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.

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.

Bifunctional enzyme-mimicking metal-organic frameworks for sensitive acetylcholine analysis.

The development of nanomaterials with multi-enzyme-like activity is crucial for addressing challenges in multi-enzyme-based biosensing systems, including cross-talk between different enzymes and the complexities and costs associated with detection. In this study, Pt nanoparticles (Pt NPs) were successfully supported on a Zr-based metal-organic framework (MOF-808) to create a composite catalyst named MOF-808/Pt NPs. This composite catalyst effectively mimics the functions of acetylcholinesterase (AChE) and peroxidase (POD). Leveraging this capability, we replaced AChE and POD with MOF-808/Pt NPs and constructed a biosensor for sensitive detection of acetylcholine (ACh). The MOF-808/Pt NPs catalyze the hydrolysis of ACh, resulting in the production of acetic acid. The subsequent reduction in pH value further enhances the POD-like activity of the MOFs, enabling signal amplification through the oxidation of a colorimetric substrate. This biosensor capitalizes on pH variations during the reaction to modulate the different enzyme-like activities of the MOFs, simplifying the detection process and eliminating cross-talk between different enzymes. The developed biosensor holds great promise for clinical diagnostic analysis and offers significant application value in the field.

Cu Aerogels with Sustainable Cu(I)/Cu(II) Redox Cycles for Sensitive Nonenzymatic Glucose Sensing.

Developing functional nanomaterials for nonenzymatic glucose electrochemical sensing platforms is vital and challenging from the perspective of pathology and physiology. Accurate identification of active sites and thorough investigation of catalytic mechanisms are critical prerequisites for the design of advanced catalysts for electrochemical sensing. Herein, Cu aerogels are synthesized as a model system for sensitive nonenzymatic glucose sensing. The resultant Cu aerogels exhibit good catalytic activity for glucose electrooxidation with high sensitivity and a low detection limit. Significantly, in situ electrochemical investigations and Raman characterizations reveal the catalytic mechanism of Cu-based nonenzymatic glucose sensing. During the electrocatalytic oxidation of glucose, Cu(I) is electrochemically oxidized to generate Cu(II), and the resultant Cu(II) is spontaneously reduced back to Cu(I) by glucose, achieving the sustained Cu(I)/Cu(II) redox cycles. This study provides profound insights into the catalytic mechanism for nonenzymatic glucose sensing, which provides great potential guidance for a rational design of advanced catalysts in the future.

Photothermal-Switched Single-Atom Nanozyme Specificity for Pretreatment and Sensing.

Various applications lead to the requirement of nanozymes with either specific activity or multiple enzyme-like activities. To this end, intelligent nanozymes with freely switching specificity abilities hold great promise to adapt to complicated and changeable practical conditions. Herein, a nitrogen-doped carbon-supported copper single-atom nanozyme (named Cu SA/NC) with switchable specificity is reported. Atomically dispersed active sites endow Cu SA/NC with specific peroxidase-like activity at room temperature. Furthermore, the intrinsic photothermal conversion ability of Cu SA/NC enables the specificity switch by additional laser irradiation, where photothermal-induced temperature elevation triggers the expression of oxidase-like and catalase-like activity of Cu SA/NC. For further applications in practice, a pretreatment-and-sensing integration kit (PSIK) is constructed, where Cu SA/NC can successively achieve sample pretreatment and sensitive detection by switching from multi-activity mode to specific-activity mode. This study sets the foundation for nanozymes with switchable specificity and broadens the application scope in point-of-care testing.

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.

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.

Ultrathin Ruthenium Nanosheets with Crystallinity-Modulated Peroxidase-like Activity for Protein Discrimination.

Noble-metal-based nanozymes have attracted great interest as enzyme mimics because of their unique properties. To modulate the performance and meet the requirements of practical biosensing applications, phase engineering is promising for the design of novel noble-metal-based nanomaterials. Herein, a simple salt-assist strategy was employed for the synthesis of Ru nanosheets (NSs) with the controlled crystalline degree. The crystalline degree plays a significant role in tuning peroxidase-like activity by optimizing the affinity toward the catalytic substrate. Furthermore, the inhibition effect of mercapto molecules on the peroxidase-like activity of Ru NSs was investigated. As a proof-of-concept, the Ru NSs-based colorimetric sensing arrays were developed to distinguish mercapto molecules, and five model molecules were well classified according to the different inhibition effects. Given the complexity of practical conditions, the sensing array was further applied to discriminate proteins possessing rich mercapto groups. This work not only provides an effective strategy for the design of highly active nanozymes but also achieves promising sensing arrays for practical needs.

Defect-Engineered Nanozyme-Linked Receptors.

Though nanozymes are successfully applied in various areas, the increasing demands facilitate the exploitation of nanozymes possessing higher activity and more functions. Natural enzyme-linked receptors (ELRs) are critical components for signal transductions in vivo by expressing activity variations after binding with ligands. Inspired by this, the defect-engineered carbon nitrides (DCN) are reported to serve as nanozyme-linked receptors (NLRs). For one thing, cyano defects increase the enzyme-like activity by a factor of 109.5. For another, DCN-based NLRs are constructed by employing cyano groups as receptors, and variable outputs are ensued upon the addition of ion ligands. Significantly, both the cascade effect and electronic effect are demonstrated to contribute to this phenomenon. Finally, NLRs are used for pattern recognition of metal ions, indicating the signal transduction ability of NLRs as well. This work not only provides great promise of defect engineering in nanozymes, but also contributes to the design of artificial ELRs.