Photoexcited Ru single-atomic sites for efficient biomimetic redox catalysis.

The unsatisfactory catalytic activity of nanozymes owing to their inefficient electron transfer (ET) is the major challenge in biomimetic catalysis-related biomedical applications. Inspired by the photoelectron transfers in natural photoenzymes, we herein report a photonanozyme of single-atom Ru anchored on metal-organic frameworks (UiO-67-Ru) for achieving photoenhanced peroxidase (POD)-like activity. We demonstrate that the atomically dispersed Ru sites can realize high photoelectric conversion efficiency, superior POD-like activity (7.0-fold photoactivity enhancement relative to that of UiO-67), and good catalytic specificity. Both in situ experiments and theoretical calculations reveal that photoelectrons follow the cofactor-mediated ET process of enzymes to promote the production of active intermediates and the release of products, demonstrating more favorable thermodynamics and kinetics in H2O2 reduction. Taking advantage of the unique interaction of the Zr-O-P bond, we establish a UiO-67-Ru-based immunoassay platform for the photoenhanced detection of organophosphorus pesticides.

Atomic-level design of metalloenzyme-like active pockets in metal-organic frameworks for bioinspired catalysis.

Natural metalloenzymes with astonishing reaction activity and specificity underpin essential life transformations. Nevertheless, enzymes only operate under mild conditions to keep sophisticated structures active, limiting their potential applications. Artificial metalloenzymes that recapitulate the catalytic activity of enzymes can not only circumvent the enzymatic fragility but also bring versatile functions into practice. Among them, metal-organic frameworks (MOFs) featuring diverse and site-isolated metal sites and supramolecular structures have emerged as promising candidates for metalloenzymes to move toward unparalleled properties and behaviour of enzymes. In this review, we systematically summarize the significant advances in MOF-based metalloenzyme mimics with a special emphasis on active pocket engineering at the atomic level, including primary catalytic sites and secondary coordination spheres. Then, the deep understanding of catalytic mechanisms and their advanced applications are discussed. Finally, a perspective on this emerging frontier research is provided to advance bioinspired catalysis.

Improvement in ORR Durability of Fe Single-Atom Carbon Catalysts Hybridized with CeO2 Nanozyme.

FeNC catalysts are considered one of the most promising alternatives to platinum group metals for the oxygen reduction reaction (ORR). Despite the extensive research on improving ORR activity, the undesirable durability of FeNC is still a critical issue for its practical application. Herein, inspired by the antioxidant mechanism of natural enzymes, CeO2 nanozymes featuring catalase-like and superoxide dismutase-like activities were coupled with FeNC to mitigate the attack of reactive oxygen species (ROS) for improving durability. Benefiting from the multienzyme-like activities of CeO2, ROS generated from FeNC is instantaneously eliminated to alleviate the corrosion of carbon and demetallization of metal sites. Consequently, FeNC/CeO2 exhibits better ORR durability with a decay of only 5 mV compared to FeNC (18 mV) in neutral electrolyte after 10k cycles. The FeNC/CeO2-based zinc-air battery also shows minimal voltage decay over 140 h in galvanostatic discharge-charge cycling tests, outperforming FeNC and commercial Pt/C.

Pre-Adsorbed H-Mediated Electrochemiluminescence.

In conventional electrochemiluminescence (ECL) systems, the presence of the competitive cathodic hydrogen evolution reaction (HER) in aqueous electrolytes is typically considered to be a side reaction, leading to a reduced ECL efficiency and stability due to H2 generation and aggregation at the electrode surface. However, the significant role of adsorbed hydrogen (H*) as a key intermediate, formed during the Volmer reaction in the HER process, has been largely overlooked. In this study, employing the luminol-H2O2 system as a model, we for the first time demonstrate a novel H*-mediated coreactant activation mechanism, which remarkably enhances the ECL intensity. H* facilitates cleavage of the O-O bond in H2O2, selectively generating highly reactive hydroxyl radicals for efficient ECL reactions. Experimental investigations and theoretical calculations demonstrate that this H*-mediated mechanism achieves superior coreactant activation compared to the conventional direct electron transfer pathway, which unveils a new pathway for coreactant activation in the ECL systems.

Artificial-Cofactor-Mediated Hydrogen and Electron Transfer Endows AuFe/Polydopamine Superparticles with Enhanced Glucose Oxidase-Like Activity.

Various applications related to glucose catalysis have led to the development of functional nanozymes with glucose oxidase (GOX)-like activity. However, the unsatisfactory catalytic activity of nanozymes is a major challenge for their practical applications due to their inefficient hydrogen and electron transfer. Herein, we present the synthesis of AuFe/polydopamine (PDA) superparticles that exhibit photothermal-enhanced GOX-like activity. Experimental investigations and theoretical calculations reveal that the glucose oxidation process catalyzed by AuFe/PDA follows an artificial-cofactor-mediated hydrogen atom transfer mechanism, which facilitates the generation of carbon-centered radical intermediates. Rather than depending on charged Au surfaces for thermodynamically unstable hydride transfer, Fe(III)-coordinated PDA with abundant amino and phenolic hydroxyl groups serves as cofactor mimics, facilitating both hydrogen atom and electron transfer in the catalytic process. Finally, leveraging the photothermal-enhanced GOX-like and catalase-like activities of AuFe/PDA, we establish a highly sensitive and accurate point-of-care testing blood glucose determination with exceptional anti-jamming capabilities.

Grain-Boundary-Rich Ceria Metallene Nanozyme with Abundant Metal Site Pairs Boosts Phosphatase-like Activity.

Natural phosphatases featuring paired metal sites inspire various advanced nanozymes with phosphatase-like activity as alternatives in practical applications. Numerous efforts to create point defects show limited metal site pairs, further resulting in insufficient activity. However, it remains a grand challenge to accurately engineer abundant metal site pairs in nanozymes. Herein, we report a grain-boundary-rich ceria metallene nanozyme (GB-CeO2) with phosphatase-like activity. Grain boundaries acting as the line or interfacial defects can effectively increase the content of Ce4+/Ce3+ site pairs to 72.28%, achieving a 49.28-fold enhancement in activity. Furthermore, abundant grain boundaries optimize the band structure to assist the photoelectron transfer under irradiation, which further increases the content of metal site pairs to 88.96% and finally realizes a 114.39-fold enhanced activity over that of CeO2 without irradiation. Given the different inhibition effects of pesticides on catalysts with and without irradiation, GB-CeO2 was successfully applied to recognize mixed toxic pesticides.

Nanozyme Metabolism Controls Air Pollution over an Atomic Potassium Cyano Site.

Increasing threats of air pollution prompt the design of air purification systems. As a promising initiative defense strategy, nanocatalysts are integrated to catalyze the detoxification of specific pollutants. However, it remains a grand challenge to tailor versatile nanocatalysts to cope with diverse pollutants in practice. Here, we report a nanozyme metabolism system to realize broad-spectrum protection from air pollution. Atomic K-modified carbon nitride featuring flavin oxidase-like and peroxidase-like activities was synthesized to initiate nanozyme metabolism. In situ experiments and theoretical investigations collectively show that K sites optimize the geometric and electronic structure of cyano sites for both enzyme-like activities. As a proof of concept, the nanozyme metabolism was applied to the mask against volatile organic compounds, persistent organic pollutants, reactive oxygen species, bacteria, and so on. Our finding provides a thought to tackle global air pollution and deepens the understanding of nanozyme metabolism.

Regulating Reactive Oxygen Species over M-N-C Single-Atom Catalysts for Potential-Resolved Electrochemiluminescence.

The development of potential-resolved electrochemiluminescence (ECL) systems with dual emitting signals holds great promise for accurate and reliable determination in complex samples. However, the practical application of such systems is hindered by the inevitable mutual interaction and mismatch between different luminophores or coreactants. In this work, for the first time, by precisely tuning the oxygen reduction performance of M-N-C single-atom catalysts (SACs), we present a dual potential-resolved luminol ECL system employing endogenous dissolved O2 as a coreactant. Using advanced in situ monitoring and theoretical calculations, we elucidate the intricate mechanism involving the selective and efficient activation of dissolved O2 through central metal species modulation. This modulation leads to the controlled generation of hydroxyl radical (·OH) and superoxide radical (O2·-), which subsequently trigger cathodic and anodic luminol ECL emission, respectively. The well-designed Cu-N-C SACs, with their moderate oxophilicity, enable the simultaneous generation of ·OH and O2·-, thereby facilitating dual potential-resolved ECL. As a proof of concept, we employed the principal component analysis statistical method to differentiate antibiotics based on the output of the dual-potential ECL signals. This work establishes a new avenue for constructing a potential-resolved ECL platform based on a single luminophore and coreactant through precise regulation of active intermediates.

A Controlled Release Aptasensor Utilizing AIE-Active MOFs as High-Efficiency ECL Nanoprobe for the Sensitive Detection of Adenosine Triphosphate.

Improving the sensitivity in electrochemiluminescence (ECL) detection systems necessitates the integration of robust ECL luminophores and efficient signal transduction. In this study, we report a novel ECL nanoprobe (Zr-MOF) that exhibits strong and stable emission by incorporating aggregation-induced emission ligands into Zr-based metal-organic frameworks (MOFs). Meanwhile, we designed a high-performance signal modulator through the implementation of a well-designed controlled release system with a self-on/off function. ZnS quantum dots (QDs) encapsulated within the cavities of aminated mesoporous silica nanoparticles (NH2-SiO2) serve as the ECL quenchers, while adenosine triphosphate (ATP) aptamers adsorbed on the surface of NH2-SiO2 through electrostatic interaction act as "gatekeepers." Based on the target-triggered ECL resonance energy transfer between Zr-MOF and ZnS QDs, we establish a coreactant-free ECL aptasensor for the sensitive detection of ATP, achieving an impressive low detection limit of 0.033 nM. This study not only demonstrates the successful combination of ECL with controlled release strategies but also opens new avenues for developing highly efficient MOFs-based ECL systems.

Potential-Resolved Ratiometric Aptasensor for Sensitive Acetamiprid Analysis Based on Coreactant-free Electrochemiluminescence Luminophores of Gd-MOF and "Light Switch" Molecule of [Ru(bpy)2dppz]2.

For conventional potential-resolved ratiometric electrochemiluminescence (ECL) systems, the introduction of multiplex coreactants is imperative. However, the undesirable interactions between different coreactants inevitably affect analytical accuracy and sensitivity. Herein, through the coordination of aggregation-induced emission ligands with gadolinium cations, the self-luminescent metal-organic framework (Gd-MOF) is prepared and serves as a novel coreactant-free anodic ECL emitter. By the intercalation of [Ru(bpy)2dppz]2+ with light switch effect into DNA duplex, one high-efficiency cathodic ECL probe is obtained using K2S2O8 as a coreactant. In the presence of acetamiprid, the strong affinity between the target and its aptamer induces the release of [Ru(bpy)2dppz]2+, resulting in a decreasing cathode signal and an increasing anode signal owing to the ECL resonance energy transfer from Gd-MOF to [Ru(bpy)2dppz]2+. In this way, an efficient dual-signal ECL aptasensor is constructed for the ratiometric analysis of acetamiprid, exhibiting a remarkably low detection limit of 0.033 pM. Strikingly, by using only one exogenous coreactant, the cross interference from multiple coreactants can be eliminated, thus improving the detection accuracy. The developed high-performance ECL sensing platform is successfully applied to monitor the residual level of acetamiprid in real samples, demonstrating its potential application in the field of food security.

Bioinspired FeN5 Sites with Enhanced Peroxidase-like Activity Enable Colorimetric Sensing of Uranyl Ions in Seawater.

Nanozymes with peroxidase (POD)-like activity have garnered significant attention due to their exceptional performance in colorimetric assays. However, nanozymes often possess oxidase (OD) and POD-like activity simultaneously, which affects the accuracy and sensitivity of the detection results. To address this issue, inspired by the catalytic pocket of natural POD, a single-atom nanozyme with FeN5 configuration is designed, exhibiting enhanced POD-like activity in comparison with a single-atom nanozyme with FeN4 configuration. The axial N atom in FeN5 highly mimics the amino acid residues in natural POD to optimize the electronic structure of the metal active center Fe, realizing the efficient activation of H2O2. In addition, in the presence of both H2O2 and O2, FeN5 enhances the activation of H2O2, effectively avoiding the interference of dissolved oxygen in colorimetric sensing. As a proof-of-concept application, a colorimetric detection platform for uranyl ions (UO22+) in seawater is successfully constructed, demonstrating satisfactory sensitivity and specificity.

Trace Amount of Bi-Doped Core-Shell Pd@Pt Mesoporous Nanospheres with Specifically Enhanced Peroxidase-Like Activity Enable Sensitive and Accurate Detection of Acetylcholinesterase and Organophosphorus Nerve Agents.

The urgent need for sensitive and accurate assays to monitor acetylcholinesterase (AChE) activity and organophosphorus pesticides (OPs) arises from the imperative to safeguard human health and protect the ecosystem. Due to its cost-effectiveness, ease of operation, and rapid response, nanozyme-based colorimetry has been widely utilized in the determination of AChE activity and OPs. However, the rational design of nanozymes with high activity and specificity remains a great challenge. Herein, trace amount of Bi-doped core-shell Pd@Pt mesoporous nanospheres (Pd@PtBi2) have been successfully synthesized, exhibiting good peroxidase-like activity and specificity. With the incorporation of trace bismuth, there is a more than 4-fold enhancement in the peroxidase-like performance of Pd@PtBi2 compared to that of Pd@Pt. Besides, no significant improvement of oxidase-like and catalase-like activities of Pd@PtBi2 was found, which prevents interference from O2 and undesirable consumption of substrate H2O2. Based on the blocking impact of thiocholine, a colorimetric detection platform utilizing Pd@PtBi2 was constructed to monitor AChE activity with sensitivity and selectivity. Given the inhibition of OPs on AChE activity, a biosensor was further developed by integrating Pd@PtBi2 with AChE to detect OPs, capitalizing on the cascade amplification strategy. The OP biosensor achieved a detection limit as low as 0.06 ng mL-1, exhibiting high sensitivity and anti-interference ability. This work is promising for the construction of nanozymes with high activity and specificity, as well as the development of nanozyme-based colorimetric biosensors.

CRISPR/Cas12a-Responsive Smart DNA Hydrogel for Sensitive Electrochemiluminescence Detection of the Huanglongbing Outer Membrane Protein Gene.

Citrus Huanglongbing (HLB) is known as the cancer of citrus, where Candidatus Liberibacter asiaticus (CLas) is the most prevalent strain causing HLB. In this study, we report a novel electrochemiluminescence (ECL) biosensor for the highly sensitive detection of the CLas outer membrane protein (Omp) gene by coupling rolling circle amplification (RCA) with a CRISPR/Cas12a-responsive smart DNA hydrogel. In the presence of the target, a large number of amplicons are generated through RCA. The amplicons activate the trans-cleavage activity of CRISPR/Cas12a through hybridizing with crRNA, triggering the response of smart DNA hydrogel to release the encapsulated AuAg nanoclusters (AuAg NCs) on the electrode and therefore leading to a decreased ECL signal. The ECL intensity change (I0 - I) is positively correlated with the concentration of the target in the range 50 fM to 5 nM, with a limit of detection of 40 fM. The performance of the sensor has also been evaluated with 10 samples of live citrus leaves (five HLB negative and five HLB positive), and the result is in excellent agreement with the gold standard qPCR result. The sensing strategy has expanded the ECL versatility for detecting varying levels of dsDNA or ssDNA in plants with high sensitivity.

In Situ Defect Engineering of Fe-MIL for Self-Enhanced Peroxidase-Like Activity.

Defect engineering is an effective strategy to enhance the enzyme-like activity of nanozymes. However, previous efforts have primarily focused on introducing defects via de novo synthesis and post-synthetic treatment, overlooking the dynamic evolution of defects during the catalytic process involving highly reactive oxygen species. Herein, a defect-engineered metal-organic framework (MOF) nanozyme with mixed linkers is reported. Over twofold peroxidase (POD)-like activity enhancement compared with unmodified nanozyme highlights the critical role of in situ defect formation in enhancing the catalytic performance of nanozyme. Experimental results reveal that highly active hydroxyl radical (•OH) generated in the catalytic process etches the 2,5-dihydroxyterephthalic acid ligands, contributing to electronic structure modulation of metal sites and enlarged pore sizes in the framework. The self-enhanced POD-like activity induced by in situ defect engineering promotes the generation of •OH, holding promise in colorimetric sensing for detecting dichlorvos. Utilizing smartphone photography for RGB value extraction, the resultant sensing platform achieves the detection for dichlorvos ranging from 5 to 300 ng mL-1 with a low detection limit of 2.06 ng mL-1. This pioneering work in creating in situ defects in MOFs to improve catalytic activity offers a novel perspective on traditional defect engineering.

Amino-Ligand-Coordinated Dicopper Active Sites Enable Catechol Oxidase-Like Activity for Chiral Recognition and Catalysis.

Developing highly active and selective advanced nanozymes for enzyme-mimicking catalysis remains a long-standing challenge for basic research and practical applications. Herein, we grafted a chiral histidine- (His-) coordinated copper core onto Zr-based metal-organic framework (MOF) basic backbones to structurally mirror the bimetal active site of natural catechol oxidase. Such a biomimetic fabricated process affords MOF-His-Cu with catechol oxidase-like activity, which can catalyze dehydrogenation and oxidation of o-diphenols and then transfer electrons to O2 to generate H2O2 by the cyclic conversion of Cu(II) and Cu(I). Specifically, the elaborate incorporation of chiral His arms results in higher catalytic selectivity over the chiral catechol substrates than natural enzyme. Density functional theory calculations reveal that the binding energy and potential steric effect in active site-substrate interactions account for the high stereoselectivity. This work demonstrates efficient and selective enzyme-mimicking catalytic processes and deepens the understanding of the catalytic mechanism of nanozymes.

High-Indexed Intermetallic Pt3Sn Nanozymes with High Activity and Specificity for Sensitive Immunoassay.

Great efforts have been made to expand the application fields of nanozymes, which puts forward requirements for nanozymes with both superior catalytic activity and specificity. Herein, we reported the high-indexed intermetallic Pt3Sn (H-Pt3Sn) with high peroxidase-like activity and specificity. The resultant H-Pt3Sn exhibits a specific activity of 345.3 U/mg, which is 1.82 times higher than Pt. Moreover, H-Pt3Sn possesses negligible oxidase-like and catalase-like activities, achieving superior catalytic specificity toward H2O2 activation. Experimental and theoretical calculations reveal both the splitting energy for adsorbed H2O2 and the energy barrier for the rate-determining step of H-Pt3Sn are significantly decreased compared with Pt3Sn and Pt. Finally, a nanozyme-linked immunosorbent assay is successfully developed, achieving the sensitive and accurate colorimetric detection for carcinoembryonic antigen with a low detection limit of 0.49 pg/mL and showing practical feasibility in serum sample detection.

Improving Interface Matching in MOF-on-MOF S-Scheme Heterojunction through π-π Conjugation for Boosting Photoelectric Response.

Accelerating the migration of interfacial carriers in a heterojunction is of paramount importance for driving high-performance photoelectric responses. However, the inferior contact area and large resistance at the interface limit the eventual photoelectric performance. Herein, we fabricated an S-scheme heterojunction involving a 2D/2D dual-metalloporphyrin metal-organic framework with metal-center-regulated CuTCPP(Cu)/CuTCPP(Fe) through electrostatic self-assembly. The ultrathin nanosheet-like architectures reduce the carrier migration distance, while the similar porphyrin backbones promote reasonable interface matching through π-π conjugation, thereby inhibiting the recombination of photogenerated carriers. Furthermore, the metal-center-regulated S-scheme band alignments create a giant built-in electric field, which provides a huge driving force for efficient carrier separation and migration. Coupling with the biomimetic catalytic activity of CuTCPP(Fe), the resultant heterojunction was utilized to construct photoelectrochemical uric acid biosensors. This work provides a general strategy to enhance photoelectric responses by engineering the interfacial structure of heterojunctions.

Bridged Pt-OH-Mn Mediator in N-coordinated Mn Single Atoms and Pt Nanoparticles for Electrochemical Biomolecule Oxidation and Discrimination.

The rational design of efficient catalysts for uric acid (UA) electrooxidation, as well as the establishment of structure-activity relationships, remains a critical bottleneck in the field of electrochemical sensing. To address these challenges, herein, a hybrid catalyst that integrates carbon-supported Pt nanoparticles and nitrogen-coordinated Mn single atoms (PtNPs/MnNC) is developed. The metal-metal interaction during annealing affords the construction of metallic-bonded Pt-Mn pairs between PtNPs and Mn single atoms, facilitating the electron transfer from PtNPs to the support and thereby optimizing the electronic structure of catalysts. More importantly, experiments and theoretical calculations provide visual proof for the 'incipient hydrous oxide adatom mediator' mechanism for UA oxidation. The Pt-Mn pairs first adsorb OH* to construct the bridged Pt-OH-Mn mediators to serve as a highly active intermediate for N-H bond dissociation and proton transfer. Benefiting from the unique electronic and geometric structure of the catalytic center and reactive intermediates, PtNPs/MnNC exhibits superior electrooxidation performance. The electrochemical sensor based on PtNPs/MnNC enables sensitive detection and discrimination of UA and dopamine in serum samples. This work offers new insights into the construction of novel electrocatalysts for sensitive sensing platforms.

Anisotropic Dual S-Scheme Heterojunctions Mimic Natural Photosynthetic System for Boosting Photoelectric Response.

The design of heterojunctions that mimic natural photosynthetic systems holds great promise for enhancing photoelectric response. However, the limited interfacial space charge layer (SCL) often fails to provide sufficient driving force for the directional migration of inner charge carriers. Drawing inspiration from the electron transport chain (ETC) in natural photosynthesis system, we developed a novel anisotropic dual S-scheme heterojunction artificial photosynthetic system composed of Bi2O3-BiOBr-AgI for the first time, with Bi2O3 and AgI selectively distributed along the bicrystal facets of BiOBr. Compared to traditional semiconductors, the anisotropic carrier migration in BiOBr overcomes the recombination resulting from thermodynamic diffusion, thereby establishing a potential ETC for the directional migration of inner charge carriers. Importantly, this pioneering bioinspired design overcomes the limitations imposed by the limited distribution of SCL in heterojunctions, resulting in a remarkable 55-fold enhancement in photoelectric performance. Leveraging the etching of thiols on Ag-based materials, this dual S-scheme heterojunction is further employed in the construction of photoelectrochemical sensors for the detection of acetylcholinesterase and organophosphorus pesticides.

Harmonizing Enzyme-like Cofactors to Boost Nanozyme Catalysis.

Engineering isolated metal sites resembling the primary coordination sphere of metallocofactors enables atomically dispersed materials as promising nanozymes. However, most existing nanozymes primarily focus on replicating specific metallocofactors while neglecting other supporting cofactors within active pockets, leading to reduced electron transfer (ET) efficiency and thus inferior catalytic performances. Herein, we report a metal-organic framework UiO-67 nanozyme with atomically dispersed iron sites, which involves multiple tailored enzyme-like nanocofactors that synergistically drive the ET process for enhanced peroxidase-like catalysis. Among them, the linker-coupled atomic iron site plays a critical role in substrate activation, while bare linkers and zirconia nodes facilitate the ET efficiency of intermediates. The synergy of three nanocofactors results in a 4.29-fold enhancement compared with the single effort of isolated metal site-based nanocofactor, holding promise in immunoassay for sensitive detection of chlorpyrifos. This finding opens a new way for designing high-performance nanozymes by harmonizing various nanocofactors at the atomic and molecular scale.