Designing core–shell electrode materials with desired components and architectures is a promising strategy for boosting electrochemical performance. Here, three‐dimensional hierarchical ...ZnCo2O4@Ni(OH)2 core–shell nanosheet arrays have been successfully fabricated on a Ni foam substrate, in which the porous ZnCo2O4 nanosheet “core” as the conductive scaffold was synthesized by a metal–organic framework (MOF)‐templated method, and the ultrathin Ni(OH)2 nanoflakes “shell” with rich active sites were grafted on the ZnCo2O4 nanosheet through a hydrothermal treatment. When directly used as a free‐standing electrode for supercapacitor, these hierarchical ZnCo2O4@Ni(OH)2 core–shell nanosheet arrays exhibited a high capacitance of 3063.2 mF cm−2 (1021.1 F g−1) at the current density of 1 mA cm−2. This electrode significantly outperformed individual Ni(OH)2 or ZnCo2O4 nanosheet arrays, benefiting from the robust core–shell arrays on Ni foam with good electrical conductivity and abundant active sites, as well as the synergetic effect between MOF‐derived porous ZnCo2O4 “core” and the ultrathin Ni(OH)2 “shell”. Moreover, the assembled ZnCo2O4@Ni(OH)2//activated‐carbon asymmetric supercapacitor displayed excellent energy and power densities (maximum of 40.0 Wh kg−1 and 8.02 kW kg−1) and superior cycling stability of 98.4 % retention with 91.2 % coulombic efficiency over 5 000 cycles at 10 A g−1.
Improving supercapacitors: The preparation of a structured electrode based on 3D hierarchical ZnCo2O4@Ni(OH)2 core–shell nanosheet arrays templated by metal–organic frameworks and its use in preparing high‐performance supercapacitors are described.
Co3O4@CoNi-LDH core/shell nanosheet array on Ni foam was prepared as an integrated battery-type electrode for supercapacitors and exhibits high specific capacitance and excellent cycling stability.
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•Co3O4@CoNi-LDH core/shell nanosheet array on Ni foam was prepared.•The composite material exhibits high specific capacitance and excellent cycling stability.•The assembled asymmetric supercapacitor device exhibits high energy density.•The red light-emitting diode (LED) can be illuminated by two connected ASCs.
Co3O4@CoNi-layered double hydroxide (LDH) core/shell nanosheet array on Ni foam was prepared as an integrated battery-type electrode for supercapacitors by growth of CoNi-LDH nanosheets shell on the surface of Co3O4 plates core. The resulting composite material exhibits high specific capacitance (2676.9 F g−1 at 0.5 A g−1) and excellent cycling stability. The improved electrochemical behavior is benefited from the typical mesoporous structure, which shorten the diffusion distance of OH− in the electrolyte and the strong core/shell binding interaction among Co3O4 and CoNi-LDH nanosheet arrays. Additionally, an assembled asymmetric supercapacitor (ASCs) device using as-fabricated Co3O4@CoNi-LDH as positive electrode and activated carbon (AC) as negative electrode also exhibits a high energy density of 61.23 Wh kg−1 at a high power density of 750 W kg−1, furthermore, still remains 24.8 Wh kg−1 even at a higher power density of 7500 W kg−1. Most importantly, a red light-emitting diode (LED) can be illuminated by two connected ASCs, indicating that as-synthesized Co3O4@CoNi-LDH possesses great potential for practical applications. As a result, this work demonstrates a feasible strategy for the design and fabrication of metal oxides/LDH composites for applications in energy storage systems.
Hollow double–shelled NiO nanospheres have been successfully prepared by the calcination of Ni–based MOF precursor at proper temperatures. The morphology and phase structure of NiO samples were ...characterized by SEM, TEM, XRD and FTIR. Electrochemical studies indicate that NiO nanospheres obtained under different conditions have distinct electrochemical performances. Hollow double–shelled NiO nanospheres calcined at 400 °C (N400) exhibit the best charge storage with a specific capacitance of 473 F g−1 at the current density of 0.5 A g−1 and with 94% capacitance retention even after 3000 cycling tests. For this merits, the N400//active carbon (AC) asymmetric supercapacitor (ASC) was assembled to examine the practical application of the N400 sample, which presents high energy density of 21.4 Wh kg−1 at power density of 375.8 W kg−1. Particularly, the N400//AC ASC exhibits outstanding cycling stability, and its capacitance retention can still reach up to 92.3% after 3000 cycles. These results indicate that the N400 sample is a promising electroactive candidate for supercapacitors.
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•Hollow double-shelled NiO nanospheres were prepared from MOF precursors.•The NiO nanospheres show high specific capacitance.•The NiO nanospheres exhibit excellent cycling performance.•The assembled asymmetric supercapacitor presents high energy density.
The shish-kebab type MnCo2O4@Co3O4 nanoneedle arrays were fabricated by annealing an inorganic complex of MnCo-LDH nanoneedle and ZIF-67 rhombic dodecahedral to act as electrode materials for ...high-performance supercapacitors and as electrocatalysts for efficient oxygen evolution reaction.
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•The shish-kebab type nanoneedle array was prepared via an improved MOF-template-directed strategy.•The resulting MnCo2O4@Co3O4 exhibit high areal capacitance and excellent cycling stability.•The red light-emitting diode (LED) can be illuminated about 6 min by two connected asymmetric supercapacitors.•The MnCo2O4@Co3O4 exhibits much better electrocatalytic activity for oxygen evolution reaction.
One-dimensional micro-/nanostructure arrays with excellent synergistic effect have attracted considerable interest for their potential applications in energy storge and conversion devices. In this work, the uniform ZIF-67 rhombic dodecahedron penetrated CoMn-LDH nanoneedle arrays were firstly synthesized and then transformed into shish-kebab type MnCo2O4@Co3O4 nanoneedle arrays by thermal annealing in air. The resulting nanoneedle arrays exhibit high specific capacitance (1440C cm−2 at 1.0 mA cm−2) and excellent cycling stability while evaluated as promising electrodes for battery-type supercapacitor. An assembled asymmetric supercapacitor (ASC) device using MnCo2O4@Co3O4 as positive electrode and activated carbon (AC) as negative electrode also exhibits a high energy density of 31 Wh kg−1 at a power density of 208.5 W kg−1, furthermore, still remains 14.6 Wh kg−1 even at a higher power density of 3326.6 W kg−1. Importantly, a red light-emitting diode (LED) can be illuminated about 6 min, indicating a great potential for practical applications of the ASC. Besides, the MnCo2O4@Co3O4 exhibits much better electrocatalytic activity for the oxygen evolution reaction (OER). As a result, this work demonstrates a feasible strategy for the design and fabrication of 1D shish-kebab type nanoneedle arrays with multiple functions.
Integrating desirable light absorption, energy levels, and morphology in one matrix is always the aspiration to construct high‐performance organic solar cells (OSCs). Herein, an asymmetric acceptor ...Y6‐1O is incorporated into the binary blends of acceptor Y7‐BO and donor PM6 to prepare ternary OSCs. Two isogenous asymmetric–symmetric acceptors with similar chemical skeletons tend to form alloy‐like state in blends due to their good compatibility, which contributes to optimizing the morphology for efficient charge generation and extraction. The complementary absorption of two acceptors helps to improve the photon harvesting of ternary blends, and the higher lowest unoccupied molecular orbital (LUMO) energy level of Y6‐1O offers the chance to uplift the mixed LUMO energy levels of acceptors. Combining the aforesaid benefits, the ternary OSCs with 10 wt% Y6‐1O produce a top‐ranked power conversion efficiency (PCE) of 18.11% with simultaneously elevated short‐circuit current density, open‐circuit voltage, and fill factor in comparison to Y7‐BO‐based binary devices. Furthermore, the optimized ternary OSCs with ≈300 nm active layers obtain a champion PCE of 16.61%, which is the highest value for thick‐film devices reported so far. This work puts forward an avenue for further boosting the performance of OSCs with two isogenous acceptors but different asymmetric structures.
The synergistically optimized light absorption, energy levels, and morphology, by incorporating an asymmetric isogenous acceptor Y6‐1O in PM6:Y7‐BO‐based ternary organic solar cells (OSCs), is demonstrated. The optimized ternary OSCs produce a top‐ranked power conversion efficiency (PCE) of 18.11% and with ≈300 nm active layers obtain a champion PCE of 16.61%, which is the highest value for thick‐film devices reported so far.
To gain more information on the prevalence of germline mutations in BRCA1/2 and PALB2 genes in the Chinese population, and to explore the effects of the mutation status of these genes on clinical ...outcomes in patients with breast cancer, we performed a screening for BRCA1/2 and PALB2 mutations in a consecutive series of unselected breast cancer patients in the Chinese population. A total of 2,769 cases were enrolled between June 1993 and September 2017. All of the exons and exon–intron boundaries of the BRCA1/2 and PALB2 genes were screened with next‐generation sequencing. Of the 2,769 breast cancer patients, BRCA1, BRCA2 and PALB2 mutations accounted for 2.7% (n = 74), 2.7% (n = 76), and 0.9% (n = 24), respectively. The BRCA1 gene had the highest mutation frequency in patients with triple‐negative breast cancer (TNBC), which was 9.6% (n = 42), while the BRCA2 gene had the highest mutation frequency in patients with Luminal, which was 3.2% (n = 58). The disease‐free survival (DFS) of BRCA1 mutation carriers was significantly lower than that of noncarriers (adjusted HR = 2.20, 95% CI = 1.15–4.18, p = 0.017). The mutation status of the PALB2 gene was significantly associated with the decline in overall survival (OS) (adjusted HR = 8.38, 95% CI = 2.19–32.11, p = 0.002). No significant difference was found between BRCA2 pathogenic mutation carriers and noncarriers. These results demonstrate that BRCA1 mutation status may be associated with a worse disease progression in patients with breast cancer, and women who harbored a PALB2 mutation might be at a higher risk of death due to breast cancer compared to noncarriers.
What's new?
To date, little data has been reported on the prevalence and clinical outcomes of mutations in the BRCA1/2 and PALB2 genes in Chinese breast cancer patients. This screening study of 2,769 consecutive unselected breast cancer patients in the Chinese population found the prevalence of BRCA1, BRCA2, and PALB2 mutations to be 2.7%, 2.7%, and 0.9%, respectively. BRCA1 mutation status may be associated with a worse disease progression in patients with breast cancer, and women who harbor a PALB2 mutation might be at a higher risk of death due to breast cancer compared with non‐carriers.
Chemodynamic therapy (CDT) employs Fenton catalysts to kill cancer cells by converting intracellular hydrogen peroxide (H2O2) into hydroxyl radicals (OH•). Although many studies on H2O2 ...supplementation have been conducted to improve the therapeutic effect of CDT, few studies have focused on the application of superoxide radical (O2−•) in CDT, which may result in better efficacy. A major concern about O2−•‐mediated CDT is its tendency to induce serious oxidative damage to normal tissues, which may be addressed by using a degradable O2−• scavenger. Here, a harmless‐harmful switchable and uninterrupted laccase (LAC)‐instructed killer (HULK) is constructed, which is the first CDT agent accelerated by LAC‐instructed O2−• generation and possesses a harmless‐harmful switchable effect because of the photodegradation of the O2−• scavenger iron‐chlorin e6 (FeCe6). LAC‐instructed substrate oxidation effectively catalyzes O2−• production with the help of intracellular reduction, thereby promoting the conversion of Fe3+ to Fe2+, accelerating the generation of OH•, and inducing tumor cell apoptosis and necrosis. The introduced O2−• scavenger FeCe6 is quickly photodegraded during irradiation, while LAC‐instructed O2−• generation proceeds as before, resulting in activatable CDT. This work not only provides the first strategy for LAC‐instructed O2−• generation but also presents new insight into activatable CDT.
A harmless–harmful switchable and uninterrupted laccase (LAC)‐instructed killer (HULK) is designed as a chemodynamic therapy (CDT) agent, which is the first CDT agent accelerated by LAC‐instructed superoxide radical (O2−•) generation and possesses harmless–harmful switchable effect because of the photodegradation of O2−• scavenger Fe‐chlorin e6, showing great potential as a safe and effective CDT agent.
•The CoNi-MOF-74 that anchored on nickel foam is successfully fabricated.•The CoNi-MOF-74 is transformed into Co(OH)2/Ni(OH)2 with specific structure.•The Co(OH)2/Ni(OH)2 with largest BET achieves ...superior performance.
Thanks to the rich porosity, high specific surface area and tunable components, MOFs-derived hydroxides have become outstanding electrode materials for supercapacitors. According to an ion etching/exchange reaction method, the self-sacrifice template of CoNi-MOF-74 micro-rods that anchored on Ni foam are controllably transformed into a series of composites of Co(OH)2/Ni(OH)2 with specific structure. They are nanoflakes-wrapped solid micro-rods (CoNi-2), nanoflakes self-assembled micro-rods (CoNi-6) and nanoflakes self-assembled micro-tubes (CoNi-12), respectively. Among them, the CoNi-2 demonstrates the largest BET surface area (208.8 m2/g) and the highest areal capacitance (16.3 F/cm2 at 2 mA/cm2), exhibiting the most promising electrochemical energy storage ability. A corresponding asymmetric supercapacitor (CoNi-2//AC) delivers high energy density of 0.5 mWh/cm2 at power density of 1.6 mW/cm2 and excellent cycling stability (86.6 % capacitance retention after 10 000 cycles at 50 mA/cm2). Moreover, an all-solid-state asymmetric supercapacitor successfully lighten a light-emitting diode (LED) for one minute, implying great potential for practical applications in energy storage.
Oxygen plays an essential role in the photodynamic therapy (PDT) of cancer. However, hypoxia inside tumors severely attenuates the therapeutic effect of PDT. To address this issue, a novel strategy ...is reported for cutting off the oxygen consumption pathway by using sub‐50 nm dual‐drug nanoparticles (NPs) to attenuate the hypoxia‐induced resistance to PDT and to enhance PDT efficiency. Specifically, dual‐drug NPs that encapsulate photosensitizer (PS) verteporfin (VER) and oxygen‐regulator atovaquone (ATO) with sub‐50 nm diameters can penetrate deep into the interior regions of tumors and effectively deliver dual‐drug into tumor tissues. Then, ATO released from NPs efficiently reduce in advance cellular oxygen consumption by inhibition of mitochondria respiratory chain and further heighten VER to generate greater amounts of 1O2 in hypoxic tumor. As a result, accompanied with the upregulated oxygen content in tumor cells and laser irradiation, the dual‐drug NPs exhibit powerful and overall antitumor PDT effects both in vitro and in vivo, and even tumor elimination. This study presents a potential appealing clinical strategy in photodynamic eradication of tumors.
A novel strategy for reducing oxygen consumption to attenuate the hypoxia‐induced resistance to photodynamic therapy (PDT) by using sub‐50 nm dual‐drug nanoparticles (ATO/VER NPs) is described. ATO has the ability of alleviating hypoxic regions and can eliminate tumors by enhancing PDT, which provides a valuable reference for research on targeted treatment of hypoxic tumor tissues.
During liver fibrogenesis, the reciprocal crosstalk among capillarized liver sinusoidal endothelial cells (LSECs), activated hepatic stellate cells (HSCs), and dysfunctional hepatocytes constructs a ...self‐amplifying vicious cycle, greatly exacerbating the disease condition and weakening therapeutic effect. Limited by the malignant cellular interactions, the previous single‐cell centric treatment approaches show unsatisfactory efficacy and fail to meet clinical demand. Herein, a vicious cycle‐breaking strategy is proposed to target and repair pathological cells separately to terminate the malignant progression of liver fibrosis. Chondroitin sulfate‐modified and vismodegib‐loaded nanoparticles (CS‐NPs/VDG) are designed to efficiently normalize the fenestrae phenotype of LSECs and restore HSCs to quiescent state by inhibiting Hedgehog signaling pathway. In addition, glycyrrhetinic acid‐modified and silybin‐loaded nanoparticles (GA‐NPs/SIB) are prepared to restore hepatocytes function by relieving oxidative stress. The results show successful interruption of vicious cycle as well as distinct fibrosis resolution in two animal models through multiregulation of the pathological cells. This work not only highlights the significance of modulating cellular crosstalk but also provides a promising avenue for developing antifibrotic regimens.
The manuscript prompts a vicious cycle breaking therapy to terminate the endless malignant interplay among various pathological hepatic cells in liver fibrosis. Far beyond single cell‐centric approaches, the precise regulation of cellular crosstalk of “hepatic stellate cells‐liver sinusoidal endothelial cells‐hepatocytes” shows synergetic effect in two animal models and reverses the vicious cycle back to the virtuous loop.
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