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Polymer photosensitizers (PPSs) with the distinctive properties of good light-harvesting capability, high photostability, and excellent tumor retention effects have aroused great research interest in photodynamic therapy (PDT). However, their potential translation into clinic was often constrained by the hypoxic nature of tumor microenvironment, the aggregation-caused reduced production of reactive oxygen species (ROS), and the tedious procedure of manufacture. As a powerful and versatile strategy, vacancy engineering possesses the unique capability to effectively improve the photogenerated electron efficiency of nanomaterials for high-performance O2 and ROS production. Herein, by introducing vacancy engineering into the design of PPSs for PDT for the first time, we synthesized a novel PPS of Au-decorated polythionine (PTh) nanoconstructs (PTh@Au NCs) with the unique integrated features of distinguished O2 self-evolving function and highly efficient ROS generation for achieving the greatly enhanced PDT efficacy toward hypoxic tumor both in vitro and in vivo. The incorporation of Au into PTh leads to the special PTh-Au heterostructure-induced sulfur vacancies in PTh@Au NCs, which results in an efficient electron-hole separation performance and also plays a key role in a long lifetime of free electrons and holes. Accordingly, an ∼2- to 3-fold ROS generation and an ∼1.5-fold increase of O2 self-supply than the pure PTh nanoparticles (NPs) were obtained even under hypoxic conditions upon exposure to 650 nm light. By combining such superior ROS generation and O2 self-supply performances with the outstanding cellular internalization and tumor accumulation capacities, an advanced antitumor effect with the achievement of almost complete hypoxic tumor elimination in vivo or 88% cell destruction in vitro was acquired by the PTh@Au NCs. In addition, the distinctive facile one-step redox strategy for PTh@Au NCs synthesis compared to the reported PPSs for PDT also makes it beneficial for potential practical application. The first introduction of vacancy engineering concept into PPSs in the field of PDT proposed in this work offers a new strategy for the development and design highly efficient PPSs for PDT applications.

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Reactive oxygen species (ROS)-mediated antitumor modalities that induced oxidative damage of cancer cells have recently acquired increasing attention on account of their noninvasiveness, low systemic toxicity, and high specificity. However, their clinical efficacy was often constrained by complex and various tumor microenvironment (TME), especially hypoxia characteristic and antioxidation effect of glutathione (GSH). Herein, we constructed a multinanozyme system based on hyaluronic acid (HA)-stabilized CuMnOx nanoparticles (CMOH) loaded with indocyanine green (ICG) with high-efficient ROS generation, O2 self-evolving function, GSH depletion ability and hyperthermia effect for achieving hypoxic tumor therapy. The CMOH nanozymes exhibited peroxidase-like and oxidase-like activities, which could efficiently catalyze H2O2 or O2 to generate hydroxyl radicals (•OH) or superoxide radicals (•O2-) in acidic tumor microenvironment (TME), elevating oxidative stress of tumor. Indocyanine green (ICG) was further loaded into HA-CuMnOx to form HA-CuMnOx@ICG nanocomposites (CMOI NCs), which can effectively generate singlet oxygen (1O2) and local hyperthermia under light irradiation. The hyperthermia generated by CMOI NCs further enhances the catalytic activities of nanozymes for ROS generation. Meanwhile, the CMOI with catalase-like activity could catalyze H2O2 into O2 for relieving tumor hypoxia and elevate O2-dependent ROS generation. Notably, CMOI can consume endogenous GSH, thereby impairing tumor antioxidant system and enhancing ROS-based therapy efficacy. After modified with HA, CMOI NCs with tumor targeting ability realized synergistic PTT-enhanced tumor oxidation therapy based on their multimodal properties. Thus, this work contributes to design high-performance therapeutic reagent to overcome the limitation of hypoxia and high antioxidant defense of tumor. STATEMENT OF SIGNIFICANCE: Reactive oxygen species (ROS)-mediated antitumor modalities were often constrained by complex and various tumor microenvironment (TME), especially hypoxia characteristic and antioxidation effect of glutathione (GSH). In this work, a multinanozyme system based on hyaluronic acid (HA)-stabilized CuMnOx nanoparticles (CMOH) loaded with indocyanine green (ICG) was designed to realize PTT-enhanced multiple catalysis tumor therapy. Although antitumor modalities based on multienzyme catalysis have been developed. Here, we highlighted the responsive catalysis of multienzyme system on tumor microenvironment (TME) and the promoting effect of photothermal effect on ROS production. Both in vitro and in vivo manifested that the enhanced anticancer efficacy of CMOI NCs due to their thermally amplified catalytic activity and TME regulation ability.

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In this study, a clustered carbon aerogel interconnected by carbon balls (CCAI-CB) was prepared as an electrode material to construct a multi-functional electrochemical sensor. CCAI-CB derived from taros (Colocasia esculenta (L). Schott) possesses meso-macroporous structure and plenty of defective sites, and shows notable activity in electrocatalysis as an electrode material. We investigated the application of CCAI-CB modified glassy carbon electrode (CCAI-CB/GCE) for determination of ascorbic acid (AA) and hydrogen peroxide (H2O2). Compared with carbon nanotubes (CNTs) modified GCE (CNTs/GCE) and bare GCE, CCAI-CB/GCE shows lower detection limit (0.23 µM for AA and 1.31 µM, S/N = 3), higher sensitivities (220.53, 148.86 or 94.39 µA mM-1 cm-2 for AA and 83.06 or 49.07 µA mM-1 cm-2 for H2O2). Concentrations of AA and H2O2 in real samples were determined at CCAI-CB/GCE with satisfactory detection results obtained. In addition, when the CCAI-CB/GCE was used for electrocatalysis of other biomolecules, it also exhibits high electrochemical activity. Thus, CCAI-CB could be a promising electrode material for the construction of multi-functional electrochemical sensors.

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In this paper, sweet potatoes (Ipomoea batatas) are used as low-cost precursors to synthesize carbon aerogels with a hierarchical meso-macroporous and branching nanostructure (HMM-BNCA). An HMM-BNCA-modified glassy carbon electrode (GCE) (HMM-BNCA/GCE) exhibits high electrocatalytic activity for some electroactive biomolecules. For ascorbic acid (AA), the HMM-BNCA/GCE exhibits low oxidation peak potential and detection limit (-0.005 V and 0.45 µM, S/N = 3), high sensitivities (195.43 and 121.00 µA mM-1 cm-2) and wide linear ranges (10-1250 µM and 1250-4750 µM), which are superior to those obtained at the GCE and carbon nanotube (CNT)-modified GCE (CNT/GCE). The HMM-BNCA/GCE exhibits significant resistance to fouling and the interfering substances for the detection of AA. The successful and accurate detection of AA in real samples (such as vitamin C injections and vitamin C soft drinks) in this work demonstrates the feasibility and tremendous potential of HMM-BNCA/GCE for the analysis of AA in complex systems.

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The published version of this article, unfortunately, contains error. The authors regret that one typo was present in the first author name "Cuxing Xu" when it should be "Cuixing Xu".

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In this work, the low-cost carbon nanorods assembled hierarchical meso-macroporous carbons networks aerogels (CNs-HMCNAs) was environment-friendly synthesized from a cheap and abundant biomass of apples (Malus pumila Mill) for the first time. The biomass of apples derived CNs-HMCNAs exhibited the unique hierarchical meso-macroporous structure with large specific surface area and high density of edge defective sites. At the CNs-HMCNAs modified GCE (CNs-HMCNAs/GCE), the electron transfer between the glassy carbon electrode (GCE) and the ascorbic acid (AA) (or hydrogen peroxide (H2O2)) was effectively enhanced, and thus induced a low overvoltage for AA electrooxidation (or H2O2 electroreduction). As an electrochemical AA (or H2O2) sensor, the CNs-HMCNAs/GCE exhibited wider linear range, lower detection limit, higher sensitivity and stability than GCE and the carbon nanotubes modified GCE (CNTs/GCE). In particular, the CNs-HMCNAs/GCE showed great potential feasibility in the practical determination of AA (in AA injection, Vitamin C tablet and kiwi juice) or H2O2 (in human urine, milk and beer).

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The authors describe a method for synthesis of a three-dimensional (3D) interconnected carbon nanorod aerogel (3D-ICNA) starting from wax gourd (Benincasa hispida) which is a low-cost biomass. The 3D-ICNA possesses unique 3D interconnected and porous nanostructure, with abundant edge-plane-like defective sites, a large specific surface area (823 m2 g-1) and a large pore volume (0.12 cm3 g-1). This makes the material attractive in terms of electrochemical sensing. To validate the feasibility, the voltammetric response towards ferricyanide, hydrogen peroxide (H2O2), acetaminophen, ascorbic acid (AA), dopamine, uric acid and epinephrine was investigated by using a glassy carbon electrode (GCE) modified with 3D-ICNA. The modified GCE shows higher electron-transfer capacity than a conventional GCE. In addition, as an electrochemical sensor for AA or H2O2, the electrode exhibits better analytical performance with lower detection limit [3.5 µM for AA or 0.68 µM for H2O2 based on 3σ/m criterion (where σ is the standard deviation of the blank and m is the slope of the calibration plot)], wider linear range and higher sensitivity (0.14, 0.11 and 0.080 µA µM-1 cm-2 for AA or 0.24 and 0.20 µA µM-1 cm-2 for H2O2) compared to a plain GCE or a carbon nanotube-modified GCE. The modified GCE exhibits a large potential for the amperometric determination of AA or H2O2 in real samples. Graphical abstract By employing the biomass of wax gourd (Benincasa hispida) as the precursor, a three-dimensional interconnected carbon nanorod aerogel was prepared. It is shown to be a viable material for the construction of an advanced electrochemical sensor for H2O2 and ascorbic acid.

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In this work, the three-dimensional nitrogen-doped nanostructured carbons with hierarchical architectures (3D-NNCsHAs) with high density of defective sites, high surface area and pluralities of pore size distributions was prepared through the pyrolysis of sea-tangle (Laminaria japonica), an inexpensive, eco-friendly and abundant precursor. Benefitting from their structural uniqueness, a selective and sensitive ascorbic acid (AA) sensor based on 3D-NNCsHAs was developed. Compared to the glassy carbon electrode (GCE) and the carbon nanotubes modified GCE (CNTs/GCE), the 3D-NNCsHAs modified GCE (3D-NNCsHAs/GCE) presents higher performance towards the electrocatalysis and detection of AA, such as lower detection limit (1 µM), wider linear range (10-4410 µM) and lower electrooxidation peak potential (-0.02 V vs. Ag/AgCl). In addition, 3D-NNCsHAs/GCE also exhibits high anti-interference and anti-fouling abilities for AA detection. Particularly, the fabricated 3D-NNCsHAs/GCE is able to determine AA in real samples and the results acquired are satisfactory. Therefore, the 3D-NNCsHAs can be considered as a kind of novel electrode nanomaterial for the fabrication of selective and sensitive AA sensor for the extensive practical applications ranging from food analysis, to pharmaceutical industry and clinical test.

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In this paper, kelp (Laminaria japonica), as a kind of abundant biomass, is used as the precursor for the preparation of kelp-derived hierarchical meso-macroporous carbons (K-dHMMCs) through the carbonization under nitrogen (N2) atmosphere at high temperature. The K-dHMMCs exhibits the unique structure with high specific surface area of 416.02 m2 g-1, large pore volume of 0.24 cm3 g-1, the hierarchical meso-macroporous size distribution centered at 2, 12 and 82 nm and high density of defective sites, enabling K-dHMMCs attractive for the electrocatalysis. Drop-casting K-dHMMCs on the glassy carbon (GC) surface allows the construction of K-dHMMCs based electrochemical sensing platform, which shows electrocatalytic activities towards many electroactive molecules, such as potassium ferricyanide, nicotinamide adenine dinucleotide (NADH), hydrogen peroxide (H2O2), dopamine (DA), uric acid (UA), ascorbic acid (AA), epinephrine (EP), l-tyrosine (Tyr) and acetaminophen (APAP). Especially, the K-dHMMCs modified GC (K-dHMMCs/GC) electrode exhibits higher sensitivity, wider linear range, and lower detection limit than both carbon nanotubes modified GC (CNTs/GC) and GC electrodes for H2O2 detection, which makes the K-dHMMCs/GC electrode to be able to determine the H2O2 levels in human urine sample and monitor the H2O2 released from human cancer cells. These results demonstrate that K-dHMMCs/GC possesses a great potential for conventional electrochemical sensing applications.

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