Enzyme-like Catalysis Research Articles

Tailored Metal-Organic Framework-Based Nanozymes for Enhanced Enzyme-Like Catalysis.

The global crisis of bacterial infections is exacerbated by the escalating threat of microbial antibiotic resistance. Nanozymes promise to provide ingenious solutions. Here, we reported a homogeneous catalytic structure of Pt nanoclusters with finely tuned metal-organic framework (ZIF-8) channel structures for the treatment of infected wounds. Catalytic site normalization showed that the active site of the Pt aggregates structure with fine-tuned pore modifications structure had a catalytic capacity of 14.903 ×105 min-1, which was 18.7 times higher than that of the Pt particles in monodisperse state in ZIF-8 (0.793 ×105 min-1). In situ tests revealed that the change from homocleavage to heterocleavage of hydrogen peroxide at the interface of the nanozyme was one of the key reasons for the improvement of nanozyme activity. Density-functional theory and kinetic simulations of the reaction interface jointly determine the role of the catalytic center and the substrate channel together. Metabolomics analysis showed that the developed nanozyme, working in conjunction with reactive oxygen species, could effectively block energy metabolic pathways within bacteria, leading to spontaneous apoptosis and bacterial rupture. This pioneering study elucidates new ideas for the regulation of artificial enzyme activity and provides new perspectives for the development of efficient antibiotic substitutes.

Chiral FeNC single-atom nanozymes with multi-enzyme activity for dye degradation

The application of single-atom nanozymes in the removal of organic dye pollution by advanced oxidation process (AOPs) have been widely concerned. However, the application of single-atom nanozymes in AOPs is rarely reported. In this work, a kind of Fe-and nitrogen-codoped carbon (Fe-N-C) with peroxidase-like and laccase-like activities was prepared by calcining Fe-doped MOF, then the chiral peptides were introduced into single-atom nanozymes, and chiral single-atom nanozymes (L-Au@FeNC) were successfully prepared. The L-Au@FeNC can effectively activate PMS to degrade different kinds of organic dyes and also shows high cycle stability. In addition, the results of quenching experiment and electron paramagnetic resonance (EPR) test show that 1O2 produced during PMS activation plays an important role in the degradation of organic dyes, and O2·-, ·OH, and SO4·- are also produced during PMS activation, suggesting that the degradation of selected organic dyes include radical and non-radical pathways. It should be noted that L-Au@FeNC showed higher activity than D-Au@FeNC in enzyme-like activity (laccase-like and peroxidase-like) experiment and organic dye degradation, the results of molecular docking simulation indicated that it may be due to the better binding force of L peptide to the substrate of enzyme-like reaction and organic dye than D peptide. This chiral single-atom nanozymes provide a new idea for the application of organic dye degradation and enzyme-like catalysis design.

Responsive Magnetic Particle Imaging Tracer: Overcoming "Always-On" Limitation, Eliminating Interference, and Ensuring Safety in Adaptive Therapy.

Magnetic particle imaging (MPI) has emerged as a novel technology utilizing superparamagnetic nanoparticles as tracers, essential for disease diagnosis and treatment guidance in preclinical animal models. Unlike other modalities, MPI provides high sensitivity, deep tissue penetration, and no signal attenuation. However, existing MPI tracers suffer from "always-on" signals, which complicate organ-specific imaging and hinder accuracy. To overcome these challenges, we have developed a responsive MPI tracer using pH-responsive PdFe alloy particles coated with a gatekeeper polymer. This tracer exhibits pH-sensitive Fe release and modulation of the MPI signal, enabling selective imaging with a higher signal-to-noise ratio and intratumoral pH quantification. Notably, this responsive tracer facilitates subtraction-enhanced MPI imaging, effectively eliminating interference from liver uptake and expanding the scope of abdominal imaging. Additionally, the tracer employs a dual-function mechanism for adaptive cancer therapy, combining pH-switchable enzyme-like catalysis with dual-key co-activation of ROS generation, and Pd skeleton that scavenges free radicals to minimize Fe-related toxicity. This advancement promises to significantly expand MPI's applicability in diagnostics and therapeutic monitoring, marking a leap forward in imaging technology.

Construction of COFs@MoS2-Pd Hierarchical Tubular Heterostructures for Enhanced Catalytic Performance.

Here, we report ternary COFs@MoS2-Pd hybrids with an innovative self-sacrificial approach. MoO3@Covalent organic frameworks (COFs) microcables were first prepared and then two-dimensional MoS2 nanosheets (NSs) were integrated onto the surface of COFs, as COFs@MoS2, after treatment with hydrothermal reaction. The MoS2 NSs were used as an excellent support to introduce Pd nanoparticles (NPs) thanks to their reducing ability for the formation of the ternary COFs@MoS2-Pd hybrids. While COF microtubes improved the electrical conductivity of the hybrid materials, they also decreased the aggregation of MoS2 NSs, as a contribution to the enhanced catalytic performance. The mild reaction between MoS2 and Pd2+ ions realized the dense distribution of Pd NPs onto COFs@MoS2 for abundant active sites to further improve the catalytic performance. Thus, the hierarchical MoS2-based ternary hybrids were prepared with the enhanced catalytical performance as validated with the enzyme-like catalysis and the reduction of 4-nitrophenol.

Construction of Smartphone-Integrated Nanozyme Sensor Based on Amino Acid-Modulated Gold Nanoparticles.

Amino acids are not only the building blocks of proteins but also lead to the development of novel nanomaterials with unique properties. Herein, we proposed a simple strategy to produce gold nanoparticles (Au NPs) with peroxidase-like (POD-like) activities by using a series of amino acids as reducing agents, named Au NPs@M (M represents different amino acids). The Au NPs@His was identified as the nanozyme with the most potent catalytic performance, which was used in combination with smartphones to achieve rapid detection of hydrogen peroxide with a detection limit of 0.966 μM. It also enables rapid detection of glucose with a detection limit of 2.904 μM, highlighting the significant contribution of Au NPs@His in expediting the detection of critical biomolecules. This work not only provides a convenient and highly efficient method to identify glucose but also shows the potential of histidine as a reducing agent in constructing Au nanomaterials exerting enzyme-like catalysis.

Enzyme-Like Catalysis of Vinyl Copolymer Carrying Boron Directly Connected to Backbone: Catalytic Esterification through Cooperation of Boron with Neighboring Carboxylic Anhydride.

Alternating-rich copolymer of vinylboronic acid pinacol ester (VBpin) and maleic anhydride (MAH) was found to catalyze direct dehydrative esterification of carboxylic acid and alcohol. The key to the catalytic function is the activation of the MAH unit by the neighboring Lewis acidic boron directly connected to the backbone through the formation of five-membered ring. The effects of the side-chain cooperation were clarified through comparisons with the polymers having similar structures and a conventional titanium catalyst as well as the analyses of reactions with carboxylic acid or alcohol. The catalytic activity was enhanced as the molecular weight was higher, which is owing to the structural feature that boron is directly attached to the backbone. The cooperative catalysis is of interest because of its conceptual similarity with enzyme.

Shape-Complementary Multicomponent Assembly of Low-Symmetry Co(III)Salphen-Based Coordination Cages.

While metal-mediated self-assembly is a popular technique to construct discrete nanosized objects, highly symmetric structures, built from one type of ligand at a time, are dominating reported systems. The tailored integration of a set of different ligands requires sophisticated approaches to avoid narcissistic separation or formation of statistical mixtures. Here, we demonstrate how the combination of three structure-guiding effects (metal-templated macrocyclization, additional bridging ligands and shape-complementarity) based on Co(III)salphen metal nodes allows for a rational and high-yielding synthesis of structurally complex, lantern-shaped cages with up to four differentiable bridges. Three new heteroleptic coordination cages based on dinuclear Co(III)salphen macrocycles were synthesized in a one-pot reaction approach and fully characterized, including single crystal X-ray analyses. One cage groups two of the same ligands, another two different ligands around a symmetric Co2-bis-salphen ring. In the most complex structure, this ring is unsymmetric, rendering all four connections between the two metal centers distinguishable. While heteroleptic assembly around Pd(II) nodes has been shown to be dynamic, beneficial for cage-to-cage transformations, assembly cascades and adaptive systems, the herein introduced cages based on kinetically more inert Co(III)salphen will be advantageous for applications in enzyme-like catalysis and molecular machinery that require enhanced structural and chemical stability.

Spatially confining copper atom in flowerlike-CoFe hydroxides for smartphone-based ratiometric colorimetric dual-mode detection of nitrite

Great progress in nanozyme catalysis for distinct catalytic reactions have been made. However, more current nanozyme-induced sensing platforms are depended on oxidase-like nanozymes with multienzymatic catalytic behavior, which can affect the determination accuracy and reliability. Designing high active and stable advanced nanozymes for enzyme-like catalysis remains a huge challenge for analytic chemistry. Herein, a three-atom site catalyst of CoFeCu hydroxide nanozyme is rationally prepared for constructing sensing platform by utilizing oxidase-like catalytic activity. The CoFeCu nanozyme can mimic the behavior of oxidase by trigging O2 into O2·− via its highly dispersed metal active sites, which exhibits good oxidase-like activities with of 2.22 mM and of 3.69 × 10−8 M·s−1 toward 3, 3′, 5, 5′-tetramethylbenzidine (TMB). Specifically, the elaborate doping of low content Cu leads to higher catalytic activity and adequate detection sensitivity. Interestingly, with the addition of nitrite, a redox and diazotized reaction can be induced to generate visual color change from blue to yellow, resulting in the nitrite level-related ratio variation for the absorbance intensity at 665 and 450 nm. Besides, to the realize the demand of point-of-care monitor of nitrite, a portable sensor was built containing a dark box by a UV lamp and an intelligent smartphone. In the colorimetry-smartphone modes, the linear ranges of nitrite are 1–290, and 3.3–250 μM, with related detection limits of 0.9, and 2.96 μM, respectively. This strategy was further used to detect nitrite in river water with outstanding results with the dual mode. Therefore, the proposed dual-mode detection approach provides promising potential for self-house monitor of nitrite, which will greatly improve the analysis efficiency and large-scale determination in human life quality.

Effect of the U-Shaped Cavity of Conformationally Flexible Chiral Lewis-Acidic Boron-Based Catalysts in Multiselective Diels-Alder Reactions.

The effect of the U-shaped cavity of conformationally flexible chiral Lewis acidic boron-based catalysts in multiselective Diels-Alder reactions was investigated. The U-shaped catalysts can recognize substituents at the terminal acetylene moiety of propynal based on steric factors and can also recognize alkyne and alkene substrates based on the match/mismatch between the catalysts and substrates. Moreover, even in a mixture of different catalysts and substrates, the desired competitive reactions can proceed multiselectively. This proof-of-concept study should contribute to the development of artificial enzyme-like catalysis in vitro.

Colloidal Chiral Carbon Dots: An Emerging System for Chiroptical Applications.

Chiral CDots (c-CDots) not only inherit those merits from CDots but also exhibit chiral effects in optical, electric, and bio-properties. Therefore, c-CDots have received significant interest from a wide range of research communities including chemistry, physics, biology, and device engineers. They have already made decent progress in terms of synthesis, together with the exploration of their optical properties and applications. In this review, the chiroptical properties and chirality origin in extinction circular dichroism (ECD) and circularly polarized luminescence (CPL) of c-CDots is briefly discussed. Then, the synthetic strategies of c-CDots is summarized, including one-pot synthesis, post-functionalization of CDots with chiral ligands, and assembly of CDots into chiral architectures with soft chiral templates. Afterward, the chiral effects on the applications of c-CDots are elaborated. Research domains such as drug delivery, bio- or chemical sensing, regulation of enzyme-like catalysis, and others are covered. Finally, the perspective on the challenges associated with the synthetic strategies, understanding the origin of chirality, and potential applications is provided. This review not only discusses the latest developments of c-CDots but also helps toward a better understanding of the structure-property relationship along with their respective applications.

Electron Lock Manipulates the Catalytic Selectivity of Nanozyme.

Nanomaterials with enzyme-mimicking functions, termed nanozymes, offer attractive opportunities for biocatalysis and biomedicine. However, manipulating nanozyme selectivity poses an insurmountable hurdle. Here, we propose the concept of an energy-governed electron lock that controls electron transfer between nanozyme and substrates to achieve selectivity manipulation of enzyme-like catalysis. An electron lock can be constructed and opened, via modulating the nanozyme's electron energy to match the energy barrier of enzymatic reactions. An iron-doped carbon dot (FeCD) nanozyme with easy-to-regulate electron energy is selected as a proof of concept. Through regulating the conduction band which dominates electron energy, activatable oxidase and selective peroxidase (POD) with substrate affinity 123-fold higher than that of natural horseradish peroxidase (HRP) is achieved. Furthermore, while maintaining selectivity, FeCDs exhibit catalytic kinetics comparable to that of HRP upon transforming photons into electrons. Superior selectivity, efficient catalysis, and undetectable biotoxicity energize FeCDs as potent targeted drugs on antibiotic-resistant bacterial abscesses. An electron lock provides a robust strategy to manipulate selectivity toward advanced nanozymes.

A Pt1Pd Single-Atom Alloy Nanozyme with Boosted Enzyme-Like Activity for Efficient Photo-Mediated Tumor Therapy.

Single-atom nanozymes (SAzymes) are emerging natural enzyme mimics and have attracted much attention in the biomedical field. SAzymes with Metal─Nx sites designed on carbon matrixes are currently the mainstream in research. It is of great significance to further expand the types of SAzymes to enrich the nanozyme library. Single-atom alloys (SAAs) are a material in which single-atom metal sites are dispersed onto another active metal matrix, and currently, there is limited research on their enzyme-like catalytic performance. In this work, a biodegradable Pt1Pd SAA is fabricated via a simple galvanic replacement strategy, and for the first time reveals its intrinsic enzyme-like catalytic performance including catalase-, oxidase-, and peroxidase-like activities, as well as its photodynamic effect. Experimental characterizations demonstrate that the introduction of single-atom Pt sites contributes to enhancing the affinity of Pt1Pd single-atom alloy nanozyme (SAAzyme) toward substrates, thus exhibiting boosted catalytic efficiency. In vitro and in vivo experiments demonstrate that Pt1Pd SAAzyme exhibits a photo-controlled therapeutic effect, with a tumor inhibition rate of up to 100%. This work provides vital guidance for opening the research direction of SAAs in enzyme-like catalysis.

Histidine modulates amyloid-like assembly of peptide nanomaterials and confers enzyme-like activity

Amyloid-like assembly is not only associated with pathological events, but also leads to the development of novel nanomaterials with unique properties. Herein, using Fmoc diphenylalanine peptide (Fmoc–F–F) as a minimalistic model, we found that histidine can modulate the assembly behavior of Fmoc–F–F and induce enzyme-like catalysis. Specifically, the presence of histidine rearranges the β structure of Fmoc–F–F to assemble nanofilaments, resulting in the formation of active site to mimic peroxidase-like activity that catalyzes ROS generation. A similar catalytic property is also observed in Aβ assembled filaments, which is correlated with the spatial proximity between intermolecular histidine and F-F. Notably, the assembled Aβ filaments are able to induce cellular ROS elevation and damage neuron cells, providing an insight into the pathological relationship between Aβ aggregation and Alzheimer’s disease. These findings highlight the potential of histidine as a modulator in amyloid-like assembly of peptide nanomaterials exerting enzyme-like catalysis.

Sensitive Detection of Trace Vitamin C via Enzyme-like Catalysis of S Defect-Rich Ultrathin 2D MoS2: Comprehensive Innovative Experiments on Two-Dimensional Materials for Undergraduates

Sensitive Detection of Trace Vitamin C via Enzyme-like Catalysis of S Defect-Rich Ultrathin 2D MoS₂: Comprehensive Innovative Experiments on Two-Dimensional Materials for Undergraduates

Synergistic photocatalytic nanozymes to promote contaminant removal and hydrogen production

Photocatalytic nanozymes, which combine light-induced redox reactions and enzyme-like catalysis, have emerged as a promising class of nanomaterials. This alliance offers tremendous potential for light-enhanced enzyme-like activity and expands the applications of nanozymes in energy and environmental fields. In this study, a photocatalytic nanozyme OVs-TiO2/Pd hybrid nanosheets (HNSs) with abundant oxygen vacancies (OVs) and controllable Pd components was prepared by a one-step solid-phase reduction method. Benefiting from the synergistic effect and the strong metal-support interaction, OVs-TiO2/Pd HNSs exhibit remarkable light-enhanced oxidase-like and hydrogenase-like activity, they efficiently catalyze the degradation of antibiotics and the production of hydrogen, respectively. Electron spin resonance and transient photovoltage techniques elucidated that the enhanced enzyme-like activities are attributed to the increased generation of charge carriers and reactive oxygen species. This study builds a bridge between photocatalysis and enzyme-like catalysis, opening up a new avenue to explore the multiple functional nanomaterials for a myriad of applications.

Structural Analysis of Non-native Peptide-Based Catalysts Using 2D NMR-Guided MD Simulations.

Proteins and enzymes generally achieve their functions by creating well-defined 3D architectures that pre-organize reactive functionalities. Mimicking this approach to supramolecular pre-organization is leading to the development of highly versatile artificial chemical environments, including new biomaterials, medicines, artificial enzymes, and enzyme-like catalysts. The use of β-turn and α-helical motifs is one approach that enables the precise placement of reactive functional groups to enable selective substrate activation and reactivity/selectivity that approaches natural enzymes. Our recent work has demonstrated that helical peptides can serve as scaffolds for pre-organizing two reactive groups to achieve enzyme-like catalysis. In this study, we used CYANA and AmberTools to develop a computational approach for determining how the structure of our peptide catalysts can lead to enhancements in reactivity. These results support our hypothesis that the bifunctional nature of the peptide enables catalysis by pre-organizing the two catalysts in reactive conformations that accelerate catalysis by proximity. We also present evidence that the low reactivity of monofunctional peptides can be attributed to interactions between the peptide-bound catalyst and the helical backbone, which are not observed in the bifunctional peptide.

Reactive Template-Engaged Synthesis of NiSx/MoS2 Nanosheets Decorated on Hollow and Porous Carbon Microtubes with Optimal Electronic Modulation toward High-Performance Enzyme-like Performance

As a promising cost-effective nanozyme, MoS2 nanosheets (NSs) have been considered as a good candidate for the enzyme-like catalysis. However, their catalytic activity is still restricted by the insufficient active sites and poor conductivity, and thus, the comprehensive performances are still unsatisfactory. To address these issues, herein, we design and fabricate an intelligent tubular nanostructure of hierarchical hollow nanotubes, which are assembled by NiSx/MoS2 NSs encapsulated into N-doped carbon microtubes (NiSx/MoS2@NCMTs). The N-doped carbon microtubes (NCMTs) serve as a conductive skeleton, integrating with NiSx/MoS2 NSs and ensuring their well-distribution, thereby maximally exposing more active sites. Additionally, the tube-like structure is favorable for increasing the mass transfusion to ensure their excellent catalytic performance. Profiting from their component and structural advantages, the obtained NiSx/MoS2@NCMTs exhibit a surprisingly enhanced enzyme-like activity. Based on these, a facile colorimetric sensing platform to detect H2O2 and GSH has been developed. This proposed approach can be expected to synthesize a series of tubular heterostructured MoS2-based composites, which will be widely applied in catalysis, energy storage, disease diagnosis, etc.

Dynamic assembly of DNA-ceria nanocomplex in living cells generates artificial peroxisome

Intracellular accumulation of reactive oxygen species (ROS) leads to oxidative stress, which is closely associated with many diseases. Introducing artificial organelles to ROS-imbalanced cells is a promising solution, but this route requires nanoscale particles for efficient cell uptake and micro-scale particles for long-term cell retention, which meets a dilemma. Herein, we report a deoxyribonucleic acid (DNA)-ceria nanocomplex-based dynamic assembly system to realize the intracellular in-situ construction of artificial peroxisomes (AP). The DNA-ceria nanocomplex is synthesized from branched DNA with i-motif structure that responds to the acidic lysosomal environment, triggering transformation from the nanoscale into bulk-scale AP. The initial nanoscale of the nanocomplex facilitates cellular uptake, and the bulk-scale of AP supports cellular retention. AP exhibits enzyme-like catalysis activities, serving as ROS eliminator, scavenging ROS by decomposing H2O2 into O2 and H2O. In living cells, AP efficiently regulates intracellular ROS level and resists GSH consumption, preventing cells from redox dyshomeostasis. With the protection of AP, cytoskeleton integrity, mitochondrial membrane potential, calcium concentration and ATPase activity are maintained under oxidative stress, and thus the energy of cell migration is preserved. As a result, AP inhibits cell apoptosis, reducing cell mortality through ROS elimination.

Electrospinning of n-hemin/PAN Nanocomposite Membranes and Its Photo-Enhanced Enzyme-like Catalysis.

Hemin possesses great potential in eliminating organic pollutants due to its mild reaction condition, light-harvesting efficiency, and environmental friendliness. However, it has drawbacks such as being easy to aggregate and hard to recycle, and poor stability should be improved in practical application. Herein, the subject developed an electrospinning approach to enable the hemin particulates to be immobilized onto polyacrylonitrile (PAN) nanofibers stably. Hydrogen peroxide (H2O2) was adopted as an oxidant in the system to simulate the enzymatic catalysis of hemin in an organism. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflection spectroscopy (DRS), and electron spin resonance spectroscopy (ESR) analysis was employed to discuss the morphology, structure, and mechanism of the prepared n-hemin/PAN nanocomposite membranes, and 0.02 mmol L-1 of the rhodamine B (RhB) removal activity in different conditions was also verified with these membranes. The kinetic studies showed that n-hemin/PAN nanocomposite membranes maintained excellent properties both in adsorption and degradation. Around 42% RhB could be adsorbed in the dark, while 91% RhB decolorized under xenon lamp irradiation in 110 min, suggesting the catalytic performance of n-hemin/PAN was greatly driven by light irradiation. Differing from the axial coordinated hemin complexes, n-hemin/PAN would catalyze hydrogen peroxide into •OH radicals rather than •OOH and high-valent metal-oxo species. This work provides an effective way to support hemin as nanocomposite membranes, in which the molecular interaction between polymer and hemin made their light adsorption an obvious red shift.

Rational Design of Conducting Polymer-Derived Tubular Carbon Nanoreactors for Enhanced Enzyme-like Catalysis and Total Antioxidant Capacity Bioassay Application.

The design of void-confined tubular nanostructures has aroused significant interest for catalytic applications because of their distinct microenvironment to modulate the reaction kinetics. Herein, we propose a facile wrapping-pyrolysis strategy to confine Fe0 nanoparticles (Fe NPs) inside N-doped carbon nanotubes (Fe@NC NTs) derived from Fe2O3@polypyrrole (PPy) core-sheath nanofibers (NFs). The resultant Fe@NC NTs can act as efficient enzyme mimics and exhibit a significantly higher peroxidase (POD)-like catalytic activity than unconfined Fe NPs and bare NC NTs. Kinetic experiments demonstrate that the optimized void structure benefits the affinity with the POD substrates and achieves excellent catalytic efficiency. The mechanism study reveals that the generation of •OH from H2O2 endows Fe@NC NTs with excellent POD-like performance. Furthermore, we develop a total antioxidant capacity (TAC) sensing platform on account of this efficient POD-like system, expanding their applications in the field of food safety and human healthcare.