Wireless Gas Sensor Based on the Mesoporous ZnO-SnO2 Heterostructure Enables Ultrasensitive and Rapid Detection of 3-Methylbutyraldehyde.

Achieving ultrasensitive and rapid detection of 3-methylbutyraldehyde is crucial for monitoring chemical intermediate leakage in pharmaceutical and chemical industries as well as diagnosing ventilator-associated pneumonia by monitoring exhaled gas. However, developing a sensitive and rapid method for detecting 3-methylbutyraldehyde poses challenges. Herein, a wireless chemiresistive gas sensor based on a mesoporous ZnO-SnO2 heterostructure is fabricated to enable the ultrasensitive and rapid detection of 3-methylbutyraldehyde for the first time. The mesoporous ZnO-SnO2 heterostructure exhibits a uniform spherical shape (∼79 nm in diameter), a high specific surface area (54.8 m2 g-1), a small crystal size (∼4 nm), and a large pore size (6.7 nm). The gas sensor demonstrates high response (18.98@20 ppm), short response/recovery times (13/13 s), and a low detection limit (0.48 ppm) toward 3-methylbutyraldehyde. Furthermore, a real-time monitoring system is developed utilizing microelectromechanical systems gas sensors. The modification of amorphous ZnO on the mesoporous SnO2 pore wall can effectively increase the chemisorbed oxygen content and the thickness of the electron depletion layer at the gas-solid interface, which facilitates the interface redox reaction and enhances the sensing performance. This work presents an initial example of semiconductor metal oxide gas sensors for efficient detection of 3-methylbutyraldehyde that holds great potential for ensuring safety during chemical production and disease diagnosis.

Synergistic sensitization effects of single-atom gold and cerium dopants on mesoporous SnO2 nanospheres for enhanced volatile sulfur compound sensing.

The real-time monitoring of volatile sulfur compounds is indispensable; however, it continues to pose a significant challenge due to issues such as limited performance towards parts-per-billion (ppb)-level gas. Herein, a concept of synergistic sensitization effects involving single-atom gold (Au) and cerium (Ce) dopants is proposed to boost the sensing performance of allyl mercaptan, a common volatile sulfur compound. As a proof-of-concept, a chemiresistive gas sensor based on mesoporous SnO2 nanospheres with single-atom Au decoration and Ce dopant (denoted Au/Ce-SnO2) is successfully synthesized. The synthesis of Au/Ce-SnO2 is achieved through the utilization of a self-template strategy, employing metal-phenolic hybrids as a precursor. The obtained materials exhibit high specific surface area (89.4 m2 g-1), and small particle size (∼86 nm). The gas sensor reveals unprecedented sensitivity (0.097 ppb-1) and ultra-low detection limit (0.74 ppb), surpassing all state-of-the-art allyl mercaptan gas sensors. Furthermore, a wireless gas sensor is constructed for highly selective and real-time monitoring of allyl mercaptan. The decoration of single-atom Au facilitates the adsorption and dissociation of oxygen and target gases. Simultaneously, the Ce dopant enhances the oxidation of allyl mercaptan. The sensing performance is boosted by the mesoporous framework of SnO2, as well as the synergistic sensitization effects resulting from single-atom Au decoration and Ce doping, thereby facilitating its potential application in environmental and health-related domains.

Mussel-inspired interface deposition strategy for mesoporous metal-phenolic nanospheres with superior antioxidative, photothermal and antibacterial performance.

Metal-phenolic networks (MPNs) have emerged as a versatile and multifunctional platform applied in bioimaging, disease treatment, electrocatalysis, and water purification. The synthesis of MPNs with mesoporous frameworks and ultra-small diameters (<200 nm), crucial for post-modification, cargo loading, and mass transport, remains a formidable challenge. Inspired by mussel chemistry, mesoporous metal-phenolic nanospheres (MMPNs) are facilely prepared by direct deposition of the metal-polyphenol complex on the interface of oil nano-droplets composed of block copolymers/1,3,5-trimethylbenzene followed by a spontaneous template-removal process. Due to the penetrable and stable networks, the oil nano-droplets gradually leak from the networks driven by shear stress during the stirring process. As a result, MMPNs are obtained without additional template removal procedures such as solvent extraction or high-temperature calcination. The materials have a large pore size (∼12.1 nm), uniform spherical morphology with a small particle size (∼99 nm), and a large specific surface area (49.8 m2 g-1). Due to the abundant phenolic hydroxyl groups, the MMPNs show excellent antioxidative property. The MMPNs also have excellent photothermal property, whose photothermal conversion efficiency was 40.9 %. Moreover, the phenolic hydroxyl groups can reduce Ag+ in situ to prepare Ag nanoparticles loaded MMPNs composites, which have excellent inhibition performance of drug-resistant bacteria biofilm.

Single-Atom Au-Functionalized Mesoporous SnO2 Nanospheres for Ultrasensitive Detection of Listeria monocytogenes Biomarker at Low Temperatures.

Semiconductor metal oxide gas sensors have been proven to be capable of detecting Listeria monocytogenes, one kind of foodborne bacteria, through monitoring the characteristic gaseous metabolic product 3-hydroxy-2-butanone. However, the detection still faces challenges because the sensors need to work at high temperatures and output limited gas sensing performance. The present study focuses on the design of single-atom Au-functionalized mesoporous SnO2 nanospheres for the sensitive detection of ppb-level 3-hydroxy-2-butanone at low temperatures (50 °C). The fabricated sensors exhibit high sensitivity (291.5 ppm-1), excellent selectivity, short response time (10 s), and ultralow detection limit (10 ppb). The gas sensors exhibit exceptional efficacy in distinguishing L. monocytogenes from other bacterial strains (e.g., Escherichia coli). Additionally, wireless detection of 3-hydroxy-2-butanone vapor is successfully achieved through microelectromechanical systems sensors, enabling real-time monitoring of the biomarker 3-hydroxy-2-butanone. The superior sensing performance is ascribed to the mesoporous framework with accessible active Au-O-Sn sites in the uniform sensing layer consisting of single-atom Au-modified mesoporous SnO2 nanospheres, and such a feature facilitates the gas diffusion, adsorption, and catalytic conversion of 3-hydroxy-2-butanone molecules in the sensing layer, resulting in excellent sensing signal output at relatively low temperature that is favorable for developing low-energy-consumption gas sensors.

Mesoporous zinc-polyphenol nanozyme for attenuating renal ischemia-reperfusion injury.

Aim: To target the reactive oxygen species (ROS) accumulation and renal tubular epithelial cell (rTEC) death in renal ischemia-reperfusion injury (IRI), we constructed a nanoparticle that offers ROS scavenging and rTEC-death inhibition: mesoporous zinc-tannic acid nanozyme (ZnTA). Materials & methods: After successfully constructing ZnTA, we proceeded to examine its effect on ROS accumulation, cellular ferroptosis and apoptosis, as well as injury severity. Results: Malondialdehyde, Fe2+ amounts and 4-HNE staining demonstrated that ZnTA effectively attenuated rTEC ferroptosis. TUNEL staining confirmed that Zn2+ carried by ZnTA could effectively inhibit caspase 3 and caspase 9, mitigating apoptosis. Finally, it reduced renal IRI through the synergistic effect of ROS scavenging and cell-death inhibition. Conclusion: This study is expected to provide a paradigm for a combined therapeutic strategy for renal IRI.

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Reactive Oxygen Species-Scavenging Mesoporous Poly(tannic acid) Nanospheres Alleviate Acute Kidney Injury by Inhibiting Ferroptosis.

Acute kidney injury (AKI), predominantly associated with the excess production of endogenous ROS, is a serious renal dysfunction syndrome. Ferroptosis characterized by iron-dependent regulated cell death has significant involvement in AKI pathogenesis. As symptomatic treatment of AKI remains clinically limited, a new class of effective therapies has emerged, which is referred to as nanozyme. In our research, a natural mesoporous poly(tannic acid) nanosphere (referred to as PTA) was developed that can successfully mimic the activity of superoxide dismutase (SOD) by Mussel-inspired interface deposition strategy, for effective ROS scavenging and thus inhibition of ferroptosis to attenuate AKI. As anticipated, PTA mitigated oxidative stress and inhibited ferroptosis, as opposed to other modes of cell death such as pyroptosis or necrosis. Furthermore, PTA exhibited favorable biocompatibility and safeguarded the kidney against ferroptosis by enhancing the expression of SLC7a11/glutathione peroxidase 4(GPX4) and Nrf2/HO-1, while reducing the levels of ACSL4 protein in the ischemia and reperfusion injury (IRI)-induced AKI model. Moreover, PTA effectively suppressed aberrant expression of inflammatory factors. Overall, this study introduced antioxidative nanozymes in the form of mesoporous polyphenol nanospheres, showcasing exceptional therapeutic efficacy in addressing ROS-related diseases. This novel approach holds promise for clinical AKI treatment and broadens the scope of biomedical applications for nanozymes.

Synthesis of Mesoporous Lanthanum-Doped SnO2 Spheres for Sensitive and Selective Detection of the Glutaraldehyde Disinfectant.

Glutaraldehyde disinfectant has been widely applied in aquaculture, farming, and medical treatment. Excessive concentrations of glutaraldehyde in the environment can lead to serious health hazards. Therefore, it is extremely important to develop high-performance glutaraldehyde sensors with low cost, high sensitivity, rapid response, fabulous selectivity, and low limit of detection. Herein, mesoporous lanthanum (La) doped SnO2 spheres with high specific surface area (52-59 m2 g-1), uniform mesopores (with a pore size concentrated at 5.7 nm), and highly crystalline frameworks are designed to fabricate highly sensitive gas sensors toward gaseous glutaraldehyde. The mesoporous lanthanum-doped SnO2 spheres exhibit excellent glutaraldehyde-sensing performance, including high response (13.5@10 ppm), rapid response time (28 s), and extremely low detection limit of 0.16 ppm. The excellent sensing performance is ascribed to the high specific surface area, high contents of chemisorbed oxygen species, and lanthanum doping. DFT calculations suggest that lanthanum doping in the SnO2 lattice can effectively improve the adsorption energy toward glutaraldehyde compared to pure SnO2 materials. Moreover, the fabricated gas sensors can effectively detect commercial glutaraldehyde disinfectants, indicating a potential application in aquaculture, farming, and medical treatment.

Self-template synthesis of mesoporous vanadium oxide nanospheres with intrinsic peroxidase-like activity and high antibacterial performance.

Mesoporous vanadium oxide nanospheres are a very promising nanozyme for antibacterial and chemical sensing. However, controllable synthesis of mesoporous vanadium oxide nanospheres with uniform structure and small diameter (<200 nm) remains challenging. Herein, mesoporous vanadium oxide nanospheres (MVONs) with a small, uniform and adjustable particle size (52-105 nm), large mesopore size (5.1-5.8 nm), and high specific surface area (up to 63.7 m2 g-1) are constructed via a self-template strategy using tannic acid, formaldehyde and vanadium compounds as a polymerizable ligand, cross-linking agent and metal source, respectively. The relationships between synthesis conditions and material nanostructure are systematically investigated. The particle size and peroxidase-like activity of MVONs can be easily changed by adding different amounts of Pluronic block copolymer F127. Owing to the mesoporous structure, high specific surface area and small particle size, MVONs can effectively convert H2O2 into extremely toxic reactive oxygen species, and further kill Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). This research establishes a universal, reliable method for synthesizing mesoporous vanadium oxide nanospheres, which might be used in catalysis, biosensors, and antibacterial treatment.

Spherical mesoporous Fe-N-C single-atom nanozyme for photothermal and catalytic synergistic antibacterial therapy.

Nanozyme has been regarded as an efficient antibiotic to kill bacteria using the reactive oxygen species (ROS) generated by Fenton-like reaction. However, its activity is still unsatisfied and requires large amount of hydrogen peroxide with side effects toward normal tissues. Herein, spherical mesoporous Fe-N-C single-atom nanozyme (SAzyme) is designed for antibacterial therapy via photothermal treatment enhanced Fenton-like catalysis process. Due to the large pore size (4.0 nm), high specific surface area (413.9 m2 g-1) and uniform diameter (100 nm), the catalytic performance of Fe-N-C SAzyme is greatly improved. The Michaelis-Menten constant (Km) is 4.84 mmol L-1, which is similar with that of horseradish peroxidase (3.7 mmol L-1). Moreover, mesoporous Fe-N-C SAzyme shows high photothermal conversion efficiency (23.3 %) owing to the carbon framework. The catalytic activity can be enhanced under light irradiation due to the elevated reaction temperature. The bacteria can also be killed via physical heat effect. Due to the synergistic effect of nanozyme catalysis and photothermal treatment, the antibacterial performance is much higher than that using single antibacterial method. This work provides an alternative for combined antibacterial treatment via photothermal treatment assisted catalytic process using spherical mesoporous single-atom nanozyme as an antibiotic.

Synthesis of Mesoporous Ag2O/SnO2 Nanospheres for Selective Sensing of Formaldehyde at a Low Working Temperature.

Formaldehyde (HCHO) is a prevalent indoor gas pollutant that has been seriously endangering human health. Developing semiconductor metal oxide (SMO) gas sensors for selective measurement of formaldehyde at low working temperatures remains a great challenge. In this work, silver/tin-polyphenol hybrid spheres are applied as a sacrificial template for the fabrication of spherical mesoporous Ag2O/SnO2 sensing materials. The obtained mesoporous Ag2O/SnO2 spheres have a uniform particle size (∼80 nm), large pore size (5.8 nm), and high specific surface area (71.3 m2 g-1). The response is 140 toward formaldehyde (10 ppm) at a low working temperature (75 °C). The detection limit reaches a low level of 23.6 ppb. Most importantly, it has excellent selectivity toward interfering gases. When the concentration of the interfering gas (e.g., ethanol) is 5 times as high as that of formaldehyde, the response is little affected. Theoretical calculations suggest that the addition of Ag2O can significantly enhance the adsorption energy toward formaldehyde, thus improving formaldehyde sensing performance. This work demonstrates an efficient self-template synthesis strategy for noble metal catalyst-decorated mesoporous metal oxide spheres, which could boost gas sensing performance at a lower working temperature.

Synthesis of Mesoporous CuO Hollow Sphere Nanozyme for Paper-Based Hydrogen Peroxide Sensor.

Point-of-care monitoring of hydrogen peroxide is important due to its wide usage in biomedicine, the household and industry. Herein, a paper sensor is developed for sensitive, visual and selective detection of H2O2 using a mesoporous metal oxide hollow sphere as a nanozyme. The mesoporous CuO hollow sphere is synthesized by direct decomposition of copper-polyphenol colloidal spheres. The obtained mesoporous CuO hollow sphere shows a large specific surface area (58.77 m2/g), pore volume (0.56 cm3/g), accessible mesopores (5.8 nm), a hollow structure and a uniform diameter (~100 nm). Furthermore, they are proven to show excellent peroxidase-like activities with Km and Vmax values of 120 mM and 1.396 × 10-5 M·s-1, respectively. Such mesoporous CuO hollow spheres are then loaded on the low-cost and disposable filter paper test strip. The obtained paper sensor can be effectively used for detection of H2O2 in the range of 2.4-150 µM. This work provides a new kind of paper sensor fabricated from a mesoporous metal oxide hollow sphere nanozyme. These sensors could be potentially used in bioanalysis, food security and environmental protection.

Construction of a Mesoporous Ceria Hollow Sphere/Enzyme Nanoreactor for Enhanced Cascade Catalytic Antibacterial Therapy.

Nanozyme has been regarded as one of the antibacterial agents to kill bacteria via a Fenton-like reaction in the presence of H2O2. However, it still suffers drawbacks such as insufficient catalytic activity in near-neutral conditions and the requirement of high H2O2 levels, which would minimize the side effects to healthy tissues. Herein, a mesoporous ceria hollow sphere/enzyme nanoreactor is constructed by loading glucose oxidase in the mesoporous ceria hollow sphere nanozyme. Due to the mesoporous framework, large internal voids, and high specific surface area, the obtained nanoreactor can effectively convert the nontoxic glucose into highly toxic hydroxyl radicals via a cascade catalytic reaction. Moreover, the generated glucose acid can decrease the localized pH value, further boosting the peroxidase-like catalytic performance of mesoporous ceria. The generated hydroxyl radicals could damage severely the cell structure of the bacteria and prevent biofilm formation. Moreover, the in vivo experiments demonstrate that the nanoreactor can efficiently eliminate 99.9% of bacteria in the wound tissues and prevent persistent inflammation without damage to normal tissues in mice. This work provides a rational design of a nanoreactor with enhanced catalytic activity, which can covert glucose to hydroxyl radicals and exhibits potential applications in antibacterial therapy.

Synthesis of gadolinium/iron-bimetal-phenolic coordination polymer nanoparticles for theranostic applications.

Integration of diagnostic and therapeutic components into a single coordination polymer nanoparticle is desirable for theranostic applications, but still challenging. Herein, we report the synthesis of bimetal-phenolic coordination polymer nanoparticles using gadolinium nitrate and ferrous sulphate as a metal source, and plant polyphenols (i.e., tannic acid) as an organic ligand via a metal-catechol coordination assembly process. Such coordination polymers show a tunable molar ratio of Gd/Fe and high dispersibility and stability in aqueous solution. The coordination polymers reveal composition-dependent performance for longitudinal relaxivity and photothermal conversion. The longitudinal relaxivity is positively related to the molar ratio of Gd/Fe, while the photothermal performance is negatively related to the molar ratio of Gd/Fe in the coordination polymers. The coordination polymers with an optimized molar ratio of Gd/Fe exhibit an ultra-small hydrodynamic diameter (∼23 nm), a high r1 value (9.3 mM-1 s-1) with low r2/r1 (1.26) and high photothermal conversion efficiency (η = 37%). They can be used as a contrast agent for T1-weighted magnetic resonance imaging of EMT-6 tumor bearing mice, which can effectively enhance the signals of tumors. They can also effectively suppress tumor growth via photothermal therapy. This work brings new insights for the synthesis of multifunctional coordination polymer nanoparticles and extending their potential applications in theranostics.

Sol-Gel Synthesis of Spherical Mesoporous High-Entropy Oxides.

High-entropy oxides (HEOs) have attracted increasing interest owing to their unique structures and fascinating physicochemical properties. Spherical mesoporous HEOs further inherit the advantages of spherical mesoporous materials including high surface area and tunable pore size. However, it is still a huge challenge to construct HEOs with uniform spheres and a mesoporous framework. Herein, a wet-chemistry sol-gel strategy is demonstrated for the synthesis of spherical mesoporous HEOs (e.g., Ni-Co-Cr-Fe-Mn oxide) with high specific surface area (42-143 m2/g), large pore size (5.5-8.3 nm), unique spherical morphology (∼55 nm), and spinel structure without any impure crystal phase using polyphenol as a polymerizable ligand. The metal/polyphenol-formaldehyde resin colloidal spheres are first synthesized via a sol-gel process. Because of their abundant catechol groups and strong chelating ability with different metal species, polyphenols can not only accommodate five different metal ions in their networks but also be well polymerized by formaldehyde to form colloidal spheres. After calcination, the metal species aggregate together to form HEOs, while the organic resin is fully decomposed to produce mesopores. Because of the open framework with accessible mesopores, they could be used as a peroxymonosulfate catalyst for degradation of organic pollutants and a nanoplatform for efficient detection of DNA. This work demonstrates a straightforward sol-gel strategy for design and synthesis of spherical mesoporous high-entropy materials, which would promote the exploration of new properties of high-entropy materials and extend their application.