Tumor‐Microenvironment‐Responsive Cascade Reactions by a Cobalt‐Single‐Atom Nanozyme for Synergistic Nanocatalytic ChemotherapyShuangfei Cai, Jiaming Liu, Jianwei Ding et al.|Angewandte Chemie International Edition|2022 Abstract Nanocatalytic therapy, involving the nanozyme‐triggered production of reactive oxygen species (ROS) in the tumor microenvironment (TME), has demonstrated potential in tumor therapy, but nanozymes still face challenges of activity and specificity that compromise the therapeutic efficacy. Herein, we report a strategy based on a single‐atom nanozyme to initiate cascade enzymatic reactions in the TME for tumor‐specific treatment. The cobalt‐single‐atom nanozyme, with Co−N coordination on N‐doped porous carbon (Co‐SAs@NC), displays catalase‐like activity that decomposes cellular endogenous H 2 O 2 to produce O 2 , and subsequent oxidase‐like activity that converts O 2 into cytotoxic superoxide radicals to efficiently kill tumor cells. By incorporation with doxorubicin, the therapy achieves a significantly enhanced antitumor effect in vivo. Our findings show that cascade TME‐specific catalytic therapy combined with chemotherapy is a promising strategy for efficient tumor therapy.
Highly selective and sensitive detection of Cu2+ with lysine enhancing bovine serum albumin modified-carbon dots fluorescent probeBased on the ability of lysine (Lys) to enhance the fluorescence intensity of bovine serum albumin modified-carbon dots (CDs-BSA) to decrease surface defects and quench fluorescence of the CDs-BSA-Lys system in the presence of Cu(2+) under conditions of phosphate buffer (PBS, pH = 5.0) at 45 °C for 10 min, a sensitive Lys enhancing CDs-BSA fluorescent probe was designed. The environment-friendly, simple, rapid, selective and sensitive fluorescent probe has been utilized to detect Cu(2+) in hair and tap water samples and it achieved consistent results with those obtained by inductively coupled plasma mass spectroscopy (ICP-MS). The mechanism of the proposed assay for the detection of Cu(2+) is discussed.
Multifunctional Graphdiyne–Cerium Oxide Nanozymes Facilitate MicroRNA Delivery and Attenuate Tumor Hypoxia for Highly Efficient Radiotherapy of Esophageal CancerXuantong Zhou, Min You, Fuhui Wang et al.|Advanced Materials|2021 Abstract Radioresistance is an important challenge for clinical treatments. The main causes of radioresistance include hypoxia in the tumor microenvironment, the antioxidant system within cancer cells, and the upregulation of DNA repair proteins. Here, a multiple radiosensitization strategy of high‐ Z ‐element‐based radiation enhancement is designed, attenuating hypoxia and microRNA therapy. The novel 2D graphdiyne (GDY) can firmly anchor and disperse CeO 2 nanoparticles to form GDY–CeO 2 nanocomposites, which exhibit superior catalase‐mimic activity in decomposing H 2 O 2 to O 2 to significantly alleviate tumor hypoxia, promote radiation‐induced DNA damage, and ultimately inhibit tumor growth in vivo. The miR181a‐2‐3p (miR181a) serum levels in patients are predictive of the response to preoperative radiotherapy in locally advanced esophageal squamous cell carcinoma (ESCC) and facilitate personalized treatment. Moreover, miR181a can act as a radiosensitizer by directly targeting RAD17 and regulating the Chk2 pathway. Subsequently, the GDY–CeO 2 nanocomposites with miR181a are conjugated with the iRGD‐grafted polyoxyethylene glycol (short for nano‐miR181a), which can increase the stability, efficiently deliver miR181a to tumor, and exhibit low toxicity. Notably, nano‐miR181a can overcome radioresistance and enhance therapeutic efficacy both in a subcutaneous tumor model and human‐patient‐derived xenograft models. Overall, this GDY–CeO 2 nanozyme and miR181a‐based multisensitized radiotherapy strategy provides a promising therapeutic approach for ESCC.
A Titanium Nitride Nanozyme for pH‐Responsive and Irradiation‐Enhanced Cascade‐Catalytic Tumor TherapyJiaming Liu, Jiaming Liu, Aizhu Wang et al.|Angewandte Chemie International Edition|2021 Abstract Nanozyme‐based catalytic tumor therapy is an emerging therapeutic method with high reactivity in response to tumor microenvironments (TMEs). To overcome the current limitations of deficient catalytic activity of nanozymes, we studied the contributing factors of enzymatic activity based on non‐metallic‐atom doping and irradiation. Nitrogen doping significantly enhanced the peroxidase activity of Ti‐based nanozymes, which was shown experimentally and theoretically. Based on the excellent NIR‐adsorption‐induced surface plasmon resonance and photothermal effect, the enzymatic activity of TiN nanoparticles (NPs) was further improved under NIR laser irradiation. Hence, an acidic TME‐responsive and irradiation‐mediated cascade nanocatalyst (TLGp) is presented by using TiN‐NP‐encapsulated liposomes linked with pH‐responsive PEG‐modified glucose oxidase (GOx). The integration of pH‐responsive GOx‐mediated H 2 O 2 self‐supply, nitrogen‐doping, and irradiation‐enhanced enzymatic activity of TiN NPs and mild‐photothermal therapy enables an effective tumor inhibition by TLGp with minimal side effects in vivo.
Progress and Prospects of Graphdiyne‐Based Materials in Biomedical Applications-hybridized carbon atoms. As a novel 2D carbon-based nanomaterial with unique planar structure, such as uniformly distributed nanopores and large conjugated structure, graphdiyne has shown many fascinating properties in mechanics, electronics, and optics since it was first experimentally synthesized in 2010. Up to now, graphdiyne and its derivatives have been reported to be successfully applied in many areas, such as catalysis, energy, environment, and biomedicine, due to these excellent properties. Herein, the current research progress of graphdiyne-based materials in biomedical fields is summarized, including biosensing, biological protection, cancer therapy, tissue engineering, etc. The advantages of graphdiyne and its derivatives are presented and compared with other carbon-based materials. Considering the potential biomedical and clinical applications of graphdiyne-based materials, the toxicity and biocompatibility are also discussed based on current studies. Finally, future perspectives and possible biomedical applications of graphdiyne-based materials are also discussed.