Achieving optimal reactive oxygen species (ROS) production requires carefully balancing these interactions to maximize therapeutic efficacy. Herein, we have successfully developed a nanosystem through defect substitution using CuCoFe-layered double hydroxides (LDHs) as a template, followed by Pt reduction on the layer, the resulting nanoalloy, denoted as CuPt alloy@LDHs, demonstrating remarkable ROS production activity. This superior ROS production was attributed to its low Gibbs free energy barrier for generating hydroxyl radical (•OH), as confirmed by both characterizations and density functional theory (DFT) calculations. Additionally, the nanoalloy exhibits good (NOx)-like activity, effectively disrupting the intracellular NADH/NAD+ cycling balance and enabling self-cycling of endogenous H2O2. This work highlights that CuPt alloy@LDHs can effectively disrupt the redox homeostasis in tumor regions, significantly improving therapeutic efficacy and overcoming the limitations of current nanoalloy catalytic therapies.

The partial reduction of layered double hydroxides (LDHs) is becoming a vital approach to harness their electrochemical capabilities for high-performance supercapacitors (SCs). This paper provides a synergistic experimental and theoretical data study of controlled partial reduction, density functional theory (DFT), and machine learning (ML) to design the oxygen vacancy (Vo) chemistry of cobalt vanadium layered double hydroxides (CoV-LDHs). A solution-based partial-reduction protocol introduces Vo and provides the opportunity to precisely modulate the LDH lattice with a significant enhancement of charge-storage performance. The Vo-CoV-LDH electrode exhibits a specific capacitance of 2437 F g- 1 at 2 A g- 1, significantly surpassing its unmodified CoV-LDH (1371 F g- 1). Moreover, it delivers 78.4% capacitance retention at escalating current densities (2-10 A g- 1), in contrast to 55% for the untreated LDH. Incorporated into an asymmetric supercapacitor (ASC) device, Vo-CoV-LDH attained a remarkable energy density of 47.1 W h kg- 1 at a power density of 468.1 W kg- 1. DFT simulations reveal that the availability of Vo causes the bandgap to be narrower and the number of states near the Fermi level to be higher to accelerate electronic conductivity and redox dynamics. Simultaneously, machine-learning models are used to explain quantitative relationships between the parameters of synthesis, concentration of vacancies, and electrochemical performance, with coefficients of determination of more than 0.98. The findings support experimental reproducibility and predictive accuracy. The work demonstrates the synergistic efforts of partial reduction, DFT knowledge, and ML modeling to design Vo-engineered LDHs and, thus, a generalizable approach to the creation of an advanced energy storage material is demonstrated.

Improving inefficient electron transfer in plasmonic photocatalysis requires novel plasmon-semiconductor heterojunctions. In this study, the ZnSe(Al)/Cu2Se(Al) pn-type inorganic intergrowth bulk heterojunction (pn-IIBH) was constructed via the topological selenization strategy with ZnCuAl-layered double hydroxides (ZnCuAlLDHs). The localized surface plasmon resonance (LSPR) effect of Cu2Se extends the spectral absorption range to almost the entire UV-Vis-NIR region. The unique pn-IIBH achieves atomic-level interface contact and lattice continuity, greatly promoting the efficient separation of carriers at the interface. Meanwhile, the combination of infrared thermal imaging and COMSOL multiphysics field simulation confirmed that pn-IIBH significantly enhanced the Cu2Se magnetic field enhancement effect induced by LSPR, thereby further synergically optimizing the interfacial charge separation efficiency of IIBH. The ZnSe(Al)/Cu2Se(Al) pn-IIBH exhibited a CO2 photoreduction efficiency of 720.56 mu mol center dot g-1 center dot h-1 for CO, which was 10.27 times higher than that of the ZnCuAl-LDHs. This study presents an innovative approach to designing plasmon-semiconductor heterojunction photocatalysts that facilitate efficient charge transfer.

The rapid and efficient separation of nanoscale targets in liquid matrices presents a critical yet formidable challenge. Polyamide (PA) membranes, while recognized as the benchmark for industrial-scale nanoscale separation, face ongoing limitations in performance optimization. Although advances in nanomaterials have enabled breakthroughs in PA membrane performance, scalable production remains hindered by integration challenges. Here, we present a scalable strategy to fabricate ultra-thin (<10 nm) nanofiltration membranes by constructing a layered double hydroxide (LDH) nanoplate-enhanced piperazine (PIP) intermediate layer via interfacial polymerization (IP) with trimesoyl chloride. Hydrogen-bond networks between PIP and LDH, combined with ordered water structures induced by LDH hydroxyl groups, restricted PIP diffusion, thus yielding ultrathin membranes with high ionization. Moreover, the rough LDH intermediate layer promoted a rougher membrane surface, enhancing the effective filtration area and permeability. The optimized membranes achieved a pure water permeance of 89.6 +/- 3.5 L m(-2) h(-1) bar(-1) and a Na2SO4 rejection rate of 95.7%, achieving one of the best-reported levels. Leveraging the accessibility of LDH colloids and the scalable fabrication process, this strategy enables the production of large-area membranes via spraying and IP, making it highly promising for purifying and recovering antibiotics.

Thermogalvanic cells(TGC) are a means of converting thermal energy into electrical energy. However, for quasi-solid-state TGC, it is difficult to simultaneously balance ion conductivity(sigma), Seebeck coefficient(Se), and mechanical properties. To achieve a delicate balance among these factors, this study employs ZnAl-layered double hydroxide (ZnAl-LDH) as a crosslinker to in-situ crosslink polyacrylamide-sodium acrylate (P(AM-ANA)) and carboxymethyl chitosan (CMCS). The resulting TGC hydrogel exhibits an elongation at break exceeding 1700%. Meanwhile, ZnAl-LDH selectively binds with Fe(CN)64-, increasing the entropy difference of the [Fe(CN)6]3-/4-redox couple in water-methanol mixtures and creating additional transport pathways for anions. As a result, the ZnAl-LDH based TGC hydrogel demonstrates a high Se value of 3.53 mV K-1, a high sigma value of 27 mS/cm, and a high specific output power density(Pmax/Delta T2) value of 420 mu W & sdot;m 2 & sdot;K 2, combining excellent mechanical and thermoelectric properties. Beyond powering electronics, the TGC serves as wearable sensors for human motion monitoring. Leveraging its high sensitivity, a self-powered human-machine interaction (HMI) system was developed to remotely control robotic hands and intelligent vehicles, while a 3 & times; 3 sensor array enables precise detection of pressure magnitude and spatial distribution. These ZnAl-LDH TGC-based devices lay a solid foundation for flexible electronics in IoT-era intelligent robotic systems.

Photo-assisted Zn-air batteries (PZABs) hold promise for advancing sustainable energy systems. Herein, to address challenges associated with the cathode charging oxygen evolution reaction (OER), a photo-assisted hybrid Zn-air battery (PHZAB) was constructed by employing photoelectrocatalytic glycerol oxidation reaction (GOR), which is thermodynamically favorable as a replacement for OER during the charging process. Based on element doping and cocatalyst loading strategies, the CoFe-LDH/Mo:BiVO4 photoanode was fabricated. Systematic photoelectrochemical tests demonstrate its excellent performance, with a GOR current density of 4.78 mAcm-2 at 1.23 V vs. RHE, 2.6 times that of the BiVO4, and an applied bias photon-to-current efficiency (ABPE) of 2.21%, 3.7 times that of the BiVO4. Further analysis proves that these modification strategies enhance bulk carrier density, accelerate surface catalytic reactions, and effectively suppress carrier recombination, thus enhancing the photoelectrochemical (PEC) performance. Benefiting from the excellent performance of the CoFe-LDH/Mo:BiVO4 photoanode and the novel hybrid device structure design, the PHZAB exhibits a maximum round-trip efficiency of 206% (at 0.5 mAcm-2) and a 68.7% electricity saving ratio under 1 sun illumination. Even at 2 mAcm-2, a 156% round-trip efficiency and 64.2% electricity saving ratio were maintained. During the photoassisted-charging process, the optimized CoFe-LDH/Mo:BiVO4 photoanode yields a high GOR performance of a total production rate of 225 mmolm-2h-1 and formic acid (FA) production rate of 133 mmolm-2h-1. This work presents a novel bifunctional system toward the rational design of functional devices and materials for simultaneously converting solar energy into chemical energy and enabling reversible solar power storage for on-demand release.

Diabetic wounds represent one of the most prevalent complications in patients with diabetes mellitus. Elevated reactive oxygen species (ROS), bacterial infections, persistent inflammation, and impaired angiogenesis collectively contribute to delayed diabetic wound healing. In this study, a multifunctional, injectable, photoinitiator-free, photocrosslinkable hydrogel (G/Z@M) based on insect-derived chitosan was developed. The hydrogel system incorporated lipoic acid (LA), which possesses photopolymerization capability and potent antioxidant activity, to modify quaternized chitosan (QMCS). Through self-initiated photo-crosslinking of QMCS-LA, the hydrogel's three-dimensional network was constructed. Simultaneously, the ZIF-8@MPN nanocomposite was constructed by coating ZIF-8 with a metal-polyphenol network (MPN) functional coating formed through the coordination of epigallocatechin gallate (EGCG) with Ga3+. This nanocomposite was then loaded onto the QMCS-LA network. Both in vitro and in vivo experiments demonstrated that the G/Z@M hydrogel possesses great biocompatibility, antibacterial, anti-inflammatory, antioxidant, and pro-angiogenic activities, effectively promoting the healing of full-thickness skin defect wounds in MRSA-infected diabetic rats. In conclusion, the G/Z@M hydrogel presents an innovative therapeutic approach for diabetic infected wounds by simultaneously regulating oxidative stress, bacterial infection, persistent inflammation, and impaired angiogenesis.

Candida albicans, responsible for nearly 70% of fungal infections, is a leading cause of life-threatening invasive infections, particularly in healthcare settings, with a mortality rate approaching 40% even after medical treatment. This study introduces a novel antifungal agent such as Curcumin@Graphene Oxide/Chitosan/Arginine nanocomposite hydrogel (Cur@GO/CS/Arg), targeting Candida albicans, a primary cause of periprosthetic joint infections (PJIs). The hydrogel exhibited remarkable antifungal efficacy, characterized by a 17 mm inhibition zone, a minimum inhibitory concentration (MIC) of 1.25 mg/ml, and a minimum fungicidal concentration (MFC) of 2.5 mg/ml, confirming its fungicidal properties based on the tolerance ratio. Additionally, it significantly reduced biofilm formation, highlighting its potent antifungal action. Furthermore, it demonstrated excellent biosafety, as evidenced by a minimal hemolytic effect at 50 μg/ml. These findings underscore the synergistic interactions among curcumin, graphene oxide, chitosan, and arginine, which enhance antifungal activity. This study offers a promising strategy for managing Candida albicans-associated PJIs, enabling safer and more effective treatment.

An inorganic intergrowth bulk heterojunction (IIBH) NiO(Ti)/Ti3O5(Ni,Ga) has been constructed by a two-stage topological pyrolysis method based on the structure memory effect of NiTiGa-LDHs. The Z-scheme mechanism for regenerating oxygen vacancies was investigated by ISI-XPS. It can be speculated that the photogenerated electron transfer process between the Ni2+/Ni3+ and Ti4+/Ti3+ redox pairs across the interface of the IIBH resulted in excess oxygen vacancies, which were active in the photocatalytic CO2 reduction. This IIBH exhibited well-established photocatalytic efficiency for CO2 reduction with CO yields up to 2560.1 mu mol g-1 h-1, which were 6.97 times higher than those of NiTiGa-LDHs and 4.95 times higher than those of NiTiGa-MMO, respectively. In the 60 h cyclic photocatalytic CO2 reduction experiment, the stability could still be maintained at 96.7%. This work provided an innovative approach for designing defective catalysts by electron transfer from redox pairs thus inducing the regeneration of oxygen vacancies.

Photo-rechargeable batteries based on photocathodes that have the dual function of collecting and storing solar energy offer an efficient method for solar energy utilization. Herein, NiCo-layered double hydroxides (NiCo-LDH)/ZnIn2S4/carbon nanotubes (CNTs) (recorded as CZN), a heterostructure photocathode, has been synthesized by layer-by-layer growth for photo-driven rechargeable aqueous zinc batteries (AZBs). The proposed photocathode exhibits typical photoelectric properties and offers the following advantages: good photoresponse in the visible light range, energy level/potential matching between ZnIn2S4 and NiCo-LDH, and the conductive network formed by CNTs to promote charge transfer. The photo-driven rechargeable AZBs can harvest solar energy and store charge simultaneously, showing enhanced energy storage capability under illumination. The discharge capacity reaches 274.8 mAhg-1 with a high photo-conversion efficiency of 1.120% at 8.0 Ag-1 (100 mWcm-2, white light). In particular, the photo-driven rechargeable AZBs can be charged by light solely, achieving a discharge capacity of 116.3 mAhg-1. This study shows that the novel design and synthesis of the heterostructure photocathode is crucial and significant to enhancing the practicality of solar energy.

The burgeoning demand for sustainable energy storage solutions has intensified the pursuit of vanadium-based cathodes for aqueous zinc-ion batteries (AZIBs). However, their performance has been hampered by the limited interlayer space, poor electrical conductivity and unstable layer structure during the cycling working process. Herein, a hybrid vanadium-based composite cathode material was synthesized by in-situ polymerization to integrate poly(3,4-ethylenedioxythiophene) (PEDOT) within the interlayers of ZnxV2O5 center dot nH2O (ZVO). A variety of experimental data demonstrate that this in-situ interlayer polymerization strategy successfully induces enlarged interplanar space, valence changes of vanadium, and regular arrangement of the conductive PEDOT chain between the vanadium bronze interlayers. As a result, the ion diffusion kinetics, electron transport rate, and pseudocapacity of the prepared hybrid cathode are all improved, leading to excellent electrochemical performance with high specific capacity (420.1 mAh center dot g-1 at 50 mA center dot g-1) and good cycling performance (capacity retention of 303.3 mAh center dot g-1 after 1000 cycles at 1 A center dot g-1) compared with other reported vanadium bronze cathodes in AZIBs. This study provides a facile synthesis strategy by in-situ interlayer polymerization without any oxidant, which can potentially be applied to the fabrication of other organic-inorganic hybrid cathodes.

The efficacy of immunotherapy in triple-negative breast cancer (TNBC) is significantly hindered by its low immunogenicity and immunosuppressive tumor microenvironment. Non-invasive photodynamic therapy (PDT) is increasingly recognized as a potential immunotherapeutic stimulant in the treatment of TNBC. However, photodynamic immunotherapy is constrained by tumor hypoxia and excessive inflammation suppression during the course of treatment. Herein, a simple and efficacious biomedicine is formulated to overcome adverse influences by amplifying photodynamic immunotherapy, thereby stimulating the systemic immune response. Specifically, the approach targeted tumor delivery by employing specific agents such as the photosensitizer (verteporfin), the hypoxic ameliorator (atovaquone), and the cyclooxygenase-2/prostaglandin E2 (COX-2/PGE2) signaling blocker (celecoxib). More importantly, the biomedicine effectively ameliorated hypoxia and inhibited COX-2/PGE2 signaling, thereby amplifying PDT-induced immunogenic cell death. This, in turn, enhanced the efficacy of photodynamic immunotherapy and triggered a robust immune response cascade. Notably, the self-amplifying photodynamic biomedicine significantly inhibited primary tumors, distal tumors, lung metastases, and post-operative recurrence while maintaining high biocompatibility. To sum up, the work provides a viable cascade stimulation approach and an efficient biomedical nanoplatform, offering a novel strategy for photodynamic immunotherapy of TNBC in the clinic.

Plasmon has garnered effectively attention in photocatalysis due to its ability to enhance photoresponse substantially, but the underlying catalytic mechanism remains elusive. In this study, an inorganic intergrowth bulk heterojunction (IIBH) Cu(II)int-MgAl-LDHs/CuS(Al) with localized surface plasmon resonance (LSPR) effect was constructed via the pyrolytic topological vulcanization (PTV) method with layered double hydroxides (LDHs) as the precursor. The in-situ topological formation process of IIBH was understood by extended X-ray absorption fine structure (EXAFS). UV-Vis-NIR showed IIBH extensive absorption in the infrared region. In-situ irradiated Xray photoelectron spectroscopy (ISI-XPS) revealed the electron transport mechanism with the Z-scheme character. Real-time thermal imaging and COMSOL simulation quantified the photothermal conversion efficiency and electromagnetic field enhancement effect of the IIBH. Hot electrons kinetics of Cu(II)int-MgAl-LDHs/CuS(Al) was validated by femtosecond transient absorption spectra (FS-TAS). The efficiency of photocatalytic reduction of carbon dioxide CO2 by IIBH Cu(II)int-MgAl-LDHs/CuS(Al) (444.36 mu mol/g & sdot;h) was 6.8 times higher than that of MgCuAl-LDHs (65.43 mu mol/g & sdot;h). Based on improving the separation efficiency of photogenerated carriers, IIBH Cu(II)int-MgAl-LDHs/CuS(Al) generates a high concentration of hot electrons and a significant magnetic field enhancement at the reaction site, forming "hot spots" to promote the activation of CO2 molecules and improve the photocatalytic efficiency.

Rechargeable aqueous Zn-Mn batteries have attracted extensive attention. However, the charge storage mechanism of the MnO2 cathode suffers from poor reversibility and sluggish kinetics due to the unstable cathodic structure and the electrostatic interactions during the deintercalation reaction. In this paper, LK-birnessite is synthesized through topochemical oxidation, using MnFe layered double hydroxides as a precursor. While obtaining manganese dioxide with pre-embedded K+ and oxygen vacancies, LK-birnessite also exhibits a larger interlayer spacing compared to the control sample with monometallic hydroxide precursors. The assembled Zn// LK-birnessite shows not only high reversible capacities of 387 and 235 mA h g-1 at rates of 0.1 C and 10 C, respectively but also stable cycling performance of 255 mA h g-1 at 1 C after 1000 cycles. An integrated solarrechargeable battery was fabricated to investigate the potential of the prepared LK-birnessite cathode in intermittent solar power storage further. Leveraging the advantages of the integrated device architecture and LKbirnessite with excellent reversible zinc-ion storage kinetics, the flexible solar rechargeable Zn-Mn battery (SRZMB) achieves an overall efficiency of around 4.33 %, maintaining stability across 150 photocharging and discharging cycles. This study highlights the advantages of using layered double hydroxides (LDHs) as precursors for the preparation of layered transition metal oxide cathodes through topochemical oxidation methods and investigates the application potential of layered transition metal oxide cathodes in solar-powered off-grid electronic devices.

Periprosthetic joint infection (PJI) caused by methicillin-resistant Staphylococcus aureus (MRSA) is a significant complication in orthopedic surgery. Developing effective strategies to combat bacterial colonization and inhibit biofilm formation is crucial. This study focused on enhancing the antibacterial efficacy of titanium dioxide nanoparticles (TiO2 NPs) without relying on ultraviolet (UV) light activation, which has limitations in clinical applications. By encapsulating TiO2 NPs with gallic acid (GA@TiO2) and incorporating graphene oxide/carboxymethylated chitosan (GO/CMCh) to prevent aggregation, remarkable antibacterial activity against MRSA was observed. Surprisingly, even in the absence of UV irradiation, TiO2, GA@TiO2, and GA@TiO2/GO/CMCh exhibited substantial bactericidal effects, with inhibition zones of 14, 12, and 12 mm, respectively. Furthermore, these materials demonstrated enhanced antibiofilm formation. Importantly, they displayed favorable biocompatibility, supporting their potential for clinical applications in reducing the morbidity and mortality associated with MRSA-PJI. Our findings highlight the significant antibacterial properties of GA@TiO2/GO/CMCh as a promising strategy for combating MRSA, independent of UV light exposure, and emphasize the need for further in vivo investigations to assess its potential in addressing MRSA-PJI.

Calcination of MgCO3 is an important industrial reaction, but it causes significant and unfavorable CO2 production. Calcination in a reducing green hydrogen atmosphere can substantially reduce CO2 release and produce high value-added products such as CO or hydrocarbons, but the mechanism is still unclear. Here, the in situ transformation process of MgCO3 interacting with hydrogen and the specific formation mechanism of the high value-added products are thoroughly investigated based on reaction thermodynamic, ab initio molecular dynamics (AIMD) simulations, and density functional theory (DFT) calculations. The reaction thermodynamic parameters of MgCO3 coupled with hydrogen to produce CO or methane are calculated, revealing that increasing and decreasing the thermal reductive decomposition temperature favors the production of CO and methane, respectively. Kinetically, the energy barriers of each possible production pathway for the dominant products CO and methane are further calculated in conjunction with the AIMD simulation results of the transformation process. The results suggest that CO is produced via the MgO catalytic-carboxyl pathway (CO2*-> COOH*(trans)-> COOH*(cis)-> CO*-> CO), which is autocatalyzed by MgO derived from the thermal reductive decomposition of MgCO3. For the mechanism of methane formation, it prefers to be produced by the stepwise interaction of carbonates in the MgCO3 laminates with hydrogen adsorbed on their surfaces (direct conversion pathway: sur-O-CO -> sur-O-HCO -> sur-O-HCOH -> sur-O-HC -> sur-O-CH2 -> sur-O-CH3 -> sur-O + CH4*).

Enzyme-mimetic photocatalysis has been attracting much attention in bionic research, in which carbon monoxide dehydrogenase (CODH) is a suitable prototype for simulation to meet environmental and energy needs. In this study, we utilized the structural memory effect of layered double hydroxides (LDHs) to build inorganic intergrowth bulk heterojunctions (IIBHs) NiS/FeS@MgFe-LDHs via a pyrolytic topological vulcanization (PTV) method that imitated active C-clusters [Ni-4Fe-4S] in CODH. Enzyme mimicry was evaluated in terms of the microstructure and catalytic reaction site. The similarity between the microstructure of NiS/FeS@MgFe-LDHs and the CODH active group was demonstrated through XRD, XAFS and other characterisations. Subsequently, the obtained in situ irradiated X-ray photoelectron spectra and transient absorption spectra indicated the photogenerated electron transfer of the IIBH, wherein electrons finally accumulated in the conduction band of the NiS domain for the photocatalytic CO2 reduction reaction, which was similar to that of C-clusters [Ni-4Fe-4S] in which the Ni2+ ion was the reactive site. As a result, NiS/FeS@MgFe-LDHs achieved a high yield of CO at a rate of 2151.974 mu mol g(-1) h(-1), which was 39.8 and 9.7 times more than that of NiMgFe-LDHs and NiMgFe-MMO, respectively. The study offers an innovative design route for developing IIBHs, providing novel opportunities for enzyme-mimetic photocatalysis.

We built CuPcS/NiMgFe-LDHs composites and probed the unique photogenerated-carrier transfer mechanism. A series of long-range Forster energy transfers prolonged the lifetime of photogenerated carriers to match the timescale of surface reaction.

An intelligent delivery nanoformulation could enhance the utilization efficacy, uptake, and translocation of pesticides in plants. Herein, a redox/pH-triggered and fluorescent smart delivery nanoformulation was designed and constructed by using hollow mesoporous organosilica nanoparticles (HMONs) and ZnO quantum dots as the nanocarrier and capping agent, respectively. Boscalid was further loaded to generate Boscalid@HMONs@ZnO with a loading rate of 9.8% for controlling Botrytis cinerea (B. cinerea). The quantity of boscalid released by Boscalid@HMONs@ZnO in a glutathione environment or at pH 3.0 was 1.3-fold and 1.9-fold higher than that in a neutral condition. Boscalid@HMONs@ZnO has 1.7-fold the toxicity index of boscalid technical against B. cinerea in antifungal experiments. Pot experiments revealed that the efficacy of Boscalid@HMONs@ZnO was significantly enhanced more than 1.27-fold compared to commercially available water-dispersible granules of boscalid. Due to the fluorescence properties of Boscalid@HMONs@ZnO, pesticide transport's real-time monitoring of pesticide translocation in tomato plants could be observed by confocal laser scanning microscopy. Fluorescence images revealed that HMONs@ZnO had been effectively transported via treated leaves or roots in tomato plants. This research showed the successful application of HMONs@ZnO as a nanocarrier for controlling disease and offered an effective avenue to explore the real-time tracking of pesticide translocation in plants