Intrinsically Decoupled Coordination Chemistries Enable Quasi-Eutectic Electrolytes with Fast Kinetics toward Enhanced Zinc-Ion Capacitors.

Eutectic electrolytes show potential beyond conventional low-concentration electrolytes (LCEs) in zinc (Zn)-ion capacitors (ZICs) yet suffer from high viscosity and sluggish kinetics. Herein, we originally develop an intrinsically decoupling strategy to address these issues, producing a novel electrolyte termed "quasi-eutectic" electrolyte (quasi-EE). Joint experimental and theoretical analyses confirm its unique solution coordination structure doped with near-LCE domains. This enables the quasi-EE well inherit the advanced properties at deep-eutectic states while provide facilitated kinetics as well as lower energy barriers via a vehicle/hopping-hybridized charge transfer mechanism. Consequently, a homogeneous electroplating pattern with much enhanced Sandꞌs time is achieved on the Zn surface, followed by a twofold prolonged service-life with drastically reduced concentration polarization. More encouragingly, the quasi-EE also delivers increased capacitance output in ZICs, which is elevated by 12.4%-144.6% compared to that before decoupling. Furthermore, the pouch cell with a cathodic mass loading of 36.6 mg cm-2 maintains competitive cycling performances over 600 cycles, far exceeding other Zn-based counterparts. This work offers fresh insights into eutectic decoupling and beyond.

Water Catchers within Sub-Nano Channels Promote Step-by-Step Zinc-Ion Dehydration Enable Highly Efficient Aqueous Zinc-Metal Batteries.

Zinc metal suffers from violent and long-lasting water-induced side reactions and uncontrollable dendritic Zn growth, which seriously reduce the coulombic efficiency (CE) and lifespan of aqueous zinc-metal batteries (AZMBs). To suppress the corresponding harmful effects of the highly active water, a stable zirconium-based metal-organic framework with water catchers decorated inside its sub-nano channels is used to protect Zn-metal. Water catchers within narrow channels can constantly trap water molecules from the solvated Zn-ions and facilitate step-by-step desolvation/dehydration, thereby promoting the formation of an aggregative electrolyte configuration, which consequently eliminates water-induced corrosion and side reactions. More importantly, the functionalized sub-nano channels also act as ion rectifiers and promote fast but even Zn-ions transport, thereby leading to a dendrite-free Zn metal. As a result, the protected Zn metal demonstrates an unprecedented cycling stability of more than 10 000 h and an ultra-high average CE of 99.92% during 4000 cycles. More inspiringly, a practical NH4V4O10//Zn pouch-cell is fabricated and delivers a capacity of 98 mAh (under high cathode mass loading of 25.7 mg cm-2) and preserves 86.2% capacity retention after 150 cycles. This new strategy in promoting highly reversible Zn metal anodes would spur the practical utilization of AZMBs.

Zinc-Ion Anchor Induced Highly Reversible Zn Anodes for High Performance Zn-Ion Batteries.

Unstable Zn interface with serious detrimental parasitic side-reactions and uncontrollable Zn dendrites severely plagues the practical application of aqueous zinc-ion batteries. The interface stability was closely related to the electrolyte configuration and Zn2+ depositional behavior. In this work, a unique Zn-ion anchoring strategy is originally proposed to manipulate the coordination structure of solvated Zn-ions and guide the Zn-ion depositional behavior. Specifically, the amphoteric charged ion additives (denoted as DM), which act as zinc-ion anchors, can tightly absorb on the Zn surface to guide the uniform zinc-ion distribution by using its positively charged -NR4 + groups. While the negatively charged -SO3 - groups of DM on the other hand, reduces the active water molecules within solvation sheaths of Zn-ions. Benefiting from the special synergistic effect, Zn metal exhibits highly ordered and compact (002) Zn deposition and negligible side-reactions. As a result, the advanced Zn||Zn symmetric cell delivers extraordinarily 7000 hours long lifespan (0.25 mA cm-2, 0.25 mAh cm-2). Additionally, based on this strategy, the NH4V4O10||Zn pouch-cell with low negative/positive capacity ratio (N/P ratio=2.98) maintains 80.4 % capacity retention for 180 cycles. A more practical 4 cm*4 cm sized pouch-cell could be steadily cycled in a high output capacity of 37.0 mAh over 50 cycles.

Unleashing the high energy potential of zinc-iodide batteries: high-loaded thick electrodes designed with zinc iodide as the cathode.

The realization of high energy is of great importance to unlock the practical potential of zinc-iodine batteries. However, significant challenges, such as low iodine loading (mostly less than 50 wt%), restricted iodine reutilization, and severe structural pulverization during cycling, compromise its intrinsic features. This study introduces an optimized, fully zincified zinc iodide loaded onto a hierarchical carbon scaffold with high active component loading and content (82 wt%) to prepare a thick cathode for enabling high-energy Zn-I2 batteries. The synergistic interactions between nitrogen heteroatoms and cobalt nanocrystals within the porous matrix not only provide forceful chemisorption to lock polyiodide intermediates but also invoke the electrocatalytic effects to manipulate efficient iodine conversion. The ZnI2 cathode could effectively alleviate continuous volumetric expansion and maximize the utilization of active species. The electrochemical examinations confirm the thickness-independent battery performance of assembled Zn-I2 cells due to the ensemble effect of composite electrodes. Accordingly, with a thickness of 300 µm and ZnI2 loading of up to 20.5 mg cm-2, the cathode delivers a specific capacity of 92 mA h gcathode-1 after 2000 cycles at 1C. Moreover, the Zn-I2 pouch cell with ZnI2 cathode has an energy density of 145 W h kgcathode-1 as well as a stable long cycle life.

Chelating Additive Regulating Zn-Ion Solvation Chemistry for Highly Efficient Aqueous Zinc-Metal Battery.

Aqueous zinc-metal batteries (AZMBs) usually suffered from poor reversibility and limited lifespan because of serious water induced side-reactions, hydrogen evolution reactions (HER) and rampant zinc (Zn) dendrite growth. Reducing the content of water molecules within Zn-ion solvation sheaths can effectively suppress those inherent defects of AZMBs. In this work, we originally discovered that the two carbonyl groups of N-Acetyl-ϵ-caprolactam (N-ac) chelating ligand can serve as dual solvation sites to coordinate with Zn2+, thereby minimizing water molecules within Zn-ion solvation sheaths, and greatly inhibit water-induced side-reactions and HER. Moreover, the N-ac chelating additive can form a unique physical barrier interface on Zn surface, preventing the harmful contacting with water. In addition, the preferential adsorption of N-ac on Zn (002) facets can promote highly reversible and dendrite-free Zn2+ deposition. As a result, Zn//Cu half-cell within N-ac added electrolyte delivered ultra-high 99.89 % Coulombic efficiency during 8000 cycles. Zn//Zn symmetric cells also demonstrated unprecedented long life of more than 9800 hours (over one year). Aqueous Zn//ZnV6O16 ⋅ 8H2O (Zn//ZVO) full-cell preserved 78 % capacity even after ultra-long 2000 cycles. A more practical pouch-cell was also obtained (90.2 % capacity after 100 cycles). This method offers a promising strategy for accelerating the development of highly efficient AZMBs.

Solid-State Electrolytes and Electrode/Electrolyte Interfaces in Rechargeable Batteries.

Solid-state batteries (SSBs) are considered to be one of the most promising candidates for next-generation energy storage systems due to the high safety, high energy density and wide operating temperature range of solid-state electrolytes (SSEs) they use. Unfortunately, the practical application of SSEs has rarely been successful, which is largely attributed to the low chemical stability and ionic conductivity, ineluctable solid-solid interface issues including limited ion transport channels, high energy barriers, and poor interface contact. A comprehensive understanding of ion transport mechanisms of various SSEs, interactions between fillers and polymer matrixes and the role of the interface in SSBs are indispensable for rational design and performance optimization of novel electrolytes. The categories, research advances and ion transport mechanism of inorganic glass/ceramic electrolytes, polymer-based electrolytes and corresponding composite electrolytes are detailly summarized and discussed. Moreover, interface contact and compatibility between electrolyte and cathode/anode are also briefly discussed. Furthermore, the electrochemical characterization methods of SSEs used in different types of SSBs are also introduced. On this basis, the principles and prospects of novel SSEs and interface design are curtly proposed according to the development requirements of SSBs. Moreover, the advanced characterizations for real-time monitoring of interface changes are also brought forward to promote the development of SSBs.

Aligned Dipoles Induced Electric-Field Promoting Zinc-Ion De-Solvation toward Highly Stable Dendrite-Free Zinc-Metal Batteries.

Water-induced parasitic reactions and uncontrolled dendritic Zn growth are long-lasting tricky problems that severely hinder the development of aqueous zinc-metal batteries. Those notorious issues are closely related to electrolyte configuration and zinc-ion transport behavior. Herein, through constructing aligned dipoles induced electric-field on Zn surface, both the solvation structure and transport behavior of zinc-ions are fundamentally changed. The vertically ordered zinc-ion migration trajectory and gradually concentrated zinc-ion achieved inside the polarized electric-field remarkably eliminate water related side-reactions and Zn dendrites. Zn-metal under the polarized electric-field demonstrated significantly improve reversibility and a dendrite-free surface with strong (002) Zn deposition texturing. Zn||Zn symmetric cell delivers greatly prolonged lifespan up to 1400 h (17 times longer than that of the cell based on bare Zn) while the Zn||Cu half-cell demonstrate ultrahigh 99.9% coulombic efficiency. NH4 V4 O10 ||Zn half-cell delivered exceptional-high 132 mAh g-1 capacity after ultralong 2000 cycles (≈100% capacity retention). In addition, MnO2 ||Zn pouch-cell under aligned dipoles induced electric-field maintains 87.9% capacity retention after 150 cycles under practical condition of high MnO2 mass loading (≈10 mg cm-2 ) and limited N/P ratio. It is considered that this new strategy can also be implemented to other metallic batteries and spur the development of batteries with long-lifespan and high-energy-density.

Highly Stable Aqueous Zinc Metal Batteries Enabled by an Ultrathin Crack-Free Hydrophobic Layer with Rigid Sub-Nanochannels.

Aqueous zinc-metal batteries (AZMBs) have received tremendous attentions due to their high safety, low cost, environmental friendliness, and simple process. However, zinc-metal still suffer from uncontrollable dendrite growth and surface parasitic reactions that reduce the Coulombic efficiency (CE) and lifetime of AZMBs. These problems which are closely related to the active water are not well-solved. Here, an ultrathin crack-free metal-organic framework (ZIF-7x -8) with rigid sub-nanopore (0.3 nm) is constructed on Zn-metal to promote the de-solvation of zinc-ions before approaching Zn-metal surface, reduce the contacting opportunity between water and Zn, and consequently eliminate water-induced corrosion and side-reactions. Due to the presence of rigid and ordered sub-nanochannels, Zn-ions deposits on Zn-metal follow a highly ordered manner, resulting in a dendrite-free Zn-metal with negligible by-products, which significantly improve the reversibility and lifespan of Zn-metals. As a result, Zn-metal protected by ultrathin crack-free ZIF-7x -8 layer exhibits excellent cycling stability (over 2200 h) and extremely-high 99.96% CE during 6000 cycles. The aqueous PANI-V2 O5 //ZIF-7x -8@Zn full-cell preserves 86% high-capacity retention even after ultra-long 2000 cycles. The practical pouch-cell can also be cycled for more than 120 cycles. It is believed that the simple strategy demonstrated in this work can accelerate the practical utilizations of AZMBs.

Unique ion rectifier intermediate enabled by ultrathin vermiculite sheets for high-performance Zn metal anodes.

Metallic Zn represents as a primary choice in fabricating various aqueous Zn-ion batteries (ZIBs), however challenging issues including dendrite growth and parasitic reactions at the anode/electrolyte interface, considerably hamper its practical implementation in large-scale energy storage. Herein, we report a low-cost multifunctional ion rectifier (IRT) as an artificial intermediate to reform Zn anode, which can practically eliminate the above issues. The hydrophobic shell (polyvinylidene difluoride) can suppress Zn interfacial corrosion with an inhibition efficiency of 94.8% by repelling water molecules from the bulk electrolyte. Additionally, negatively-charged ion channels inside the zincophilic core (ultrathin vermiculite sheets) induce de-solvating redistribution effect on Zn2+ ions flux, enabling a high ions transference number (0.79) for dendrite-free Zn deposition. This leads to exceptional Zn/Zn2+ reversibility in metallic Zn with IRT stabilization. The remarkable Coulombic efficiency (99.8%, 2000 cycles) for asymmetrical batteries, and a long lifespan (1600 h) with ultrahigh cumulative capacity of 2400 mAh cm-2 for symmetrical batteries, are successfully achieved. More encouragingly, the Zn//NH4V4O10 pouch cell retains 94.3% of its original capacity after 150 cycles at 1 A g-1. We believe that this low-cost and high-efficiency tactic could pave a promising path for anode surface modification.

Lithiophilic Magnetic Host Facilitates Target-Deposited Lithium for Practical Lithium-Metal Batteries.

Lithium-metal shows promising prospects in constructing various high-energy-density lithium-metal batteries (LMBs) while long-lasting tricky issues including the uncontrolled dendritic lithium growth and infinite lithium volume expansion seriously impede the application of LMBs. In this work, it is originally found that a unique lithiophilic magnetic host matrix (Co3 O4 -CCNFs) can simultaneously eliminate the uncontrolled dendritic lithium growth and huge lithium volume expansion that commonly occur in typical LMBs. The magnetic Co3 O4 nanocrystals which inherently embed on the host matrix act as nucleation sites and can also induce micromagnetic field and facilitate a targeted and ordered lithium deposition behavior thus, eliminating the formation of dendritic Li. Meanwhile, the conductive host can effectively homogenize the current distribution and Li-ion flux, thus, further relieving the volume expansion during cycling. Benefiting from this, the featured electrodes demonstrate ultra-high coulombic efficiency of 99.1% under 1 mA cm-2 and 1 mAh cm-2 . Symmetric cell under limited Li (10 mAh cm-2 ) inspiringly delivers ultralong cycle life of 1600 h (under 2 mA cm-2 , 1 mAh cm-2 ). Moreover, LiFePO4 ||Co3 O4 -CCNFs@Li full-cell under practical condition of limited negative/positive capacity ratio (2.3:1) can deliver remarkably improved cycling stability (with 86.6% capacity retention over 440 cycles).

Enzyme-Triggered Size-Switchable Nanosystem for Deep Tumor Penetration and Hydrogen Therapy.

The poor penetration of nanocarriers within tumor dense extracellular matrices (ECM) greatly restricts the access of anticancer drugs to the deep tumor cells, resulting in low therapeutic efficacy. Moreover, the high toxicity of the traditional chemotherapeutics inevitably causes undesirable side effects. Herein, taking the advantages of biosafe H2 and small-sized nanoparticles in diffusion within tumor ECM, we develop a matrix metalloprotease 2 (MMP-2) responsive size-switchable nanoparticle (UAMSN@Gel-PEG) that is composed of ultrasmall amino-modified mesoporous silica nanoparticles (UAMSN) wrapped within a PEG-conjugated gelatin to deliver H2 to the deep part of tumors for effective gas therapy. Ammonia borane (AB) is chosen as the H2 prodrug that can be effectively loaded into UAMSN by hydrogen-bonding adsorption. Gelatin is used as the substrate of MMP-2 to trigger size change and block AB inside UAMSN during blood circulation. PEG is introduced to further increase the particle size and endow the nanoparticle with long blood circulation to achieve effective tumor accumulation via the EPR effect. After accumulation into the tumor site, MMP-2 promptly digests gelatin to expose UAMSN loading AB for deep tumor penetration. Upon stimulation by the acidic tumor microenvironment, AB decomposes into H2 for further intratumor diffusion to achieve effective hydrogen therapy. Consequently, such a simultaneous deep tumor penetration of nanocarriers and H2 results in an evident suppression on tumor growth in a 4T1 tumor-bearing model without any obvious toxicity on normal tissues. Our synthetic nanosystem provides a promising strategy for the development of nanomedicines with enhanced tumor permeability and good biosafety for efficient tumor treatment.

In/Ce Co-doped Li3VO4 and Nitrogen-modified Carbon Nanofiber Composites as Advanced Anode Materials for Lithium-ion Batteries.

Li3VO4 (LVO) is considered as a novel alternative anode material for lithium-ion batteries (LIBs) due to its high capacity and good safety. However, the inferior electronic conductivity impedes its further application. Here, nanofibers (nLICVO/NC) with In/Ce co-doped Li3VO4 strengthened by nitrogen-modified carbon are prepared. Density functional theory calculations demonstrate that In/Ce co-doping can substantially reduce the LVO band gap and achieve orders of magnitude increase (from 2.79 × 10-4 to 1.38 × 10-2 S cm-1) in the electronic conductivity of LVO. Moreover, the carbon-based nanofibers incorporated with 5LICVO nanoparticles can not only buffer the structural strain but also form a good framework for electron transport. This 5LICVO/NC material delivers high reversible capacities of 386.3 and 277.9 mA h g-1 at 0.1 and 5 A g-1, respectively. Furthermore, high discharge capacities of 335 and 259.5 mA h g-1 can be retained after 1200 and 4000 cycles at 0.5 and 1.6 A g-1, respectively (with the corresponding capacity retention of 98.4 and 78.7%, respectively). When the 5LICVO/NC anode assembles with commercial LiNi1/3Co1/3Mn1/3O2 (NCM111) into a full cell, a high discharge capacity of 191.9 mA h g-1 can be retained after 600 cycles at 1 A g-1, implying an inspiring potential for practical application in high-efficiency LIBs.

An improved 9 micron thick separator for a 350 Wh/kg lithium metal rechargeable pouch cell.

The use of separators that are thinner than conventional separators (> 20 µm) would improve the energy densities and specific energies of lithium batteries. However, thinner separators increase the risk of internal short circuits from lithium dendrites formed in both lithium-ion and lithium metal batteries. Herein, we grow metal-organic frameworks (MOFs) inside the channels of a polypropylene separator (8 µm thick) using current-driven electrosynthesis, which aggregates the electrolyte in the MOF channels. Compared to unmodified polypropylene separators, the MOF-modified separator (9 µm thick) vastly improves the cycling stability and dendrite resistance of cells assembled with Li metal anodes and carbonate-based electrolytes. As a demonstration, a 354 Wh kg-1 pouch cell with a lithium metal anode and LiNi0.8Co0.15Al0.05O2 (NCA)-based cathode (N/P = 3.96) is assembled with 9 µm layer of the MOF-modified separator and retains 80% of its capacity after 200 cycles (charged at 75 mA g-1, discharged at 100 mA g-1) at 25 °C.

Mesoporous peroxidase nanozyme for synergistic chemodynamic therapy and chemotherapy.

Peroxidase nanozyme, enabling decomposition of hydrogen peroxide (H2O2) into highly toxic hydroxyl radical (•OH), is an emerging technology for tumor treatment. However, limited by the low H2O2 level in the tumor microenvironment, the standalone peroxidase nanozyme-mediated therapy usually fails to achieve desirable therapeutic outcomes. Herein, we presented a mesoporous nanozyme that not only had peroxidase-like activity but also could deliver anticancer drug for synergistic tumor therapy. The nanozyme, that was, iron-doped mesoporous silica nanoparticle (FeMSN), was prepared by a sol-gel method and then a calcination treatment. The introduction of iron endowed FeMSN with peroxidase-like activity that could decompose H2O2 into •OH under acidic condition for chemodynamic therapy of tumors. Meanwhile, the mesoporous structure enabled FeMSN to deliver anticancer drug doxorubicin (DOX) for chemotherapy and enhanced chemodynamic therapy through H2O2 production, ultimately achieving synergistic effect to improve the efficacy of tumor treatment. The in-vitro and in-vivo results demonstrated that DOX-loaded FeMSN exhibited significant cancer cell-killing effect and potently inhibited tumor growth. Collectively, this study represented a paradigm for achieving efficient tumor therapy through design of peroxidase-like nanozyme with drug delivery capability, which might advance the development of nanozyme in tumor chemodynamic therapy.

Multichannel Ca2+ Generator for Synergistic Tumor Therapy via Intracellular Ca2+ Overload and Chemotherapy.

Ca2+ overload has attracted an increasing attention due to its benefit of precise cancer therapy, but its efficacy is limited by the strong Ca2+ excretion of cancer cells. Moreover, monotherapy of Ca2+ overload usually fails to treat tumors satisfactorily. Herein, we develop a multifunctional nanosystem that could induce Ca2+ overload by multipathway and simultaneously produce chemotherapy for synergistic tumor therapy. The nanosystem (CaMSN@CUR) is prepared by synthesizing a Ca-doped mesoporous silica nanoparticle (CaMSN) followed by loading the anticancer drug curcumin (CUR). CaMSN serves as the basis Ca2+ generator to induce Ca2+ overload directly in the intracellular environment by acid-triggered Ca2+ release, while CUR could not only exhibit chemotherapy but also facilitate Ca2+ release from the endoplasmic reticulum to the cytoplasm and inhibit Ca2+ efflux out of cells to further enhance Ca2+ overload. The in vitro and in vivo results show that CaMSN@CUR could exhibit a remarkable cytotoxicity against 4T1 cells and significantly inhibit tumor growth in 4T1 tumor-bearing mice via the synergy of Ca2+ overload and CUR-mediated chemotherapy. It is expected that the designed CaMSN@CUR has a great potential for effective tumor therapy.

Autocatalytic oncotherapy nanosystem with glucose depletion for the cascade amplification of hypoxia-activated chemotherapy and H2O2-dependent chemodynamic therapy.

Employing hypoxia-activated prodrugs is an appealing oncotherapy strategy, but limited by insufficient tumor hypoxia. Moreover, a standalone prodrug fails to treat tumors satisfactorily due to tumor complexity. Herein, a nanosystem (TPZ@FeMSN-GOX) was established for triple synergetic cancer starvation therapy, hypoxia-activated chemotherapy and chemodynamic therapy (CDT). TPZ@FeMSN-GOX was prepared by synthesizing iron-doped mesoporous silica nanoparticles (FeMSNs) followed by surface conjugation with glucose oxidase (GOX), and then loading with hypoxia-activated prodrug tirapazamine (TPZ). When TPZ@FeMSN-GOX entered the tumor cells, GOX could not only exhaust glucose to starve cancer cells and concomitantly produce H2O2, but also consume O2 to aggravate the hypoxia environment and amplify TPZ-mediated chemotherapy. Meanwhile, the released Fe3+ was reduced to reactive Fe2+ by endogenous glutathione, which ultimately decomposed the produced H2O2 and endogenous H2O2 into highly toxic ˙OH, guaranteeing highly efficient CDT. Together, TPZ@FeMSN-GOX could effectively kill cancer cells and significantly inhibit tumor growth, providing a good paradigm for effective tumor treatment.

Building Ultra-Stable and Low-Polarization Composite Zn Anode Interface via Hydrated Polyzwitterionic Electrolyte Construction.

Aqueous zinc metal batteries are noted for their cost-effectiveness, safety and environmental friendliness. However, the water-induced notorious issues such as continuous electrolyte decomposition and uneven Zn electrochemical deposition remarkably restrict the development of the long-life zinc metal batteries. In this study, zwitterionic sulfobetaine is introduced to copolymerize with acrylamide in zinc perchlorate (Zn(ClO4)2) solution. The designed gel framework with hydrophilic and charged groups can firmly anchor water molecules and construct ion migration channels to accelerate ion transport. The in situ generated hybrid interface, which is composed of the organic functionalized outer layer and inorganic Cl- containing inner layer, can synergically lower the mass transfer overpotential, reduce water-related side reactions and lead to uniform Zn deposition. Such a novel electrolyte configuration enables Zn//Zn cells with an ultra-long cycling life of over 3000 h and a low polarization potential (~ 0.03 V) and Zn//Cu cells with high Coulombic efficiency of 99.18% for 1000 cycles. Full cells matched with MnO2 cathodes delivered laudable cycling stability and impressive shelving ability. Besides, the flexible quasi-solid-state batteries which are equipped with the anti-vandalism ability (such as cutting, hammering and soaking) can successfully power the LED simultaneously. Such a safe, processable and durable hydrogel promises significant application potential for long-life flexible electronic devices.

Intelligent Nanoplatform with Multi Therapeutic Modalities for Synergistic Cancer Therapy.

Chemodynamic therapy (CDT) has attracted increasing attention in tumor treatment but is limited by insufficient endogenous H2O2. Moreover, it is challenging for monotherapy to achieve a satisfactory outcome due to tumor complexity. Herein, we developed an intelligent nanoplatform that could respond to a tumor microenvironment to induce efficient CDT without complete dependence on H2O2 and concomitantly generate chemotherapy and oncosis therapy (OT). The nanoplatform was constructed by a calcium- and iron-doped mesoporous silica nanoparticle (CFMSN) loaded with dihydroartemisinin (DHA). After entering into cancer cells, the nanoplatform could directly convert the intracellular H2O2 into toxic •OH due to the Fenton-like activity of CFMSN. Meanwhile, the acidic microenvironment and endogenous chelating molecules triggered Ca2+ and Fe3+ release from the nanoplatform, causing particle collapse with accompanying DHA release for chemotherapy. Simultaneously, the released Ca2+ induced intracellular Ca2+-overloading for OT, which was further enhanced by DHA, while the released Fe3+ was reduced to reactive Fe2+ by intracellular glutathione, guaranteeing efficient Fenton reaction-mediated CDT. Moreover, Fe2+ cleaved the peroxy bonds of DHA to generate C-centered radicals to further amplify CDT. Both in vitro and in vivo results confirmed that the nanoplatform exhibited excellent anticancer efficacy via the synergistic effect of multi therapeutic modalities, which is extremely promising for high-efficient cancer therapy.

pH-Responsive size-shrinkable mesoporous silica-based nanocarriers for improving tumor penetration and therapeutic efficacy.

Poor tumor penetration is a major obstacle to nanomedicine for achieving effective anticancer therapy. Tumor microenvironment-induced nanomedicine size shrinkage is a promising strategy to overcome the drug penetration barrier across the dense tumor matrix. Herein, we design a size-shrinkable nanocarrier that uses acid as a means of triggering a change in particle size for co-achievement of efficient tumor accumulation followed by deep tumor penetration and rapid clearance from the body. This nanocarrier is constructed from a pH-sensitive lipid layer shell and an ultrasmall amino-functionalized mesoporous silica nanoparticle core capable of loading drugs. After intravenous injection into mice bearing the 4T1 tumor, the nanocarrier with an initial hydrodynamic size of about 33 nm could effectively accumulate at the tumor site through the enhanced permeability and retention effect. Subsequently, in the acidic tumor microenvironment, the lipid layer comprising 9 alkyl-spiropyran (SP-C9) undergoes a volume shrinkage due to the conversion of hydrophobic SP-C9 to amphiphilic 9 alkyl-merocyanine (MC-C9), thus leading to a significant decrease in the entire particle size (hydrodynamic size ∼17 nm) for enhanced intratumoral penetration. Moreover, we find that this size-shrinkable nanocarrier could be rapidly excreted out of the body based on the ICP analysis, significantly reducing biosafety issues. Benefiting from the effective tumor accumulation and penetration of the nanocarrier, the released doxorubicin shows potent antitumor efficacy. This demonstrates the high potential of the designed nanocarrier in solid tumor treatment.

Organic-Inorganic Hybrid Cathode with Dual Energy-Storage Mechanism for Ultrahigh-Rate and Ultralong-Life Aqueous Zinc-Ion Batteries.

The exploitation of cathode materials with high capacity as well as high operating voltage is extremely important for the development of aqueous zinc-ion batteries (ZIBs). Yet, the classical high-capacity materials (e.g., vanadium-based materials) provide a low discharge voltage, while organic cathodes with high operating voltage generally suffer from a low capacity. In this work, organic (ethylenediamine)-inorganic (vanadium oxide) hybrid cathodes, that is, EDA-VO, with a dual energy-storage mechanism, are designed for ultrahigh-rate and ultralong-life ZIBs. The embedded ethylenediamine (EDA) can not only increase the layer spacing of the vanadium oxide, with improved mobility of Zn ions in the V-O layered structure, but also act as a bidentate chelating ligand participating in the storage of Zn ions. This hybrid provides a high specific capacity (382.6 mA h g-1 at 0.5 A g-1 ), elevated voltage (0.82 V) and excellent long-term cycle stability (over 10 000 cycles at 5 A g-1 ). Assistant density functional theory (DFT) calculations indicate the cathode has remarkable electronic conductivity, with an ultralow diffusion barrier of 0.78 eV for an optimal Zn-ion diffusion path in the EDA-VO. This interesting idea of building organic-inorganic hybrid cathode materials with a dual energy-storage mechanism opens a new research direction toward high-energy secondary batteries.