ILs are under nanoconfinement. Correlation of experimental results and simulation evidently prove the diffusion behaviors of ILs are remarkably accelerated when confined in nanochannels, ascribing from the promoted dissociation of ILs. Concurrently, nanoconfined ILs demonstrate a highly ordered distribution, lower interplay, and higher free volume compared against bulk systems. This work reveals and analyzes the phenomenon of ionic conductivity elevation in nanoconfined ILs, and offers inspiring opportunities to fabricate the highly stable and efficient QLSEs based on layered nanomaterials for energy storage applications., (© 2022 Wiley-VCH GmbH.)

High-performance droplet transport is crucial for diverse applications including biomedical detection, chemical micro-reaction, and droplet microfluidics. Despite extensive progress, traditional passive and active strategies are restricted to limited liquid types, small droplet volume ranges, and poor biocompatibilities. Moreover, more challenges occur for biological fluids due to large viscosity and low surface tension. Here, a vibration-actuated omni-droplets rectifier (VAODR) consisting of slippery ratchet arrays fabricated by femtosecond laser and vibration platforms is reported. Through the relative competition between the asymmetric adhesive resistance originating from the lubricant meniscus on the VAODR and the periodic inertial driving force originating from isotropic vibration, the fast (up to ≈60 mm s -1 ), programmable, and robust transport of droplets is achieved for a large volume range (0.05-2000 µL, V max /V min  ≈ 40 000) and in various transport modes including transport of liquid slugs in tubes, programmable and sequential transport, and bidirectional transport. This VAODR is general to a high diversity of biological and medical fluids, and thus can be used for biomedical detection including ABO blood-group tests and anticancer drugs screening. These strategies provide a complementary and promising platform for maneuvering omni-droplets that are fundamental to biomedical applications and other high-throughput omni-droplet operation fields., (© 2022 Wiley-VCH GmbH.)

Yangwei decoction, a classical traditional Chinese medicine prescription, has been widely used to treat exogenous cold and internal injury with damp stagnation for many centuries. However, its systematic chemical profiling remains ambiguous, which has hampered the interpretation of pharmacology and the mechanism of its formula. In the present study, ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry method was successfully established for the first time to separate and identify the complicated components of Yangwei decoction. The accurate mass data of the protonated molecules, deprotonated molecules, and fragment ions were detected in positive and negative ion modes. A total of 226 compounds in Yangwei decoction were tentatively identified and unambiguously characterized by comparing their retention times and mass spectrometry data with those of reference standards and literature, including 24 lignans, 18 alkaloids, 9 phenylpropanoid glycosides, 76 flavonoids, 59 triterpenoids, 17 organic acids, 7 gingerols, 8 lactones, and 8 other compounds. The present study provides a novel method of constituents characterization for well-known Chinese medicine prescriptions. The study aims to lay a robust foundation for future research, providing the holistic quality control and pharmacology of Yangwei decoction., (© 2022 Wiley-VCH GmbH.)