Algae-derived biochar nanozyme array for discrimination and detection of multiple pesticides in soil, water and food.

Despite the potential of nanozymes combined with sensor arrays for discriminating multiple pesticides simultaneously, they have few practical pesticide sensing uses due to the limited performance of existing nanozymes and the complexity of their preparation. Here, agricultural waste is utilized for the facile synthesis of high-performance biochar nanozymes and the fabrication of biochar nanozyme sensor arrays. The production of autogenous N-doped biochars with abundant surface functional groups and good peroxidase-like activities is achieved with different types of algae. High-performance biochar nanozyme sensor arrays can discriminate pesticides in a concentration range from 1 to 500 µM and in real samples from soil, lake water, seawater, apples, cucumbers, peaches, tomatoes and cabbages. Furthermore, pesticides can be quantified down to 1 µM. The development of high-performance nanozyme sensor arrays based on waste conversion could be a step toward pesticide discrimination and detection, which would improve human and environmental safety.

A Glutathione Peroxidase-Mimicking Nanozyme Precisely Alleviates Reactive Oxygen Species and Promotes Periodontal Bone Regeneration.

The use of oxidoreductase nanozymes to regulate reactive oxygen species (ROS) has gradually emerged in periodontology treatments. However, current nanozymes for treating periodontitis eliminate ROS extensively and non-specifically, ignoring the physiological functions of ROS under normal conditions, which may result in uncontrolled side effects. Herein, using the MIL-47(V)-F (MVF) nanozyme, which mimics the function of glutathione peroxidase (GPx), it is proposed that ROS can be properly regulated by specifically eliminating H2 O2 , the most prominent ROS. Through H2 O2 elimination, MVF contributes to limiting inflammation, regulating immune microenvironment, and promoting periodontal regeneration. Moreover, MVF stimulates osteogenic differentiation of periodontal stem cells directly, further promoting regeneration due to the vanadium in MVF. Mechanistically, MVF regulates ROS by activating the nuclear factor erythroid 2-related factor 2/heme oxygenase 1 (Nrf2/HO-1) pathway and promotes osteogenic differentiation directly through the phosphatidylinositol 3-kinase/protein kinase B (PI3K/Akt) pathway. A promising periodontitis therapy strategy is presented using GPx-mimicking nanozymes through their triple effects of antioxidation, immunomodulation, and bone remodeling regulation, making nanozymes an excellent tool for developing precision medicine.

Spray-Drying Hydrophobic Cellulose Nanocrystal Coatings with Degradable Biocide Release for Marine Antifouling.

With increasing awareness about the ecological environment, increased attention has been paid to the application of eco-friendly materials in the field of marine antifouling. In this work, a novel coating having good mechanical strength and static marine antifouling characteristics was fabricated using cellulose nanocrystals (CNCs) as the skeleton material, with in situ growth of SiO2 as the basic superhydrophobic material and introducing hexadecyl trimethyl ammonium bromide (CTAB) and 4-bromo2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (Econea) into the coating. Due to the high strength and rod structure of CNCs, the coating maintained super-hydrophobicity after 50 cycles of abrasion tests. Moreover, the addition of CTAB during the synthesis of SiO2 led to the hydrolysis and polycondensation of tetraethyl orthosilicate at the micellar interface. Econea was fully mixed with SiO2 nanoparticles, thus slowing down the rate of release of Econea. Meanwhile, the adhesion between the coating and the substrate reached 1.9 MPa, which can meet the application requirements for marine environments. The bioassay using bacteria (Escherichia coli) and diatoms (Nitzschia closterium) showed that the rate of inhibition of the coating on bacteria and diatoms could reach 99 and 90%, respectively, after immersion in artificial seawater for 28 days. This research provides a facile and promising fabricating solution of an eco-friendly CNC-based coating having strong antifouling characteristics suitable for marine environments.

Anisotropic cellulose nanocrystalline sponge sheets with ultrahigh water fluxes and oil/water selectivity.

Oily sewage caused by oil spill accidents has become a severe problem in the last decades. Hence, two-dimensional sheet-like filter materials for oil/water separation have received widespread attention. Porous sponge materials were developed using cellulose nanocrystals (CNCs) as raw materials. They are environmentally friendly and easy to prepare, with high flux and separation efficiency. The 1,2,3,4-butane tetracarboxylic acid cross-linked anisotropic cellulose nanocrystalline sponge sheet (B-CNC) exhibited ultrahigh water fluxes driven by gravity alone, depending on the aligned structure of channels and the rigidity of CNCs. Meanwhile, the sponge gained superhydrophilic/underwater superhydrophobic wettability with an underwater oil contact angle of up to 165.7° due to its ordered micro/nanoscale structure. B-CNC sheets displayed high oil/water selectivity without additional material doping or chemical modification. For oil/water mixtures, high separation fluxes of approximately 100,000 L·m-2·h-1 and separation efficiencies of up to 99.99 % were obtained. For a Tween 80-stabilized toluene-in-water emulsion, the flux reached >50,000 L·m-2·h-1, and the separation efficiency was above 99.7 %. B-CNC sponge sheets showed significantly higher fluxes and separation efficiencies than other bio-based two-dimensional materials. This research provides a facile and straightforward fabrication method of environmental-friendly B-CNC sponges for rapid, selective oil/water separation.

Novel Mixed Matrix Membranes Based on Poly(vinylidene fluoride): Development, Characterization, Modeling.

Membrane technology is an actively developing area of modern societies; with the help of high-performance membranes, it is possible to separate various mixtures for many industrial tasks. The objective of this study was to develop novel effective membranes based on poly(vinylidene fluoride) (PVDF) by its modification with various nanoparticles (TiO2, Ag-TiO2, GO-TiO2, and MWCNT/TiO2). Two types of membranes have been developed: dense membranes for pervaporation and porous membranes for ultrafiltration. The optimal content of nanoparticles in the PVDF matrix was selected: 0.3 wt% for porous membranes and 0.5 wt% for dense ones. The structural and physicochemical properties of the developed membranes were studied using FTIR spectroscopy, thermogravimetric analysis, scanning electron and atomic force microscopies, and measuring of contact angles. In addition, the molecular dynamics simulation of PVDF and the TiO2 system was applied. The transport properties and cleaning ability under ultraviolet irradiation of porous membranes were studied by ultrafiltration of a bovine serum albumin solution. The transport properties of dense membranes were tested in pervaporation separation of a water/isopropanol mixture. It was found that membranes with the optimal transport properties are as follows: the dense membrane modified with 0.5 wt% GO-TiO2 and the porous membrane modified with 0.3 wt% MWCNT/TiO2 and Ag-TiO2.

Glutathione peroxidase-like nanozymes: mechanism, classification, and bioapplication.

The field of nanozymes is developing rapidly. In particular, glutathione peroxidase (GPx)-like nanozymes, which catalytically reduce H2O2/organic hydroperoxides to H2O/alcohols, have attracted considerable attention. GPx-like nanozymes are powerful antioxidant enzymes known to combat oxidative stress. They have broad applications, including cytoprotection, anti-inflammation, neuroprotection, tumor therapy, and anti-aging. Although much progress has been made, GPx-like nanozymes have not been well discussed or fully reviewed as other nanozymes. This review aims to summarize recent advances on GPx-like nanozymes from the vantage point of mechanism, classification, and bioapplication. Future prospects for advancing their design and application are also discussed.

Eco-friendly marine antifouling coating consisting of cellulose nanocrystals with bioinspired micromorphology.

Nanomaterial-incorporated surfaces with microstructures have been widely used for marine antifouling coatings, yet limited green antifouling coatings are currently available for sustainable application, given the potential environmental effects of nanomaterial-based nanofillers. Here, by using natural sourced nanomaterials (cellulose nanocrystals, CNCs) as nanofillers, a nanocomposite superhydrophobic coating was fabricated via a simple sol-gel synthesis method. Notably, CNCs were firstly applied in the marine antifouling realm to form uniform and stable coatings, which were condensed with hydroxyl groups of hydrolyzed tetrapropyl zirconate, 3-glycidyloxypropyltrimethoxysilane, and methyltrimethoxysilane. The synthesized coatings gained a biomimetic microscopic ridge-like surface, where more CNCs contents contributed to finer microstructures. As a result of the influence of CNCs content on surface wettability and antifouling properties, the coating with CNCs accounting for 20 wt% of the total solid content (CNC20) delivered the best antifouling performance. Furthermore, 90-day marine field tests verified CNC20's excellent antifouling ability, reducing fouling by 82 % in comparison to the control group. Such a biomimicry study provides a novel strategy for the development of environmentally friendly coatings with CNCs nanofillers.

Introducing Nanozymes: New Horizons in Periodontal and Dental Implant Care.

The prevalence of periodontal and peri-implant diseases has been increasing worldwide and has gained a lot of attention. As multifunctional nanomaterials with enzyme-like activity, nanozymes have earned a place in the biomedical field. In periodontics and implantology, nanozymes have contributed greatly to research on maintaining periodontal health and improving implant success rates. To highlight this progress, we review nanozymes for antimicrobial therapy, anti-inflammatory therapy, tissue regeneration promotion, and synergistic effects in periodontal and peri-implant diseases. The future prospects of nanozymes in periodontology and implantology are also discussed along with challenges.

Cerium oxide nanozyme attenuates periodontal bone destruction by inhibiting the ROS-NFκB pathway.

Periodontitis, an inflammatory disease of oxidative stress, occurs due to excess reactive oxygen species (ROS) contributing to cell and tissue damage which in turn leads to alveolar bone resorption as well as the destruction of other periodontal support tissues. With significant recent advances in nanomaterials, we considered a unique type of nanomaterials possessing enzyme-like characteristics (called nanozymes) for potential future clinical applications, especially in light of the increasing number of studies evaluating nanozymes in the setting of inflammatory diseases. Here, we introduced a therapeutic approach for the management of periodontitis utilizing an injection of cerium oxide nanoparticles (CeO2 NPs) in situ. In this study, our synthesized CeO2 NPs could act as ROS scavengers in the inflammatory microenvironment with ideal outcomes. In vitro and in vivo experiments provide strong evidence on the roles of CeO2 NPs in scavenging multiple ROS and suppressing ROS-induced inflammation reactions stimulated by lipopolysaccharides. Moreover, CeO2 NPs could inhibit the MAPK-NFκB signalling pathway to suppress inflammatory factors. In addition, the results from a rat periodontitis model demonstrate that CeO2 NPs could exhibit a remarkable capacity to attenuate alveolar bone resorption, decrease the osteoclast activity and inflammation, and consequently improve the restoration of destroyed tissues. Collectively, our present study underscores the potential of CeO2 NPs for application in the treatment of periodontitis, and provides valuable insights into the application of nanozymes in inflammatory diseases.

Accelerated discovery of superoxide-dismutase nanozymes via high-throughput computational screening.

The activity of nanomaterials (NMs) in catalytically scavenging superoxide anions mimics that of superoxide dismutase (SOD). Although dozens of NMs have been demonstrated to possess such activity, the underlying principles are unclear, hindering the discovery of NMs as the novel SOD mimics. In this work, we use density functional theory calculations to study the thermodynamics and kinetics of the catalytic processes, and we develop two principles, namely, an energy level principle and an adsorption energy principle, for the activity. The first principle quantitatively describes the role of the intermediate frontier molecular orbital in transferring electrons for catalysis. The second one quantitatively describes the competition between the desired catalytic reaction and undesired side reactions. The ability of the principles to predict the SOD-like activities of metal-organic frameworks were verified by experiments. Both principles can be easily implemented in computer programs to computationally screen NMs with the intrinsic SOD-like activity.

Synthesis-temperature-regulated multi-enzyme-mimicking activities of ceria nanozymes.

Ceria (CeO2) nanozymes have drawn much attention in recent years due to their unique physiochemical properties and excellent biocompatibility. It is therefore very important to establish a simple and robust guideline to regulate CeO2 with desired multi-enzyme-mimicking activities that are ideal for practical bioapplications. In this work, the multi-enzyme-mimicking activities of CeO2 were regulated in a facile manner by a wet-chemical method with different synthesis temperatures. Interestingly, a distinct response in multi-enzyme-mimicking activities of CeO2 was observed towards different synthesis temperatures. And the regulation was ascribed to the comprehensive effect of the oxygen species, size, and self-restoring abilities of CeO2. This study demonstrates that high-performance CeO2 can be rationally designed by a specific synthesis temperature, and the guidelines from radar chart analysis established here can advance the biomedical applications of ceria-based nanozymes.

Hammett Relationship in Oxidase-Mimicking Metal-Organic Frameworks Revealed through a Protein-Engineering-Inspired Strategy.

While the unique physicochemical properties of nanomaterials that enable regulation of nanozyme activities are demonstrated in many systems, quantitative relationships between the nanomaterials structure and their enzymatic activities remain poorly understood, due to the heterogeneity of compositions and active sites in these nanomaterials. Here, inspired by metalloenzymes with well-defined metal-ligand coordination, a set of substituted metal-organic frameworks (MOFs) with similar coordination is employed to investigate the relationship between structure and oxidase-mimicking activity. Both experimental results and density functional theory calculations reveal a Hammett-type structure-activity linear free energy relationship (H-SALR) of MIL-53(Fe) (MIL = Materials of Institute Lavoisier) nanozymes, in which increasing the Hammett σm value with electron-withdrawing ligands increases the oxidase-mimicking activity. As a result, MIL-53(Fe) NO2 with the strongest electron-withdrawing NO2 substituent shows a tenfold higher activity than the unsubstituted MIL-53(Fe). Furthermore, the generality of H-SALR is demonstrated for a range of substrates, one other metal (Cr), and even one other MOF type (MIL-101). Such biologically inspired quantitative studies demonstrate that it is possible to identify quantitative structure-activity relationships of nanozymes, and to provide detailed insight into the catalytic mechanisms as those in native enzymes, making it possible to use these relationships to develop high-performance nanomaterials.

Ligand-Dependent Activity Engineering of Glutathione Peroxidase-Mimicking MIL-47(V) Metal-Organic Framework Nanozyme for Therapy.

Glutathione peroxidase (GPx) plays an important role in maintaining the reactive oxygen metabolic balance, yet limited GPx-mimicking nanozymes are currently available for in vivo therapy. Herein, a ligand engineering strategy is developed to modulate the GPx-mimicking activity of a metal-organic framework (MOF) nanozyme. With different substituted ligands, the GPx-mimicking activities of MIL-47(V)-X (MIL stands for Materials of Institute Lavoisier; X=F, Br, NH2 , CH3 , OH, and H) MOFs are rationally regulated. With the best one as an example, both in vitro and in vivo experiments reveal the excellent antioxidation ability of MIL-47(V)-NH2 , which alleviates the inflammatory response effectively for both ear injury and colitis, and is more active than MIL-47(V). This study proves that high-performance GPx-mimicking nanozymes can be rationally designed by a ligand engineering strategy, and that structure-activity relationships can direct the in vivo therapy. This study enriches nanozyme research and expands the range of biomimetic MOFs.

Nanozyme Sensor Arrays Based on Heteroatom-Doped Graphene for Detecting Pesticides.

Pesticides, widely used for pest control and plant growth regulation, have posed a threat to the environment and human health. Conventional methods to analyze pesticide residues are not applied to resource-limited areas because of their high cost, complexity, and requirements for expensive instruments (such as GC/MS and LC/MS). To address these challenges, herein we fabricated colorimetric nanozyme sensor arrays based on heteroatom-doped graphene for detection of aromatic pesticides. The active sites of nanozymes could be differentially masked when different pesticides were adsorbed on the graphene, which in turn resulted in the decrease of their peroxidase-mimicking activities. On the basis of this principle, five pesticides (i.e., lactofen, fluoroxypyr-meptyl, bensulfuron-methyl, fomesafen, and diafenthiuron) from 5 to 500 µM were successfully discriminated by the sensor arrays. In addition, discrimination for different concentrations of each pesticide and different ratios of two mixed pesticides were also demonstrated. The practical application of the sensor arrays was further validated by successfully discriminating the pesticides in soil samples. This work not only provides a facile and cost-effective method to detect pesticides but also makes a positive contribution to food safety and environmental protection.

Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II).

Nanozymes are nanomaterials with enzyme-like characteristics (Chem. Soc. Rev., 2013, 42, 6060-6093). They have been developed to address the limitations of natural enzymes and conventional artificial enzymes. Along with the significant advances in nanotechnology, biotechnology, catalysis science, and computational design, great progress has been achieved in the field of nanozymes since the publication of the above-mentioned comprehensive review in 2013. To highlight these achievements, this review first discusses the types of nanozymes and their representative nanomaterials, together with the corresponding catalytic mechanisms whenever available. Then, it summarizes various strategies for modulating the activity and selectivity of nanozymes. After that, the broad applications from biomedical analysis and imaging to theranostics and environmental protection are covered. Finally, the current challenges faced by nanozymes are outlined and the future directions for advancing nanozyme research are suggested. The current review can help researchers know well the current status of nanozymes and may catalyze breakthroughs in this field.

ROS scavenging Mn3O4 nanozymes for in vivo anti-inflammation.

Reactive oxygen species (ROS)-induced oxidative stress is linked to various diseases, including cardiovascular disease and cancer. Though highly efficient natural ROS scavenging enzymes have been evolved, they are sensitive to environmental conditions and hard to mass-produce. Therefore, enormous efforts have been devoted to developing artificial enzymes with ROS scavenging activities. Among them, ROS scavenging nanozymes have recently attracted great interest owing to their enhanced stability, multi-functionality, and tunable activity. It has been implicated that Mn-contained nanozymes would possess efficient ROS scavenging activities, however only a few such nanozymes have been reported. To fill this gap, herein we demonstrated that Mn3O4 nanoparticles (NPs) possessed multiple enzyme mimicking activities (i.e., superoxide dismutase and catalase mimicking activities as well as hydroxyl radical scavenging activity). The Mn3O4 nanozymes therefore significantly scavenged superoxide radical as well as hydrogen peroxide and hydroxyl radical. Moreover, they were not only more stable than the corresponding natural enzymes but also superior to CeO2 nanozymes in terms of ROS elimination. We showed that the Mn3O4 NPs not only exhibited excellent ROS removal efficacy in vitro but also effectively protected live mice from ROS-induced ear-inflammation in vivo. These results indicated that Mn3O4 nanozymes are promising therapeutic nanomedicine for treating ROS-related diseases.

Integrated nanozymes: facile preparation and biomedical applications.

Nanozymes have been viewed as the next generation of artificial enzymes due to their low cost, large specific surface area, and good robustness under extreme conditions. However, the moderate activity and limited selectivity of nanozymes have impeded their usage. To overcome these shortcomings, integrated nanozymes (INAzymes) have been developed by encapsulating two or more different biocatalysts (e.g., natural oxidases and peroxidase mimics) together within confined frameworks. On the one hand, with the assistance of natural enzymes, INAzymes are capable of specifically recognizing targets. On the other hand, nanoscale confinement brought about by integration significantly enhances the cascade reaction efficiency. In this Feature Article, we highlight the newly developed INAzymes, covering from synthetic strategies to versatile applications in biodetection and therapeutics. Moreover, it is predicted that INAzymes with superior activities, specificity, and stability will enrich the research of nanozymes and pave new ways in designing multifunctional nanozymes.

Rational Design of Au@Pt Multibranched Nanostructures as Bifunctional Nanozymes.

One of the current challenges in nanozyme-based nanotechnology is the utilization of multifunctionalities in one material. In this regard, Au@Pt nanoparticles (NPs) with excellent enzyme-mimicking activities due to the Pt shell and unique surface plasmon resonance features from the Au core have attracted enormous research interest. However, the unique surface plasmon resonance features from the Au core have not been widely utilized. The practical problem of the optical-damping nature of Pt hinders the research into the combination of Au@Pt NPs' enzyme-mimicking properties with their surface-enhanced Raman scattering (SERS) activities. Herein, we rationally tuned the Pt amount to achieve Au@Pt NPs with simultaneous plasmonic and enzyme-mimicking activities. The results showed that Au@Pt NPs with 2.5% Pt produced the highest Raman signal in 2 min, which benefited from the remarkably accelerated catalytic oxidation of 3,3',5,5'-tetramethylbenzidine with the decorated Pt and strong electric field retained from the Au core for SERS. This study not only demonstrates the great promise of combining bimetallic nanomaterials' multiple functionalities but also provides rational guidelines to design high-performance nanozymes for potential biomedical applications.

Multifunctional nanozymes: enzyme-like catalytic activity combined with magnetism and surface plasmon resonance.

Over decades, as alternatives to natural enzymes, highly-stable and low-cost artificial enzymes have been widely explored for various applications. In the field of artificial enzymes, functional nanomaterials with enzyme-like characteristics, termed as nanozymes, are currently attracting immense attention. Significant progress has been made in nanozyme research due to the exquisite control and impressive development of nanomaterials. Since nanozymes are endowed with unique properties from nanomaterials, an interesting investigation is multifunctionality, which opens up new potential applications for biomedical sensing and sustainable chemistry due to the combination of two or more distinct functions of high-performance nanozymes. To highlight the progress, in this review, we discuss two representative types of multifunctional nanozymes, including iron oxide nanomaterials with magnetic properties and metal nanomaterials with surface plasmon resonance. The applications are also covered to show the great promise of such multifunctional nanozymes. Future challenges and prospects are discussed at the end of this review.

Monitoring of Heparin Activity in Live Rats Using Metal-Organic Framework Nanosheets as Peroxidase Mimics.

Metal-organic framework (MOF) nanosheets are a class of two-dimensional (2D) porous and crystalline materials that hold promise for catalysis and biodetection. Although 2D MOF nanosheets have been utilized for in vitro assays, ways of engineering them into diagnostic tools for live animals are much less explored. In this work, a series of MOF nanosheets are successfully engineered into a highly sensitive and selective diagnostic platform for in vivo monitoring of heparin (Hep) activity. The iron-porphyrin derivative is selected as a ligand to synthesize a series of archetypical MOF nanosheets with intrinsic heme-like catalytic sites, mimicking peroxidase. Hep-specific AG73 peptides as recognition motifs are physically adsorbed onto MOF nanosheets, blocking active sites from nonspecific substrate-catalyst interaction. Because of the highly specific interaction between Hep and AG73, the activity of AG73-MOF nanosheets is restored upon the binding of Hep, but not Hep analogues and other endogenous biomolecules. Furthermore, by taking advantages of biocompatibility and diagnostic property enabled by AG73-MOF nanosheets, the elimination process of Hep in live rats is quantitatively monitored by coupling with microdialysis technology. This work expands the biomedical applications of 2D MOF nanomaterials and provides access to a promising in vivo diagnostic platform.