Construction of anticancer drug incorporated aptamer-functionalized cationic ß-lactoglobulin: induction of cell cycle arrest and apoptosis in colorectal cancer.

Nanoscale drug delivery systems that are both multifunctional and targeted have been developed using proteins as a basis, thanks to their attractive biomacromolecule properties. A novel nanocarrier, aptamer (AS1411)-conjugated ß-lactoglobulin/poly-l-lysine (BLG/Ap/PL) nanoparticles, was developed in this study. To this unique formulation, the as-prepared nanocarrier blends the distinctive features of an aptamer as a chemotherapeutic targeting agent with those of protein nanocarriers. By loading cabazitaxel (CTX) onto the nanocarriers, the therapeutic potential of BLG/Ap/PL could be demonstrated. The CTX-loaded BLG/Ap/PL (CTX@BLG/Ap/PL) showed a regulated drug release profile in an acidic milieu, which could improve therapeutic efficacy in cancer cells and have a high drug encapsulation efficacy of up to 93%. However, compared to free CTX, CTX@BLG/Ap/PL killed colorectal HCT116 cancer cells with a higher efficacy at 24 and 48 h. Further investigation confirms the apoptosis by acridine orange and ethidium bromide (AO/EB), and DAPI staining confirms the morphological changes, chromatin condensation, and membrane blebbing in the treated cell through flow cytometry displayed the release of higher percentages of apoptosis. Cell cycle analysis revealed that CTX@BLG/Ap/PL induced sub-G1 and G2/M phase (apoptosis) at 24 and 48 h. Annexin V/propidium iodide (PI) flow cytometry analysis confirmed that CTX@BLG/Ap/PL induces apoptosis in HCT116 cells. Overall, this study proved that CTX@BLG/Ap/PL had several advantages over free chemotherapeutic drugs and showed promise as a solution to the clinical problems associated with targeted antitumor drug delivery systems.

Transmitted drug resistance and molecular transmission network among treatment-naive HIV-1 patients in Wenzhou, China, 2020-2023.

BACKGROUND: Transmitted drug resistance (TDR) increases the risk of antiretroviral therapy (ART) failure in HIV-1 patients. This study investigated the molecular epidemiology of TDR and its transmission networks among newly diagnosed HIV-1 patients in Wenzhou, China. METHODS: We enrolled 1878 ART-naive HIV-1 patients from January 2020 to October 2023. TDR was evaluated using the Stanford University HIV Drug Resistance Database. We performed phylogenetic analysis, genotyping, transmission clustering, and population-based TDR-related factor analysis. RESULTS: Among 1782 patients with successful genotyping, TDR prevalence was 5.7%. Multivariable analysis identified CRF08_BC subtype (adjusted odds ratio [aOR] 18.59, 95% CI 3.79-336.18, p = 0.004), CD4 > 500 cells/mm³ (aOR 2.19, 95% CI 1.16-4.03, p = 0.013), and year 2023 (aOR 1.83, 95% CI 1.11-4.89, p = 0.039) as factors associated with higher TDR risk. The most prevalent NNRTI mutations were K103N, E138A, and V179E. Seven TDR transmission clusters were identified, notably one with V179D that expanded during 2020-2023. CONCLUSIONS: While TDR prevalence in Wenzhou remained lower than in other Chinese regions, an upward trend was observed. Most resistant individuals were in transmission clusters, predominantly middle-aged and elderly. NNRTI resistance was severe and concentrated in efavirenz, nevirapine, and rilpivirine. Enhanced HIV surveillance and wider free antiretroviral options are crucial to control drug-resistant HIV spread in Wenzhou.

Optimized protocol for the multiomics processing of cryopreserved human kidney tissue.

Biobanking of tissue from clinically obtained kidney biopsies for later analysis with multiomic approaches, such as single-cell technologies, proteomics, metabolomics, and the different types of imaging, is an inevitable step to overcome the need of disease model systems and toward translational medicine. Hence, collection protocols that ensure integration into daily clinical routines by the usage of preservation media that do not require liquid nitrogen but instantly preserve kidney tissue for both clinical and scientific analyses are necessary. Thus, we modified a robust single-nucleus dissociation protocol for kidney tissue stored snap-frozen or in the preservation media RNAlater and CellCover. Using at first porcine kidney tissue as a surrogate for human kidney tissue, we conducted single-nucleus RNA sequencing with the widely recognized Chromium 10X Genomics platform. The resulting datasets from each storage condition were analyzed to identify any potential variations in transcriptomic profiles. Furthermore, we assessed the suitability of the preservation media for additional analysis techniques such as proteomics, metabolomics, and the preservation of tissue architecture for histopathological examination including immunofluorescence staining. In this study, we show that in daily clinical routines, the preservation medium RNAlater facilitates the collection of highly preserved human kidney biopsies and enables further analysis with cutting-edge techniques like single-nucleus RNA sequencing, proteomics, and histopathological evaluation. Only metabolome analysis is currently restricted to snap-frozen tissue. This work will contribute to build tissue biobanks with well-defined cohorts of the respective kidney disease that can be deeply molecularly characterized, opening up new horizons for the identification of unique cells, pathways and biomarkers for the prevention, early identification, and targeted therapy of kidney diseases.NEW & NOTEWORTHY In this study, we addressed challenges in integrating clinically obtained kidney biopsies into everyday clinical routines. Using porcine kidneys, we evaluated preservation media (RNAlater and CellCover) versus snap freezing for multi-omics processing. Our analyses highlighted RNAlater's suitability for single-nucleus RNA sequencing, proteome analysis and histopathological evaluation. Only metabolomics are currently restricted to snap-frozen biopsies. Our research established a cryopreservation protocol that facilitates tissue biobanking for advancing precision medicine in nephrology.

Biochar derived from straw residue prepared via combined pre-treatment designed for efficient removal of tetracycline hydrochloride and sulfadiazine sodium salt.

In this study, straw residue (SR) was prepared from corn straw by a combined pre-treatment method that involved both microbial treatment (Myrothecium verrucaria, Aspergillus niger, and Trichoderma reesei) and treatment with ρ-toluenesulfonic acid. After pre-treatment, the cellulose content of the residues reached 79.3 %, 72.1 %, 83.5 %, and 85.2 %, respectively. The results indicated that Aspergillus niger and Trichoderma reesei effectively destroyed the corn stover structure, improving the efficiency of the subsequent treatment. Following carbonation and activation processes, the SRs were converted into a series of biochars (ACCC, ACMC, ACTC, and ACNC) with large specific surface areas (2343, 2219, 2693, 2672 m2 g-1). The prepared biochars demonstrated excellent performance in adsorption tests performed using tetracycline hydrochloride (TC) and sulfadiazine sodium salt (SDZ) as adsorption models. The maximum adsorption capacities recorded for TC (908, 1117, 1216, and 1189 mg/g) and SDZ (930, 965, 1033, and 1083 mg/g) were higher than most of the other adsorbents. Furthermore, the potential adsorption mechanisms included pore filling, π-π interactions, hydrogen bonding, and electrostatic attraction. Even after 5 test cycles, the biochar retained over 75 % of its adsorption performance, highlighting its strong potential for applications in removing antibiotics from water.

Prospective Comparison of FOCUS MUSE and Single-Shot Echo-Planar Imaging for Diffusion-Weighted Imaging in Evaluating Thyroid-Associated Ophthalmopathy.

OBJECTIVE: To prospectively compare single-shot (SS) echo-planar imaging (EPI) and field-of-view optimized and constrained undistorted single-shot multiplexed sensitivity-encoding (FOCUS MUSE) for diffusion-weighted imaging (DWI) in evaluating thyroid-associated ophthalmopathy (TAO). MATERIALS AND METHODS: SS EPI and FOCUS MUSE DWIs were obtained from 39 patients with TAO (18 male; mean ± standard deviation: 48.3 ± 13.3 years) and 26 healthy controls (9 male; mean ± standard deviation: 43.0 ± 18.5 years). Two radiologists scored the visual image quality using a 4-point Likert scale. The image quality score, signal-to-noise ratio (SNR), contrast-to-noise ratio (CNR), and apparent diffusion coefficient (ADC) of extraocular muscles (EOMs) were compared between the two DWIs. Differences in the ADC of EOMs were also evaluated. The performance of discriminating active from inactive TAO was assessed using receiver operating characteristic curves. The correlation between ADC and clinical activity score (CAS) was analyzed using Spearman correlation. RESULTS: Compared with SS EPI DWI, FOCUS MUSE DWI demonstrated significantly higher image quality scores (P < 0.001), a higher SNR and CNR on the lateral rectus muscle (LRM) and medial rectus muscle (MRM) (P < 0.05), and a non-significant difference in the ADC of the LRM and MRM. Active TAO showed higher ADC than inactive TAO and healthy controls with both SS EPI and FOCUS MUSE DWIs (P < 0.001). Inactive TAO and healthy controls did not show a significant ADC difference with both DWIs. Compared with SS EPI DWI, FOCUS MUSE DWI demonstrated better discrimination of active from inactive TAO (AUC: 0.925 vs. 0.779; P = 0.007). The ADC was significantly correlated with CAS in SS EPI DWI (r = 0.391, P < 0.001) and FOCUS MUSE DWI (r = 0.645, P < 0.001). CONCLUSION: FOCUS MUSE DWI provides better images for evaluating EOMs and better performance in diagnosing active TAO than SS EPI DWI. The application of FOCUS MUSE will facilitate the DWI evaluation of TAO.

Chemical Auxiliary for Photocatalytic Active Colloids.

Active colloids with the ability to self-propel and collectively organize are emerging as indispensable elements in microrobotics and soft matter physics. For chemically powered colloids, their activity is often induced by gradients of chemical species in the particle's vicinity. The direct manipulation of these gradients, however, presents a considerable challenge, thereby limiting the extent to which active colloids can be controlled. Here, we introduce a series of rationally designed molecules, denoted as chemical auxiliary (CA), that intervene with specific chemical gradients and thus unveil new capabilities for regulating the behaviors of photocatalytic active colloids. We show that CA can alter the diffusiophoretic and osmotic interactions between active colloids and their subsequent self-organization. Also, CA can tune the self-propulsion of active particles, enabling a record high propulsion speed of over 100 µm/s and endowing high salt tolerance. Furthermore, CA is instrumental in establishing dynamic, competing gradients around active particles, which signifies an in situ, noninvasive, and reversible strategy for reconfiguring between modes of colloidal activity.

The uncleaved signal peptide of Bombyx mori nucleopolyhedrovirus GP64 preferentially activates BmSpz7 expression, contributing to protein secretion.

Bombyx mori nucleopolyhedrovirus (BmNPV) significantly impacts silkworm sericulture, causing substantial economic losses. The GP64 protein, a primary envelope protein of BmNPV budded virus (BV), retains its signal peptide (SP) in the mature form, crucial for its translocation to the plasma membrane (PM) and viral infectivity. This study investigates the role of the uncleaved SP of GP64 in activating the expression of BmSpz7, a novel Spätzle family member identified through RNA-seq analysis. We cloned and characterized BmSpz7, demonstrating its upregulated expression in BmN cells and silkworm larvae infected with BmNPV containing GP64 with an uncleaved SP. Additionally, transient expression of GP64's SP significantly enhanced BmSpz7 expression and protein secretion. These findings suggest that the uncleaved SP of GP64 plays a pivotal role in activating BmSpz7, providing new insights into the molecular interactions between BmNPV and its host, and revealing potential targets for antiviral strategies in sericulture.

Enhanced Glycosylation Caused by Overexpression of Rv1002c in a Recombinant BCG Promotes Immune Response and Protects against Mycobacterium tuberculosis Infection.

Tuberculosis (TB) is a major global health threat despite its virtual elimination in developed countries. Issues such as drug accessibility, emergence of multidrug-resistant strains, and limitations of the current BCG vaccine highlight the urgent need for more effective TB control measures. This study constructed BCG strains overexpressing Rv1002c and found that the rBCG-Rv1002c strain secreted more glycosylated proteins, significantly enhancing macrophage activation and immune protection against Mycobacterium tuberculosis (M. tb). These results indicate that Rv1002c overexpression promotes elevated levels of O-glycosylation in BCG bacteriophages, enhancing their phagocytic and antigenic presentation functions. Moreover, rBCG-Rv1002c significantly upregulated immune regulatory molecules on the macrophage surface, activated the NF-κB pathway, and facilitated the release of large amounts of NO and H2O2, thereby enhancing bacterial control. In mice, rBCG-Rv1002c immunization induced greater innate and adaptive immune responses, including increased production of multifunctional and long-term memory T cells. Furthermore, rBCG-Rv1002c-immunized mice exhibited reduced lung bacterial load and histological damage upon M. tb infection. This result shows that it has the potential to be an excellent candidate for a preventive vaccine against TB.

A Unique Wide-Spacing Fence-Type Superstructure for Robust High-Voltage O3-Type Sodium Layered Cathode.

Enhancing the energy density of layered oxide cathode materials is of great significance for realizing high-performance sodium-ion batteries and promoting their commercial application. Lattice oxygen redox at high voltage usually enables a high capacity and energy density. But the structural degradation, severe voltage decay, and the resultant poor cycling performance caused by irreversible oxygen release seriously restrict the practical application. Herein we introduce a novel fence-type superstructure (2a×3a type supercell) into O3-type layered cathode material Na0.9Li0.1Ni0.3Mn0.3Ti0.3O2 and achieve a stable cycling performance at a high voltage of 4.4 V. The fence-type superstructure effectively inhibits the formation of the vacancy clusters resulting from out-of-plane Li migration and in-plane transition metal migration at high voltage due to the wide d-spacing, thereby significantly reducing the irreversible release of lattice oxygen and greatly stabilizing the crystal structure. The cathode exhibits a high energy density of 545 Wh kg-1, a high rate capability (112.8 mAh g-1 at 5 C) and a high cycling stability (85.8 %@200 cycles with a high initial capacity of 148.6 mAh g-1 at 1 C) accompanied by negligible voltage attenuation (98.5 %@200 cycles). This strategy provides a distinct spacing effect of superstructure to design stable high-voltage layered cathode materials for Na-ion batteries.

Engineering Reversible Lattice Structure for High-Capacity Co-Free Li-Rich Cathodes with Negligible Capacity Degradation.

Co-free Li-rich Mn-based cathode materials are garnering great interest because of high capacity and low cost. However, their practical application is seriously hampered by the irreversible oxygen escape and the poor cycling stability. Herein, a reversible lattice adjustment strategy is proposed by integrating O vacancies and B doping. B incorporation increases TM─O (TM: transition metal) bonding orbitals whereas decreases the antibonding orbitals. Moreover, B doping and O vacancies synergistically increase the crystal orbital bond index values enhancing the overall covalent bonding strength, which makes TM─O octahedron more resistant to damage and enables the lattice to better accommodate the deformation and reaction without irreversible fracture. Furthermore, Mott-Hubbard splitting energy is decreased due to O vacancies, facilitating electron leaps, and enhancing the lattice reactivity and capacity. Such a reversible lattice, more amenable to deformation and forestalling fracturing, markedly improves the reversibility of lattice reactions and mitigates TM migration and the irreversible oxygen redox which enables the high cycling stability and high rate capability. The modified cathode demonstrates a specific capacity of 200 mAh g-1 at 1C, amazingly sustaining the capacity for 200 cycles without capacity degradation. This finding presents a promising avenue for solving the long-term cycling issue of Li-rich cathode.

Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High-Performance Electrocatalysts.

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in the FeCoNi/FeAl2O4 hybrid coating, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm-2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect-engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Pallidum volume as a predictor for the effectiveness of mindfulness-based cognitive therapy and psycho-education in unmedicated patients with obsessive-compulsive disorder.

BACKGROUND: Mindfulness-based cognitive therapy (MBCT) has been documented to be effective in treating obsessive-compulsive disorder (OCD). However, the neurobiological basis of MBCT remains largely elusive, which makes it clinically challenging to predict which patients are more likely to respond poorly. Hence, identifying biomarkers for predicting treatment outcomes holds both scientific and clinical values. This prognostic study aims to investigate whether pre-treatment brain morphological metrics can predict the effectiveness of MBCT, compared with psycho-education (PE) as an active placebo, among patients with OCD. METHODS: A total of 32 patients with OCD were included in this prognostic study. They received magnetic resonance imaging (MRI) brain scans before treatment. Subsequently, 16 patients received 10 weeks of MBCT, while the other 16 patients underwent a 10-week PE program. The effectiveness of the treatments was primarily assessed by the reduction rate of the Yale-Brown Obsessive-Compulsive Scale (Y-BOCS) total score before and after the treatment. We investigated whether several predefined OCD-associated brain morphological metrics, selected based on prior published studies by the ENIGMA Consortium, could predict the treatment effectiveness. RESULTS: Both the MBCT and PE groups exhibited substantial reductions in Y-BOCS scores over 10 weeks of treatment, with the MBCT group showing a larger reduction. Notably, the pallidum total volume was associated with treatment effectiveness, irrespective of the intervention group. Specifically, a linear regression model utilizing the pre-treatment pallidum volume to predict the treatment effectiveness suggested that a one-cubic-centimeter increase in pallidum volume corresponded to a 22.3% decrease in the Y-BOCS total score reduction rate. CONCLUSIONS: Pallidum volume may serve as a promising predictor for the effectiveness of MBCT and PE, and perhaps, other treatments with the shared mechanisms by MBCT and PE, among patients with OCD.

Reversing Zincophobic/Hydrophilic Nature of Metal-N-C via Metal-Coordination Interaction for Dendrite-Free Zn Anode with High Depth-of-Discharge.

Dendrite-free Zn metal anodes with high depth-of-discharge (DoD) and robust cycle performances are highly desired for the practical application of aqueous Zn-ion batteries. Herein, the zincophobic/hydrophilic nature of Metal-N-C through manipulating the electronic interactions between metal and coordination atoms is successfully reversed, thereby fabricating a zincophilic/hydrophobic asymmetric Zn-N3Py+1Pr-C (consisting of a Zn center coordinated with 3 pyridinic N atoms and 1 pyrrolic N atom) host, which realizes uniformed Zn deposition and a long lifespan with high DoD. The experimental and theoretical investigations demonstrate weakened interaction between pyrrolic N and metal center in the asymmetric Zn-N3Py+1Pr-C triggers downshift of the Zn 3d-band-center and a new localization nonbonding state in the N and C 2p-band, resulting in preferred Zn adsorption to water adsorption. Consequently, the asymmetric Zn-N3Py+1Pr-C host delivers small Zn nucleation overpotential and high Coulombic efficiency of 98.3% over 500 cycles. The symmetric cells with Zn-N3Py+1Pr-C@Zn anode demonstrate 500 h dendrite-free cycles at DoD up to 50%. The Zn-N3Py+1Pr-C@Zn/S-PANI full cell also shows a robust long-term cycle performance of 1000 cycles at 10 A g-1. This strategy of constructing zincophilic/hydrophobic Metal-N-C may open up their application for the dendrite-free metal anode.

ICP-MS and fluorescence dual-mode detection of ZIKV-RNA based on quantum dot labeling with hybridization chain reaction.

The detection of Zika virus (ZIKV) is of great significance to human life and health. Herein, we presented an ICP-MS and fluorescent dual-mode sensor for quantitative analysis of Zika virus RNA fragments (ZIKV-RNA), which employed quantum dots (QDs) as signal tags and combined with hybridization chain reaction (HCR). The dual-mode sensor realized cross-checking of the analysis results and improved the assay accuracy. Firstly, the single-stranded DNA (ssDNA) was anchored on the surface of magnetic beads (MBs). Afterward, HCR was conducted with probe DNA-CdSe quantum dots conjugates (pDNA-QDs) and link DNA (lDNA), producing the MBs-ssDNA-[pDNA-QDs-lDNA]n conjugates. In the presence of target ZIKV-RNA, a strand displacement reaction occurred, leading to the dissociation of the [pDNA-QDs-lDNA]n labels from the conjugates into the solution. Finally, the signal intensity was detected using ICP-MS and fluorescence analysis, with achieved limits of detection of 131 pM and 152 pM, respectively. The inter-assay RSD values of fluorescence and ICP-MS were 3.94 % and 4.26 % at 10 nM level, respectively, showing that the method had good precision. This method showed high selectivity and was applied to the analysis of biological fluids. There was no significant difference between the results of ICP-MS modes and fluorescence mode. This method offers a new strategy for sensitivity analysis of ZIKV-RNA and exhibits promise in clinical applications for diagnosis.

Janus particles with tunable patch symmetry and their assembly into chiral colloidal clusters.

Janus particles, which have an attractive patch on the otherwise repulsive surface, have been commonly employed for anisotropic colloidal assembly. While current methods of particle synthesis allow for control over the patch size, they are generally limited to producing dome-shaped patches with a high symmetry (C∞). Here, we report on the synthesis of Janus particles with patches of various tunable shapes, having reduced symmetries ranging from C2v to C3v and C4v. The Janus particles are synthesized by partial encapsulation of an octahedral metal-organic framework particle (UiO-66) in a polymer matrix. The extent of encapsulation is precisely regulated by a stepwise, asymmetric dewetting process that exposes selected facets of the UiO-66 particle. With depletion interaction, the Janus particles spontaneously assemble into colloidal clusters reflecting the particles' shapes and patch symmetries. We observe the formation of chiral structures, whereby chirality emerges from achiral building blocks. With the ability to encode symmetry and directional bonding information, our strategy could give access to more complex colloidal superstructures through assembly.

Self-Decoupled Oxygen Electrocatalysis for Ultrastable Rechargeable Zn-Air Batteries with Mild-Acidic Electrolyte.

Rechargeable zinc-air batteries (ZABs) have been considered promising as next-generation sustainable energy storage devices; however, their large-scale deployment is hampered by the unsatisfactory cyclic lifespan. Employing neutral and mild-acidic electrolytes is effective in extending the cyclability, but the rapid performance degradation of the bifunctional catalysts owing to different microenvironmental requirements of the alternative oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is still a serious limitation of their cyclic life. Herein, we propose a "self-decoupling" strategy to significantly improve the stability of the bifunctional catalysts by constructing a smart interface in the bifunctional air electrode. This smart interface, containing a resistance-switchable sulfonic acid doped polyaniline nanoarray interlayer, is nonconductive at high potential but conductive at low potential, which enables spontaneous electrochemical decoupling of the bifunctional catalyst for the ORR and OER, respectively, and thus protects it from degradation. The resulting self-decoupled mild-acidic ZAB delivers stable cyclic performances in terms of a negligible energy efficiency loss of 0.015% cycle-1 and 3 times longer cycle life (∼1400 h) compared with the conventional mild-acidic ZAB using a normal bifunctional air electrode and the same low-cost ZnCo phosphide/nitrogen-doped carbon bifunctional catalyst. This work provides an effective strategy for tolerating alternative oxidation-reduction reactions and emphasizes the importance of smart nanostructure design for more sustainable batteries.

Dynamic-self-catalysis as an accelerated air-cathode for rechargeable near-neutral Zn-air batteries with ultrahigh energy efficiency.

Neutral/near-neutral electrolyte rechargeable zinc-air batteries (NN-ZABs) with long cycling lifetime are an evolutionary design of the conventional alkaline ZABs, but the extremely sluggish kinetics of oxygen electrocatalysis in mild pH solutions in the air-cathode has notably affected the energy efficiency of the NN-ZABs. Herein, we present a dynamic self-catalysis as the air-cathode chemistry to boost the energy efficiency of NN-ZABs, which is based on in situ reversible generation of highly active electrocatalysts from the electrolyte during the discharge and charge operations of ZABs, respectively. Two reversible redox reactions of Cu(I)/Cu(II) and Mn(II)/Mn(IV) in the NH4Cl-ZnCl2-based electrolyte are integrated with oxygen electrocatalysis in the air-cathode to in situ generate Cu(I)-O-Cl deposits during discharging and Cu-MnO2 deposits during charging, which directly catalyze the subsequent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. The in situ generated electrocatalysts deliver good oxygen electrocatalytic activities due to their distinctive surface structures and can be dissolved by potential reversal in a subsequent battery operation. The NN-ZAB designed as such delivers a record-high energy efficiency of 69.0% and a cycling life of 1800 h with an areal capacity of 10 mA h cm-2, surpassing the performances of NN-ZABs with preloaded electrocatalysts reported to date.

Water-Trapping Single-Atom Co-N4 /Graphene Triggering Direct 4e- LiOH Chemistry for Rechargeable Aprotic Li-O2 Batteries.

Lithium-oxygen (Li-O2 ) batteries have received extensive attention owing to ultrahigh theoretical energy density. Compared to typical discharge product Li2 O2 , LiOH has attracted much attention for its better chemical and electrochemical stability. Large-scale applications of Li-O2 batteries with LiOH chemistry are hampered by the serious internal shuttling of the water additives with the desired 4e- electrochemical reactions. Here, a metal organic framework-derived "water-trapping" single-atom-Co-N4 /graphene catalyst (Co-SA-rGO) is provided that successfully mitigates the water shuttling and enables the direct 4e- catalytic reaction of LiOH in the aprotic Li-O2 battery. The Co-N4 center is more active toward proton-coupled electron transfer, benefiting - direction 4e- formation of LiOH. 3D interlinked networks also provide large surface area and mesoporous structures to trap ≈12 wt% H2 O molecules and offer rapid tunnels for O2 diffusion and Li+ transportation. With these unique features, the Co-SA-rGO based Li-O2 battery delivers a high discharge platform of 2.83 V and a large discharge capacity of 12 760.8 mAh g-1 . Also, the battery can withstand corrosion in the air and maintain a stable discharge platform for 220 cycles. This work points out the direction of enhanced electron/proton transfer for the single-atom catalyst design in Li-O2 batteries.

Electron Redistribution Enables Redox-Resistible Li6 PS5 Cl towards High-Performance All-Solid-State Lithium Batteries.

Sulfide electrolytes with high ionic conductivity hold great promise for all-solid-state lithium batteries. However, the parasitic redox reactions between sulfide electrolyte and Li metal result in interfacial instability and rapid decline of the battery performance. Herein, a redox-resistible Li6 PS5 Cl (LPSC) electrolyte is created by regulating the electron distribution in LPSC with Mg and F incorporation. The introduction of Mg triggers the electron agglomeration around S atom, inhibiting the electron acceptance from Li, and F generates the self-limiting interface, which hinders the redox reactions between LPSC and Li metal. This redox-resistible Li6 PS5 Cl-MgF2 electrolyte therefore presents a high critical current density (2.3 times that of pristine electrolyte). The LiCoO2 /Li6 PS5 Cl-MgF2 /Li cell shows an outstanding cycling stability (93.3 %@100 cycles at 0.2 C). This study highlights the electronic structure modulation to address redox issues on sulfide-based lithium batteries.