Boosting H2O2‐Guided Chemodynamic Therapy of Cancer by Enhancing Reaction Kinetics through Versatile Biomimetic Fenton Nanocatalysts and the Second Near‐Infrared Light Irradiation

Fenton reaction–based chemodynamic therapy (CDT) has attracted considerable attention for tumor treatment, because the Fenton reaction can degrade endogenous H₂O₂ within the tumor to form reactive oxygen species (ROS) to kill cancer cells. The kinetics of the Fenton reaction has significantly influenced its treatment efficacy. It is crucial to enhance the reaction kinetics at the maximum H₂O₂ concentration to quickly produce vast amounts of ROS to achieve treatment efficacy, which to date, has not been realized. Herein, reported is an efficacious CDT treatment of breast cancer using biomimetic CS‐GOD@CM nanocatalysts, which are rationally designed to significantly boost the Fenton reaction through improvement of H₂O₂ concentration within tumors, and application of the second near‐infrared (NIR‐II) light irradiation at the maximum concentration, which is monitored by photoacoustic imaging. The biomimetic nanocatalysts are composed of ultra‐small Cu_2?xSe (CS) nanoparticles, glucose oxidase (GOD), and tumor cell membrane (CM). The nanocatalysts can be retained in tumor for more than two days to oxidize glucose and produce an approximately 2.6‐fold increase in H₂O₂ to enhance the Fenton reaction under the NIR‐II irradiation. This work demonstrates for the first time the CDT treatment of cancer enhanced by the NIR‐II light.     

Co–Ferrocene MOF/Glucose Oxidase as Cascade Nanozyme for Effective Tumor Therapy

Chemodynamic therapy (CDT), enabling selective therapeutic effects and low side effect, attracts increasing attention in recent years. However, limited intracellular content of H₂O₂ and acid at the tumor site restrains the lasting Fenton reaction and thus the anticancer efficacy of CDT. Herein, a nanoscale Co–ferrocene metal–organic framework (Co‐Fc NMOF) with high Fenton activity is synthesized and combined with glucose oxidase (GOx) to construct a cascade enzymatic/Fenton catalytic platform (Co‐Fc@GOx) for enhanced tumor treatment. In this system, Co‐Fc NMOF not only acts as a versatile and effective delivery cargo of GOx molecules to modulate the reaction conditions, but also possesses excellent Fenton effect for the generation of highly toxic ?OH. In the tumor microenvironment, GOx delivered by Co‐Fc NMOF catalyzes endogenous glucose to gluconic acid and H₂O₂. The intracellular acidity and the on‐site content of H₂O₂ are consequently promoted, which in turn favors the Fenton reaction of Co‐Fc NMOF and enhances the generation of reactive oxygen species (ROS). Both in vitro and in vivo results demonstrate that this cascade enzymatic/Fenton catalytic reaction triggered by Co‐Fc@GOx nanozyme enables remarkable anticancer properties.     

Copper(I) Phosphide Nanocrystals for In Situ Self‐Generation Magnetic Resonance Imaging‐Guided Photothermal‐Enhanced Chemodynamic Synergetic Therapy Resisting Deep‐Seated Tumor

Fe‐based Fenton agents can generate highly reactive and toxic hydroxyl radicals (·OH) in the tumor microenvironment (TME) for chemodynamic therapy (CDT) with high specificity. However, the strict condition (lower pH environment: 3–4) of the highly efficient Fenton reaction limits its practical application in the clinic. Development of new CDT agents more suitable for TME is significant and challenging. A highly efficient Cu(I)‐based CDT agent, copper(I) phosphide nanocrystals (CP NCs), which is more adaptable to the pH value of TME than Fe‐based agents, thereby producing more ·OH to trigger the apoptosis of cancer cells, is prepared. Moreover, the excess glutathione (GSH) in TME can reduce the Cu(II) produced by a Fenton‐like reaction to Cu(I), further increasing the generation rate of ·OH and relieving tumor antioxidant ability. Furthermore, owing to their strong absorption in the NIR II region, CP NCs exhibit an excellent photothermal conversion effect, which can further improve the Fenton reaction. What is more, CP NCs can act as in situ self‐generation magnetic resonance imaging (MRI) agents owing to the generation of paramagnetic Cu(II) in response to excess H₂O₂ in the TME. These properties may open up the exploration of copper‐based materials in clinical application of self‐generation imaging‐guided synergetic treatment.     

GSH‐Depleted PtCu3 Nanocages for Chemodynamic‐ Enhanced Sonodynamic Cancer Therapy

The ultrahigh concentration of glutathione (GSH) inside tumors destroys reactive oxygen species (ROS)‐based therapy, improving the outcome of chemodynamic therapy (CDT)‐enhanced sonodynamic therapy (SDT) by depleting GSH is full of great challenge. Herein, PtCu₃ nanocages are first reported as acting as a sonosensitizer with highly efficient ROS generation under ultrasound irradiation. In addition, PtCu₃ nanocages can act as horseradish peroxidase‐like nanozymes, catalyzing the decomposition of H₂O₂ into ^?OH under acidic conditions for CDT. Surprisingly, PtCu₃ nanocages can act as another kind of nanozyme, mimicking glutathione peroxidase (GSH‐Px), which plays an important role in accelerating GSH depletion by oxidizing molecules, further weakening the capacity of tumor cells scavenging ROS by GSH. Both in vitro and in vivo studies demonstrate that PtCu₃ nanocages perform well in reducing GSH level for CDT‐enhanced SDT. Moreover, utilizing the high absorption in the near‐infrared region and strong X‐ray attenuation ability, the PtCu₃ nanocages are able to conduct photoacoustic/computed tomography dual‐modal imaging‐guided combined cancer therapy. It is worth mentioning that PtCu₃ nanocages cause minimal toxicity to normal tissues at therapeutic doses. This work highlights the use of PtCu₃ nanocages for effective CDT‐enhanced SDT via GSH depletion.     

Reactive Oxygen Species–Activatable Liposomes Regulating Hypoxic Tumor Microenvironment for Synergistic Photo/Chemodynamic Therapies

Tumors have adapted various cellular antidotes and microenvironmental conditions to subsist against photodynamic therapy (PDT) and chemodynamic therapy (CDT). Here, the development of reactive oxygen species (ROS)‐activatable liposomes (RALP) for therapeutic enhancement by simultaneously addressing the critical questions in PDT and CDT is reported. The design of RALP@HOC@Fe₃O₄ features ROS‐cleavable linker molecules for improved tumor penetration/uptake and ondemand cargo releasing, and integration of Fe₃O₄ and an oxaliplatin prodrug for smart regulation of hypoxia tumor microenvironment. Glutathione stored by the tumor cells is consumed by the prodrug to produce highly toxic oxaliplatin. Depletion of glutathione not only avoids the undesired annihilation of ROS in PDT, but also modulates the chemical specie equilibria in tumors for H₂O₂ promotion, leading to greatly relieved tumor hypoxia and PDT enhancement. Synergistically, Fe (II) in the hybrid RALP formulation can be fuelled by H₂O₂ to generate ?OH in the Fenton reaction, thus elevating CDT efficiency. This work offers a strategy for harnessing smart, responsive, and biocompatible liposomes to enhance PDT and CDT by regulating tumor microenvironment, highlighting a potential clinical translation beneficial to patients with cancer.     

In Situ Polymerized Hollow Mesoporous Organosilica Biocatalysis Nanoreactor for Enhancing ROS‐Mediated Anticancer Therapy

The combination of reactive oxygen species (ROS)‐involved photodynamic therapy (PDT) and chemodynamic therapy (CDT) holds great promise for enhancing ROS‐mediated cancer treatment. Herein, an in situ polymerized hollow mesoporous organosilica nanoparticle (HMON) biocatalysis nanoreactor is reported to integrate the synergistic effect of PDT/CDT for enhancing ROS‐mediated pancreatic ductal adenocarcinoma treatment. 2‐(1‐hexyloxyethyl)‐2‐devinylpyropheophorbide‐a photosensitizer is hybridized within the framework of HMON via an “in situ framework growth” approach. Then, the hollow cavity of HMONs is exploited as a nanoreactor for “in situ polymerization” to synthesize the polymer containing thiol groups, thereby enabling the immobilization of ultrasmall gold nanoparticles, which behave like glucose oxidase‐like nanozyme, converting glucose into H₂O₂ to provide self‐supplied H₂O₂ for CDT. Meanwhile, Cu²⁺‐tannic acid complexes are further deposited on the surface of HMONs (HMON‐Au@Cu‐TA) to initiate Fenton‐like reaction to covert the self‐supplied H₂O₂ into ?OH, a highly toxic ROS. Finally, collagenase (Col), which can degrade the collagen I fiber in the extracellular matrix, is loaded into HMON‐Au@Cu‐TA to enhance the penetration of HMONs and O₂ infiltration for enhanced PDT. This study provides a good paradigm for enhancing ROS‐mediated antitumor efficacy. Meanwhile, this research offers a new method to broaden the application of silica based nanotheranostics.     

Biodegradable Fe(III)@WS2‐PVP Nanocapsules for Redox Reaction and TME‐Enhanced Nanocatalytic,Photothermal, and Chemotherapy

In this study, biocompatible Fe(III) species‐WS₂‐polyvinylpyrrolidone (Fe(III) @ WS₂‐PVP) nanocapsules with enhanced biodegradability and doxorubicin (DOX) loading capacity are one‐pot synthesized. In this nanocapsule, there exists a redox reaction between Fe(III) species and WS₂ to form Fe²⁺ and WO₄^2?. The formed Fe²⁺ could be oxidized to Fe³⁺, which reacts with Fe(III) @ WS₂‐PVP again to continuously produce Fe²⁺ and WO₄^2?. Such a repeated endogenous redox reaction leads to an enhanced biodegradation and DOX release of DOX @ Fe(III) @ WS₂‐PVP. More strikingly, the Fe²⁺ generation and DOX release are further accelerated by the overexpressed H₂O₂ and the mild acidic tumor microenvironment (TME), since H₂O₂ and H⁺ can accelerate the oxidation of Fe²⁺. The continuously generated Fe²⁺ catalyzes a fast Fenton reaction with the innate H₂O₂ in tumor cells and produces abundant highly toxic hydroxyl radicals for nanocatalytic tumor therapy. Together with the high photothermal transforming capability, the DOX @ Fe(III) @WS₂‐PVP nanocapsules successfully achieve the endogenous redox reaction and exogenous TME‐augmented tumor photothermal therapy, chemo and nanocatalytic therapy outcome. The concept of material design can be innovatively extended to the synthesis of biodegradable Fe(III) @ MoS₂‐PVP nanocomposite, thus paving a promising novel way for the rational design of intelligent theranostic agents for highly efficient treatment of cancer.     

Engineering Janus Chemoreactive Nanosonosensitizers for Bilaterally Augmented Sonodynamic and Chemodynamic Cancer Nanotherapy

As a non-invasive treatment modality with high tissue-penetration depth, ultrasound-triggered sonodynamic therapy (SDT) has been extensively explored and is regarded as the alternative choice to overcome the drawbacks of conventional photo-triggered therapies. Nevertheless, the low quantum yield of sonosensitizer, tumor hypoxia, and undesirable therapeutic efficiency are still the major concerns of SDT. It is highly challenging but necessary to explore the SDT-based synergistic, augmented, and noninvasive therapeutic modalities. Herein, a distinct TiO₂ Fe₃O₄@PEG Janus nanostructure composed of the typical sonosensitizer TiO₂ and nanoenzyme Fe₃O₄ is rationally designed and engineered for bilaterally enhanced SDT and chemodynamic therapy (CDT). The deposition of Fe₃O₄ component on the surface of TiO₂ can not only endow the Janus nanosonosensitizers with Fenton-catalytic activity to generate hydroxyl radicals (•OH) from tumor-endogenous overexpressed H₂O₂ for CDT but also enhance the SDT performance of TiO₂ via narrowing the band gap of TiO₂ and reducing the recombination rate of the electrons (e^–/h⁺) pair. In turn, the US activation can both accelerate mass transfer and chemical reaction rates of the Fenton reaction to enhance the CDT effect. The high efficacy of bilaterally enhanced SDT and CDT is systematically demonstrated both in vitro and in vivo.     

Design of Hybrid MnO2‐Polymer‐Lipid Nanoparticles with Tunable Oxygen Generation Rates and Tumor Accumulation for Cancer Treatment

Manganese dioxide (MnO₂) nanoparticles (NPs) were discovered in previous work to be effective in improving tumor oxygenation (hypoxia) and reducing H₂O₂ and acidity in the tumor microenvironment (TME) via local injection. To develop MnO₂ formulations useful for clinical application, hybrid NPs are designed with tailored hydrophobicity and structure suitable for intravenous injection, with good blood circulation, biocompatibility, high tumor accumulation, and programmable oxygen generation rate. Two different hybrid NPs are constructed by embedding polyelectrolyte‐MnO₂ (PMD) in hydrophilic terpolymer/protein‐MnO₂ (TMD) or hydrophobic polymer/lipid‐MnO₂ (LMD) matrices. The in vitro reactivity of the MnO₂ toward H₂O₂ is controlled by matrix material and NP structure and dependent on pH with up to two‐fold higher O₂ generation rate at acidic (tumor) pH than at systemic pH. The hybrid NPs are found to be safe to cells in vitro and organs in vivo and effectively decrease tumor hypoxia and hypoxia‐inducible‐factor‐1alpha through local or systemic administration. Fast acting TMD reduces tumor hypoxia by 70% in 0.5 h by local injection. Slow acting LMD exhibits superior tumor accumulation and retention through the systemic administration and decreased hypoxia by 45%. These findings encourage a broader use of hybrid MD NPs to overcome TME factors for cancer treatment.     

Intracellular Mutual Promotion of Redox Homeostasis Regulation and Iron Metabolism Disruption for Enduring Chemodynamic Therapy

Intracellular redox homeostasis and the iron metabolism system in tumor cells are closely associated with the limited efficacy of chemodynamic therapy (CDT). Despite extensive attempts, maintaining high levels of intracellular catalysts (free iron) and reactants (H₂O₂) while decreasing the content of reactive oxygen species (ROS) scavengers (especially glutathione (GSH)) for enduring CDT still remains great challenges. Herein, S S bond-rich dendritic mesoporous organic silica nanoparticles (DMON) are utilized as GSH-depleting agents. After co-loading Fe⁰ and a catalase inhibitor (3-amino-1,2,4-triazole (AT)), a novel biodegradable nanocarrier is constructed as DMON@Fe⁰/AT. In the mildly acidic tumor microenvironment, on-demand ferrous ions and AT are intelligently released. AT suppresses the activity of catalase for H₂O₂ hoarding, and the exposed DMON weakens ROS scavenging systems by persistently depleting intracellular GSH. The highly efficient •OH production by DMON@Fe⁰/AT can effectively attack mitochondria and downregulate the expression of ferroportin 1, which can disrupt the cellular iron metabolism system, leading to the desired retention of iron in the cytoplasm. More importantly, DMON@Fe⁰/AT exhibits a much more efficient CDT killing effect on 4T1 tumor cells than plain Fe⁰ nanoparticles, benefiting from their synergistic redox regulation and iron metabolism disruption. Overall, the as-prepared intelligent, degradable DMON@Fe⁰/AT provides an innovative strategy for enduring CDT.     

A Robust ROS Generation Strategy for Enhanced Chemodynamic/Photodynamic Therapy via H2O2/O2 Self-Supply and Ca2+ Overloading

The efficacy of cancer therapy with reactive oxygen species (ROS) as the main therapeutic medium suffers from a deficiency of oxy-substrates, for example, insufficient endogenous hydrogen peroxide (H₂O₂) in chemodynamic therapy (CDT) and inherent hypoxia in photodynamic therapy (PDT). Herein, a smart polyethylene glycol (PEG)-ylated nanosystem CaO₂@ZIF-Fe/Ce6@PEG (abbreviation as CaZFCP) is constructed to achieve H₂O₂/O₂ self-supply and Ca²⁺ overloading in tumor cells simultaneously for enhanced CDT/PDT. Under the weakly acidic tumor microenvironment, the activity components inside CaZFCP, that is, CaO₂ nanoparticles, Fe²⁺, and photosensitizer Chlorin e6 (Ce6) are released by the degradation of zeolitic imidazole framework-90 (ZIF-90). Thereinto, CaO₂ nanoparticles are further decomposed to generate H₂O₂ and O₂, which alleviates both the insufficient endogenous H₂O₂ and hypoxia in tumor area, thus enhancing the efficiency of CDT and PDT by producing more hydroxyl radicals and singlet oxygen. Furthermore, Ca²⁺ overloading induced by the decomposition of CaO₂ is available for amplifying intracellular oxidative stress, resulting in mitochondrial dysfunction, which further improves the efficacy of combined CDT/PDT. In vitro and in vivo experimental results confirm excellent tumor inhibition effect, which also provides a facile paradigm in ROS-involved cancer therapies.     

Nanoscale Refractive Index Tuning of Siloxane‐Based Self‐Assembled Electro‐Optic Superlattices

The refractive indices of self‐assembled organic electro‐optic superlattices can be tuned by intercalating high‐Z optically transparent group 13 metal oxide sheets into the structures during the self‐assembly process. Microstructurally regular acentricity and sizable electro‐optic responses are retained in this straightforward synthetic procedure. This “one‐pot” all wet‐chemistry approach involves: i) layer‐by‐layer covalent self‐assembly of intrinsically acentric multilayers of high‐hyperpolarizability chromophores on inorganic oxide substrates, ii) protecting group cleavage to generate a large density of reactive surface hydroxyl sites, iii) self‐limiting capping of each chromophore layer with octachlorotrisiloxane, iv) deposition of metal oxide sheets derived from THF solutions of Ga(OⁱC₃H₇)₃ or In(OⁱC₃H₇)₃, and v) covalent capping of the resulting superlattices.     

Solution‐Processed GaSe Nanoflake‐Based Films for Photoelectrochemical Water Splitting and Photoelectrochemical‐Type Photodetectors

Gallium selenide (GaSe) is a layered compound, which has been exploited in nonlinear optical applications and photodetectors due to its anisotropic structure and pseudodirect optical gap. Theoretical studies predict that its 2D form is a potential photocatalyst for water splitting reactions. Herein, the photoelectrochemical (PEC) characterization of GaSe nanoflakes (single‐/few‐layer flakes), produced via liquid phase exfoliation, for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both acidic and alkaline media is reported. In 0.5 m H₂SO₄, the GaSe photoelectrodes display the best PEC performance, corresponding to a ratiometric power‐saved metric for HER (Φ_saved,HER) of 0.09% and a ratiometric power‐saved metric for OER (Φ_saved,OER) of 0.25%. When used as PEC‐type photodetectors, GaSe photoelectrodes show a responsivity of ≈0.16 A W^?1 upon 455 nm illumination at a light intensity of 63.5 µW cm^?2 and applied potential of ?0.3 V versus reversible hydrogen electrode (RHE). Stability tests of GaSe photodetectors demonstrated a durable operation over tens of cathodic linear sweep voltammetry scans in 0.5 m H₂SO₄ for HER. In contrast, degradation of photoelectrodes occurred in both alkaline and anodic operation due to the highly oxidizing environment and O₂‐induced (photo)oxidation effects. The results provide new insight into the PEC properties of GaSe nanoflakes for their exploitation in photoelectrocatalysis, PEC‐type photodetectors, and (bio)sensors.     

Long Minority‐Carrier Diffusion Length and Low Surface‐Recombination Velocity in Inorganic Lead‐Free CsSnI3 Perovskite Crystal for Solar Cells

Sn‐based perovskites are promising Pb‐free photovoltaic materials with an ideal 1.3 eV bandgap. However, to date, Sn‐based thin film perovskite solar cells have yielded relatively low power conversion efficiencies (PCEs). This is traced to their poor photophysical properties (i.e., short diffusion lengths (<30 nm) and two orders of magnitude higher defect densities) than Pb‐based systems. Herein, it is revealed that melt‐synthesized cesium tin iodide (CsSnI₃) ingots containing high‐quality large single crystal (SC) grains transcend these fundamental limitations. Through detailed optical spectroscopy, their inherently superior properties are uncovered, with bulk carrier lifetimes reaching 6.6 ns, doping concentrations of around 4.5 × 10¹⁷ cm^?3, and minority‐carrier diffusion lengths approaching 1 µm, as compared to their polycrystalline counterparts having ≈54 ps, ≈9.2 × 10¹⁸ cm^?3, and ≈16 nm, respectively. CsSnI₃ SCs also exhibit very low surface recombination velocity of ≈2 × 10³ cm s^?1, similar to Pb‐based perovskites. Importantly, these key parameters are comparable to high‐performance p‐type photovoltaic materials (e.g., InP crystals). The findings predict a PCE of ≈23% for optimized CsSnI₃ SCs solar cells, highlighting their great potential.     

Magnetic Hyperthermia–Synergistic H2O2 Self‐Sufficient Catalytic Suppression of Osteosarcoma with Enhanced Bone‐Regeneration Bioactivity by 3D‐Printing Composite Scaffolds

Chemotherapy resistance and bone defects caused by surgical excision of osteosarcoma have been formidable challenges for clinical treatment. Although recently developed nanocatalysts based on Fenton‐like reactions for catalytic therapy demonstrate high potential to eliminate chemotherapeutic‐insensitive tumors, insufficient concentration of intrinsic hydrogen peroxide (H₂O₂) and low intratumoral penetrability hinder their applications and therapeutic efficiency. The synchronous enriching intratumor H₂O₂ amount or nanoagents and promoting osteogenesis are intriguing strategies to solve the dilemma in osteosarcoma therapy. Herein, a multifunctional “all‐in‐one” biomaterial platform is constructed by co‐loading calcium peroxide (CaO₂) and iron oxide (Fe₃O₄) nanoparticles into a three‐dimensional (3D) printing akermanite scaffold (AKT‐Fe₃O₄‐CaO₂). The loaded CaO₂ nanoparticles act as H₂O₂ sources to achieve H₂O₂ self‐sufficient nanocatalytic osteosarcoma therapy as catalyzed by coloaded Fe₃O₄ nanoagents, as well as provide calcium ion (Ca²⁺) pools to enhance bone regeneration. The synergistic osteosarcoma‐therapeutic effect is achieved from both magnetic hyperthermia as‐enabled by Fe₃O₄ nanoparticles under alternative magnetic fields and hyperthermia‐enhanced Fenton‐like nanocatalytic reaction for producing highly toxic hydroxyl radicals. Importantly, the constructed 3D AKT‐Fe₃O₄‐CaO₂ composite scaffolds are featured with favorable bone‐regeneration activity, providing a worthy base and positive enlightenment for future osteosarcoma treatment with bone defects by the multifunctional biomaterial platforms.     

Core–Satellite Mesoporous Silica–Gold Nanotheranostics for Biological Stimuli Triggered Multimodal Cancer Therapy

A core–satellite nanotheranostic agent with pH‐dependent photothermal properties, pH‐triggered drug release, and H₂O₂‐induced catalytic generation of radical medicine is fabricated to give a selective and effective tumor medicine with three modes of action. The nanocomplex (core–satellite mesoporous silica–gold nanocomposite) consists of amino‐group‐functionalized mesoporous silica nanoparticles (MSN‐NH₂) linked to L‐cysteine‐derivatized gold nanoparticles (AuNPs‐Cys) with bridging ferrous iron (Fe²⁺) ions. The AuNPs‐Cys serve as both removable caps that control drug release (doxorubicin) and stimuli‐responsive agents for selective photothermal therapy. Drug release and photothermal therapy are initiated by the cleavage of Fe²⁺ coordination bonds at low pH and the spontaneous aggregation of the dissociated AuNPs‐Cys. In addition, the Fe²⁺ is able to catalyze the decomposition of hydrogen peroxide abundant in cancer cells by a Fenton‐like reaction to generate high‐concentration hydroxyl radicals (·OH), which then causes cell damage. This system requires two tumor microenvironment conditions (low pH and considerable amounts of H₂O₂) to trigger the three therapeutic actions. In vivo data from mouse models show that a tumor can be completely inhibited after two weeks of treatment with the combined chemo‐photothermal method; the data directly demonstrate the efficiency of the MSN–Fe–AuNPs for tumor therapy.     

Non‐Fenton‐Type Hydroxyl Radical Generation and Photothermal Effect by Mitochondria‐Targeted WSSe/MnO2 Nanocomposite Loaded with Isoniazid for Synergistic Anticancer Treatment

Here, in terms of the highly reactive oxidative hydroxyl radical (?OH) generation ability of isoniazid (INH) catalyzed by Mn²⁺ ion and the photothermal effect of WSSe nanoflakes, a WSSe/MnO₂‐INH nanocomposite for synergistic anticancer treatment is developed. Advanced INH‐induced ?OH formation ability is systemically demonstrated in the presence of manganese and relevant non‐Fenton‐type mechanism, and good photothermal conversion efficiency of the WSSe/MnO₂ nanocomposite. After modifying with mitochondria‐targeted triphenylphosphonium bromide (TPP) moieties and camouflaging with cancer cells membrane (WSSe/MnO₂‐INH‐TPP@CM), it confers a sequential cell‐to‐mitochondria targeting ability. In vivo X‐ray computed tomography and magnetic resonance tumor imaging capability of the nanocomposite are also revealed. The mitochondria‐targeted oxidative damage and photothermal therapy by WSSe/MnO₂‐INH‐TPP@CM results in excellent anticancer treatment efficacy both in vitro and in vivo. This is the first exploration of the possibility of non‐Fenton‐type ?OH formation for anticancer treatment, which opens new opportunities for ROS‐based and combined cancer treatment strategies.     

High‐Performance Transition Metal Dichalcogenide Photodetectors Enhanced by Self‐Assembled Monolayer Doping

Most doping research into transition metal dichalcogenides (TMDs) has been mainly focused on the improvement of electronic device performance. Here, the effect of self‐assembled monolayer (SAM)‐based doping on the performance of WSe₂‐ and MoS₂‐based transistors and photodetectors is investigated. The achieved doping concentrations are ≈1.4 × 10¹¹ for octadecyltrichlorosilane (OTS) p‐doping and ≈10¹¹ for aminopropyltriethoxysilane (APTES) n‐doping (nondegenerate). Using this SAM doping technique, the field‐effect mobility is increased from 32.58 to 168.9 cm² V^?1 s in OTS/WSe₂ transistors and from 28.75 to 142.2 cm² V^?1 s in APTES/MoS₂ transistors. For the photodetectors, the responsivity is improved by a factor of ≈28.2 (from 517.2 to 1.45 × 10⁴ A W^?1) in the OTS/WSe₂ devices and by a factor of ≈26.4 (from 219 to 5.75 × 10³ A W^?1) in the APTES/MoS₂ devices. The enhanced photoresponsivity values are much higher than that of the previously reported TMD photodetectors. The detectivity enhancement is ≈26.6‐fold in the OTS/WSe₂ devices and ≈24.5‐fold in the APTES/MoS₂ devices and is caused by the increased photocurrent and maintained dark current after doping. The optoelectronic performance is also investigated with different optical powers and the air‐exposure times. This doping study performed on TMD devices will play a significant role for optimizing the performance of future TMD‐based electronic/optoelectronic applications.     

“Trade‐Off” Hidden in Condensed State Solvation: Multiradiative Channels Design for Highly Efficient Solution‐Processed Purely Organic Electroluminescence at High Brightness

Actualizing highly efficient solution‐processed thermally activated delayed fluorescent (TADF) organic light‐emitting diodes (OLEDs) at high brightness becomes significant to the popularization of purely organic electroluminescence. Herein, a highly soluble emitter benzene‐1,3,5‐triyltris((4‐(9,9‐dimethylacridin‐10(9H)‐yl)phenyl)methanone was developed, yielding high delayed fluorescence rate (k_TADF > 10⁵ s^?1) ascribed to the multitransition channels and tiny singlet–triplet splitting energy (ΔE_ST ≈ 32.7 meV). The triplet locally excited state is 0.38 eV above the lowest triplet charge‐transfer state, assuring a solely thermal equilibrium route for reverse intersystem crossing. Condensed state solvation effect unveils a hidden “trade‐off”: the reverse upconversion and triplet concentration quenching processes can be promoted but with a reduced radiative rate from the increased dopant concentration and the more polarized surroundings. Striking a delicate balance, corresponding vacuum‐evaporated and solution‐processed TADF‐OLEDs realized maximum external quantum efficiencies (EQEs) of ≈26% and ≈22% with extremely suppressed efficiency roll‐off. Notably, the wet‐processed one achieves to date the highest EQEs of 20.7%, 18.5%, 17.1%, and 13.6%, among its counterparts at the luminance of 1000, 3000, 5000, and 10 000 cd m^?2, respectively.     

Smart Tumor Microenvironment‐Responsive Nanotheranostic Agent for Effective Cancer Therapy

The tumor microenvironment (TME), which includes acidic and hypoxic conditions, severely impedes the therapeutic efficacy of antitumor agents. Herein, MnO₂‐loaded, bovine serum albumin, and PEG co‐modified mesoporous CaSiO₃ nanoparticles (CaM‐PB NPs) are developed as a nanoplatform with sequential theranostic functions for the engineering of TME. The MnO₂ NPs generate O₂ in situ by reacting with endogenous H₂O₂, relieving the hypoxic state of the TME that further modulates the cancer cell cycle status to S phase, which improves the potency of co‐loaded S phase‐sensitive chemotherapeutic drugs. After the hypoxia relief, CaM‐PB can sustainably release drugs due to the enlarged pores of mesoporous CaSiO₃ in the acidic TME, preventing the drug pre‐leakage into the blood circulation and insufficient drug accumulation at tumor sites. Moreover, the Mn²⁺ released from the MnO₂ NPs at tumor sites can potentially serve as a diagnostic agent, enabling the identification of tumor regions by T₁‐weighted magnetic resonance imaging during therapy. In vivo pharmacodynamics results demonstrate that these synergetic effects caused by CaM‐PB NPs significantly contribute to the inhibition of tumor progression. Therefore, the CaM‐PB NPs with sequential theranostic functions are a promising system for effective cancer therapy.