Enzyme Mimics Research Articles

IrO2 clusters loaded on dendritic mesoporous silica nanospheres with superior peroxidase-like activity for sensitive detection of acetylcholinesterase and its inhibitors

Nanomaterials-based enzyme mimics (nanozymes), by simulating enzyme catalysis, have shown potential in numerous biocatalytic applications, but nanozymes face significant challenges of catalytic activity and reusability that may restrict their practical uses. Herein, we report facile fabrication of surface-clean IrO2 clusters supported on dendritic mesoporous silica nanospheres (DMSNs), which exhibit superior peroxidase-like activity, high thermal/long-term stability, and good recyclability. The IrO2 clusters (1.4 ± 0.2 nm in size) are obtained by the laser ablation without any ligands and possess negative surface charge, which are efficiently loaded on the amino-functionalized DMSNs by electrostatic adsorption. Owing to morphological and structural advantages, the resulted DMSN/IrO2 heterostructure displays outstanding peroxidase-like catalytic performance. Compared with horseradish peroxidase, it shows comparable affinities but higher reaction rate (2.95 × 10−7 M·s−1) towards H2O2, resulting from rapid electron transfer during the catalysis. This value is also larger than those of mesoporous silicas supported metal or metal oxides nanoparticles/clusters in the previous studies. Benefitting from excellent peroxidase-catalysis of the DMSN/IrO2, the colorimetric assays are further successfully established for the detection of acetylcholine esterase and its inhibitor, showing high sensitivity and selectivity. The work provides novel design of supported nanozymes for biosensing.

A Simple Substitution on Thyroid Hormones Remarkably Alters the Regioselectivity of Deiodination by a Deiodinase Mimic.

The regioselective deiodinations of L-thyroxine (T4) play key roles in the thyroid hormone homeostasis. These reactions are catalyzed by three isoforms of the selenoenzymes, iodothyronine deiodinases (Dio1, Dio2 and Dio3), which are highly homologous in nature. Dio1 mediates 5'- or 5-deiodinations of T4 to produce T3 and rT3, respectively. In contrast, Dio2 and Dio3 are selective to 5'- or 5-deiodination to produce T3 and rT3, respectively. Understanding of the regioselectivity of deiodination at the molecular level is important as abnormal levels of thyroid hormone have been implicated in various clinical conditions, such as hypoxia, myocardial infarction, neuronal ischemia and cancer. In this paper, we report that the electronic properties of the iodine atoms in thyroxine (T4) can be modulated through a simple substitution in the 4'-phenolic moiety. This leads to the change in the regioselectivity of deiodination by different small molecule mimics of Dio enzymes. By using this chemical approach, we also show that the substitution of a strong electron withdrawing group facilitates the removal of all four iodine atoms in the T4 derivative. Theoretical investigations on the hydrogen bonded adducts of T4 with imidazole indicate that the charge on the iodine atoms depend on the nature of hydrogen bond between the -OH group of T4 and the imidazole moiety. While the imidazole can act as either hydrogen bond acceptor (HBA) or hydrogen bond donor (HBD), the protonated imidazole acts exclusively as HBD in T4-imidazole complex. These studies support the earlier observations that the histidine residue at the active sites of the deiodinases play an important role not only in the substrate binding, but also in altering the regioselectivity of the deiodination reactions.

Influence of the chemically reduced graphene oxide interface on the antioxidant multienzyme properties of Prussian blue nanoparticles

Prussian blue nanoparticles (PB NPs) stabilized with surface capping agents as functional mimics of major antioxidant enzymes are attracting attention for use in reactions mediated by reactive oxygen species. However, influence of a stabilizing agent or interface on the enzyme-like properties of the nanomaterial remains unclear. In this study, we investigate the effect of the chemically reduced graphene oxide (rGO) interface on the morphology, stability, and multienzymatic activity of PB NPs. The rGO stabilized PB NPs nanocomposite (PB/rGO) demonstrated different morphology, dynamics of the superoxide scavenging, and lower peroxidase- and catalase-mimicking activities in comparison with the non-stabilized PB NPs. Electrochemical studies showed improved immobilization of PB/rGO on the graphite felt, while the sensitivity of hydrogen peroxide determination was higher for the non-stabilized PB NPs. This study enhances our understanding of the role of the rGO structuring interface in altering the properties of nanomaterials for oxidation protection and nanozyme-based sensing approaches.

Highly Sensitive Colorimetric Detection of Glutathione in Human Serum Based on Iron-Copper Metal-Organic Frameworks.

Emerging metal-organic framework (MOF)-based mimic enzymes have been exploited to design a colorimetric sensor for the detection of biomolecules. However, it is challenging to figure out the glutathione (GSH) detection method and the corresponding sensing mechanism using an MOF-based colorimetric sensor. In this work, a novel iron-copper MOF with high activity is synthesized by a wet-chemical method. A GSH colorimetric sensor based on the peroxidase-like properties of the iron-copper MOF is developed. Hydrogen peroxide is converted to hydroxyl radicals by the peroxidase-like properties of the iron-copper MOF mimic enzyme, which can catalyze the colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB (ox-TMB). The kinetic constant of the MOF mimic enzyme (0.02 mM for H2O2) is superior to horseradish peroxidase (HRP). The GSH content can be quantified by proposing a sensor based on the colorimetric method and color turn-off mechanism. The turn-off mechanism of GSH analysis includes two aspects. On the one hand, the blue ox-TMB can be deoxidized to colorless TMB by GSH. On the other hand, hydroxyl radicals (•OH) can be consumed by GSH. The linear range and limit of detection are 2-20 and 0.439 μM, respectively. At the same time, GSH detection also shows good specificity and anti-interference characteristics. Therefore, MOF-based colorimetric sensors have been used to qualitatively and quantitatively measure GSH contents in human serum. The mechanism and application of the iron-copper MOF pave a way for the development of mimic enzymes with polymetallic active sites in the field of colorimetric sensing.

Albumin-Based Zn (II)-Quercetin Enzyme Mimic Scavenging ROS for Protection against Cardiotoxicity Induced by Doxorubicin.

Doxorubicin (DOX) is a chemotherapeutic agent that can cause cardiotoxicity leading to progressive, chronic, life-threatening cardiomyopathy, called DOX-induced cardiomyopathy (DIC). DIC is a fatal cardiomyopathy with a worse prognosis compared to other cardiomyopathies and limits the use of DOX in malignancies due to its cardiotoxicity. DIC has been proven to be associated with reactive oxygen species (ROS)-induced side effect damage in cardiac myocytes. Currently, scavenging of reactive oxygen species is a practical strategy to reduce chemotherapy-associated DIC. Although quercetin has already been reported to have superior antioxidant activity, its clinical application is severely limited due to its rapid degradation and poor tissue absorption. Herein, we reported the preparation of a novel enzyme mimic via coordinated albumin, Zinc Ion (Zn2+) and quercetin. The enzyme mimics were capable of simultaneously increasing the biocompatibility and efficiently overcame the drawbacks of free quercetin, and were achieved by long circulation in vivo. Most importantly, these quercetin-based enzyme mimics had no effect on the antioxidant activity of quercetin. These beneficial therapeutic properties, together with high drug-carrying capacity and redox stimuli, will significantly improve quercetin's alleviation of chemotherapeutic cardiotoxicity without causing significant side effects. Therefore, nanoparticles of albumin-based Zn (II)-Quercetin have a promising clinical application as an effective agent for mitigating the cardiotoxicity of chemotherapy.

ROS scavenging Manganese-loaded mesoporous silica nanozymes for catalytic anti-inflammatory therapy

Reactive oxygen species (ROS) are reactive substances closely related to the inflammatory response, and previous studies have shown that anti-inflammatory therapy can achieve significant effects by scavenging ROS. Nanozymes are synthetic mimics of natural enzymes that are more stable, customizable, inexpensive, and catalytic for ROS. Therefore, we prepared a novel manganese-loaded mesoporous silica nanozyme (MnMSN) by template method and KMnO4 oxidation surfactant templates. The physicochemical properties of the nanomaterials were investigated by XRD, TEM, SEM, size, Zeta potential and BET, etc. The results showed that MnMSN contains MnO2 (Mn4+) and MnSiO3 (Mn2+), and the particle size of MnMSN is smaller with the increase of KMnO4 oxidation surfactant templates time, and the in vitro scavenging of ROS (H2O2, ·OH and ·O2–) is more effective. MnMSN has good cytocompatibility, scavenging intracellular ROS and inducing a shift from M1 to anti-inflammatory M2 phenotype. Furthermore, the intrinsic mechanism of MnMSN regulation of macrophage polarization was investigated by ELISA and qPCR, and the results showed that MnMSN is through scavenging ROS, leading to the down-regulation of NF-κB, which further leads to the down-regulation of TNF-α and IL-Iβ. The results of this work highlight the potential of MnMSN in catalyzing anti-inflammatory therapy.

Artificial metalloenzyme with peroxidase-like activity based on periodic mesoporous organosilica with ionic-liquid framework

Artificial enzymes were developed as alternatives to natural enzymes. Considering the unique characteristics of periodic mesoporous organosilica (PMO) materials, a rational design approach was investigated to simulate the coordination sphere around the iron active center in natural horseradish peroxidase (HRP) and fabricate a new peroxidase-like nanozyme. Well-ordered mesoscopic structure, high surface area, tunable pore size, high thermal-hydrothermal stability, and facile surface functionalization are unique properties of PMOs which allow them be potential candidate for enzyme mimic catalysis. In the present study, a monofunctional PMO with ionic-liquid framework (PMO-IL) was prepared as a support to incorporate the iron protoporphyrin IX hemin. The interior surface of mesochannels were also modified by imidazole functional groups. The synthetic peroxidase-like nanomaterial was fully characterized using several techniques such as N2 adsorption-desorption analysis, Thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) spectroscopy, powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray analysis (EDAX). Peroxidase-like activity of the current nanomaterial was evaluated using 2,2′-Azinobis [3-ethylbenzothiazoline-6-sulfonic acid]-diammonium salt (ABTS) in the presence of hydrogen peroxide in neutral pH condition. Michaelis-Menten kinetic parameters indicated enhanced affinity toward substrate. Results imply that the biomimetic pathways can be developed to achieve a new generation of nanozymes with excellent thermal stability and long-term storage stability which are promising as peroxidase mimics for various applications.

Food-borne melanoidin based peroxidase mimic for the precise detection of total antioxidant capacity

Drawing on the structure of the natural horseradish peroxidase (HRP) active site, in this study, food-borne Melanoidin and Fe3+ were used to construct a peroxide mimic enzyme, which possessed excellent peroxidase (POD)-like activity with the Km values of 0.088 mM and 0.358 mM toward 3,3′,5,5′-tetramethylbenzidine (TMB) and hydrogen peroxide (H2O2), respectively. Given the good POD-like activity of Melanoidin/Fe3+, a convenient, selective, and sensitive method for the determination of ascorbic acid (AA) was defined. The method covered the 10–100 μM AA concentration range with a 1.19 μM detection limit. With favorable anti-interference and strong stability, Melanoidin/Fe3+ was successfully applied to the determination of AA in foods and medicines. The high activity of Melanoidin/Fe3+ provides a new strategy for designing high-performance nanozymes, which has great potential in exogenous dietary and healthcare applications.

Ascorbate oxidase-like nanozyme with high specificity for inhibition of cancer cell proliferation and online electrochemical DOPAC monitoring

Despite the extensive investigation of the nanozymes exhibit their favorable performance compared to natural enzymes, nevertheless, the highly specific nanozyme still needs to be developed so that it can meet the requirements of exploring the mechanism as well as administration of related diseases and selective monitoring in biological system. In this study, self-assembled glutathione-Cu/Cu2O nanoparticles (GSH-Cu/Cu2O NPs) that exhibits specific ascorbic acid (AA) oxidase-like catalytic activity were constructed for AA-activated and H2O2-reinforced cancer cell proliferation inhibition and selective neurochemical monitoring. Cu/Cu2O NPs demonstrates effective AA oxidase-like activity and no common characteristics of other redox mimic enzymes often present in nanozyme. In particular, we found that the AA oxidase-like activity of GSH-Cu/Cu2O nanozyme was significantly improved by about 40% by improving the activation ability toward oxygen. The synthesized nanozyme can induce the generation of active oxygen by accelerating the oxidation of AA, which effectively suppresses the proliferation of cancer cells. We constructed an online electrochemical system (OECS) though loading nanozyme with enhanced ascorbate oxidase activity into a microreactor and setting it in the upstream of the detector. This GSH-Cu/Cu2O NPs-integrated microreactor can completely eliminate AA interference of the physical level toward 3,4-dihydroxy phenylacetic acid (DOPAC) electrochemical measurement, and the nanozyme-based OECS is able to continuously capture DOPAC alteration in rat brain acidosis model. Our findings may inspire rational design of nanozymes with high specificity as well as nanozyme-based selectivity solution for in vivo detection and show promising opportunities for their involvement in neurochemistry investigation.

Albumin-based Zn (II)-Quercetin Enzyme Mimic Scavenging ROS for Protection against Cardiotoxicity Induced by Doxorubicin

Albumin-based Zn (II)-Quercetin Enzyme Mimic Scavenging ROS for Protection against Cardiotoxicity Induced by Doxorubicin

Nanozyme‐Engineered Bioglass through Supercharged Interface for Enhanced Anti‐Infection and Fibroblast Regulation

AbstractEffective therapy of infection impaired tissue defects has long been an important but challenging topic, and alternative antibiotic‐free solutions are greatly demanded to tackle bacterial infections and promote tissue repair. Herein, the use of supercharged gold nanoclusters (AuNCs) with enhanced enzyme mimic activity as novel interface modulator of bioactive glass nanoparticles (BGN) for infected wound treatment is reported. The supercharged AuNCs exhibit extraordinary affinity toward BGN, leading to the robust immobilization of AuNCs on BGN (BGN‐AuNCs). Functional AuNCs endow BGN with superior peroxidase‐like activity for catalytic antibacterial action, which can kill bacteria with a concentration down to 75 µg mL−1 within 6 h due to the production of highly toxic ·OH. Moreover, expression level of COL‐1, TGF‐β, and FGF‐2 in fibroblasts is actively up‐regulated to 2.9, 3.1, and 1.6 times higher than that of control group due to the positive effect of BGN‐AuNCs on cell proliferation. Meanwhile, intrinsic photoluminescent property of AuNCs enables the direct visualization of BGN at both in vitro and in vivo levels for potentially bioimaging‐guided therapy. Further in vivo results demonstrate that BGN‐AuNCs hold enormous promise for infectious disease therapy and pro‐regeneration, and the proposed supercharged interface engineering strategy is attractive for developing advanced functional nanomedicines.

Hybrid bilayer membranes as platforms for biomimicry and catalysis.

Hybrid bilayer membrane (HBM) platforms represent an emerging nanoscale bio-inspired interface that has broad implications in energy catalysis and smart molecular devices. An HBM contains multiple modular components that include an underlying inorganic surface with a biological layer appended on top. The inorganic interface serves as a support with robust mechanical properties that can also be decorated with functional moieties, sensing units and catalytic active sites. The biological layer contains lipids and membrane-bound entities that facilitate or alter the activity and selectivity of the embedded functional motifs. With their structural complexity and functional flexibility, HBMs have been demonstrated to enhance catalytic turnover frequency and regulate product selectivity of the O2 and CO2 reduction reactions, which have applications in fuel cells and electrolysers. HBMs can also steer the mechanistic pathways of proton-coupled electron transfer (PCET) reactions of quinones and metal complexes by tuning electron and proton delivery rates. Beyond energy catalysis, HBMs have been equipped with enzyme mimics and membrane-bound redox agents to recapitulate natural energy transport chains. With channels and carriers incorporated, HBM sensors can quantify transmembrane events. This Review serves to summarize the major accomplishments achieved using HBMs in the past decade.

Nanozyme-Enabled Treatment of Cardio- and Cerebrovascular Diseases.

Cardio- and cerebrovascular diseases are two major vascular-related diseases that lead to death worldwide. Reactive oxygen species (ROS) play a vital role in the occurrence and exacerbation of diseases. Excessive ROS induce cellular context damage and lead to tissue dysfunction. Nanozymes, as emerging enzyme mimics, offer a unique perspective for therapy through multifunctional activities, achieving essential results in the treatment of ROS-related cardio- and cerebrovascular diseases by directly scavenging excess ROS or regulating pathologically related molecules. This review first introduces nanozyme-enabled therapeutic mechanisms at the cellular level. Then, the therapies for several typical cardio- and cerebrovascular diseases with nanozymes are discussed, mainly including cardiovascular diseases, ischemia reperfusion injury, and neurological disorders. Finally, the challenges and outlooks for the application of nanozymes are also presented. This review will provide some instructive perspectives on nanozymes and promote the development of enzyme-mimicking strategies in cardio- and cerebrovascular disease therapy.

Oxygen-terminated few-layered Ti3C2Tx MXene nanosheets as peroxidase-mimic nanozyme for colorimetric detection of kanamycin

Nanomaterials-based bioinspired enzyme mimics are gaining increased attention as alternatives to biocatalysts. Herein, we report synthesizing oxygen-terminated few-layered titanium-based MXene nanosheets (OFL-Ti-MN). OFL-Ti-MN possesses horseradish peroxidase (HRP) activity in catalyzing the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2), which turns the solution color bluish-green. The solution color fades quickly when kanamycin (KAN) is added to this system. This reaction indicates that KAN can prevent color change in the OFL-Ti-MN/TMB-H2O2 system. Based on this strategy, we developed an OFL-Ti-MN-based colorimetric sensor to detect and quantify KAN. The sensor exhibited a dynamic range from 15.28 nM to 46.14 μM and a calculated limit of detection (LOD) of 15.28 nM. From the insight gained from the peroxidase-mimic property of OFL-Ti-MN, we proposed a mechanism for the inhibition effect of KAN on peroxidase and peroxidase-mimic enzymes. The proposed mechanism can potentially help elucidate the reasons for the antibacterial function of KAN and its side effects in humans.

Temporally Controlled Multienzyme Catalysis Using a Dissipative Supramolecular Nanozyme.

The development of superior functional enzyme mimics (nanozymes) is essential for practical applications, including point-of-care diagnostics, biotechnological applications, biofuels, and environmental remediation. Nanozymes with the ability to control their catalytic activity in response to external fuels offer functionally valuable platforms mimicking nonequilibrium systems in nature. Herein, we fabricated a supramolecular coordination bonding-based dynamic vesicle that exhibits multienzymatic activity. The supramolecular nanozyme shows effective laccase-like catalytic activity with a KM value better than the native enzyme and higher stability in harsh conditions. Besides, the nanostructure demonstrates an efficient peroxidase-like activity with NADH peroxidase-like properties. Generation of luminescence from luminol and oxidation of dopamine are efficiently catalyzed by the nanozyme with high sensitivity, which is useful for point-of-care detections. Notably, the active nanozyme exhibits dynamic laccase-mimetic activity in response to pH variation, which has never been explored before. While a neutral/high pH leads to the self-assembly, a low pH disintegrates the assembled nanostructures and consequently turns off the nanozyme activity. Altogether, the self-assembled Cu2+-based vesicular nanostructure presents a pH-fueled dissipative system demonstrating effective temporally controlled multienzymatic activity.

Photoresponsive Small Molecule Enzyme Mimics.

Enzyme mimics emulate the catalytic activities of their natural counterparts. Light-responsive enzyme mimics are an emerging branch of biomimetic chemistry where the catalytic activities can be controlled reversibly by light. These light-responsive systems are constructed by incorporating a suitable photoswitchable unit around the active-site mimic. As these systems are addressable by light, they do not leave back any undesired side products, and their activation–deactivation can be easily controlled. Naturally, these systems have enormous potential in the field of on-demand catalysis. The synthetic light-responsive enzyme mimics are robust and stable under harsh conditions. They do not require special handling protocols like those for real enzymes and can be tailor-made for improved solubility in a variety of solvents. How the introduction of the light-responsive systems has offered a new-edge to the field of small-molecule enzyme mimic has been elaborated in this Mini-review. Recent breakthroughs in light-responsive enzyme-like systems have been highlighted. Finally, the current obstacles and future prospects of this field have been discussed.

Decorating Zirconium on Graphene Oxide to Design a Multifunctional Nanozyme for Eco-Friendly Detection of Hydrogen Peroxide

Peroxidase enzymes are crucial in analytical chemistry owing to significant peroxide analytes and their key role in hydrogen peroxide (H2O2) detection. Therefore, exploiting appropriate catalysts for the peroxidase like reactions has become crucial for achieving desired analytical performance. Zirconium (Zr) has attracted growing interest, as a safe and stable potential eco-friendly catalyst for various organic transformations that address increasing environmental challenges. Hence, aiming at fast, sensitive and selective optical detection of H2O2, a colorimetric platform is presented here, based on the excellent peroxidase enzyme-like activity of Zr decorated on graphene oxide (GO). The synergistic effect achieved due to intimate contact between an enzyme like Zr and the high surface area 0f GO ensures efficient electron transfer that increases the chemical and catalytic activity of the composite and advances the decomposition of H2O2 into hydroxyl radicals. The designed probe, thus, efficiently catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB), via hydroxyl radicals, thereby transforming the colorless TMB into blue oxidized TMB within 2 min. The catalytic mechanism of the Zr-GO enzyme mimic is proposed herein and verified using a fluorescent probe terephthalic acid (TA) and other scavenger experiments. The multifunctional optical probe allows sensitive and highly selective recognition of H2O2 in a linear range from 100 to 1000 µM with a low detection limit of 0.57 µM. Essentially, the direct accessibility of Zr prevents having to use the complicated preparation and purification procedures mostly practiced for conventional biozymes and nanozymes. The devised method offers several gains, including being green and an inexpensive catalyst, having lower LOD, being fast, cost-effective and sensitive, and having selective work-up procedures.

Bifunctional Mn-Doped N-Rich Carbon Dots with Tunable Photoluminescence and Oxidase-Mimetic Activity Enabling Bimodal Ratiometric Colorimetric/Fluorometric Detection of Nitrite.

Multimodal detection is a promising paradigm because of its advantages of expanding usage scenarios and improving reliability. However, it is very challenging to design reasonable strategies to achieve the multimodal sensing of targets. Herein, we developed an unprecedented bimodal ratiometric colorimetric/fluorometric method by exploring a novel bifunctional artificial oxidase mimic, Mn-doped N-rich carbon dots (Mn-CDs), to achieve the high-performance determination of nitrite in complicated matrices. The Mn-CDs exhibited both tunable photoluminescence and high oxidase-like activity, effectively catalyzing the colorless 3,3',5,5'-tetramethylbenzidine (TMB) oxidation to generate blue TMB+. When nitrite was introduced, the TMB+ species generated would specifically react with nitrite to produce diazotized TMB+, resulting in a color change from blue to green and finally to yellow. Simultaneously, the fluorescence of Mn-CDs was quenched by the diazotized TMB+ product via the inner filter effect. Hence, the existence of nitrite could lead to the simultaneous variations of visual color and photoluminescence, providing the principal basis for the bimodal ratiometric colorimetric/fluorometric quantification of the target. With the method, excellent sensitivity, selectivity, reliability, and practicability for nitrite detection were verified. Our work proposes a new bimodal strategy for nitrite measurement using bifunctional CDs-based enzyme mimics, which will inspire future effort on the exploration of promising multifunctional nanozymes and their advanced applications in biochemical sensing.

Ultrathin Graphdiyne/Graphene Heterostructure as a Robust Electrochemical Sensing Platform.

Graphdiyne (GDY) has been considered as an appealing electrode material for electrochemical sensing because of its alkyne-rich structure and high degrees of π-conjugation, which shows great affinity to heavy metal ions and pollutant molecules via d-π and π-π interactions. However, the low surface area and poor conductivity of bulk GDY limit its electrochemical performance. Herein, a two-dimensional ultrathin GDY/graphene (GDY/G) nanostructure was synthesized and used as an electrode material for electrochemical sensing. Graphene plays the role of an epitaxy template for few-layered GDY growth and conductive layers. The formed few-layered GDY with a high surface area possesses abundant affinity sites toward heavy metal ions (Cd2+, Pb2+) and toxic molecules, for example, nitrobenzene and 4-nitrophenol, via d-π and π-π interactions, respectively. Moreover, hemin as a key part of the enzyme catalytic motif was immobilized on GDY/G via π-π interactions. The artificial enzyme mimic hemin/GDY/G-modified electrode exhibited promising ascorbic acid and uric acid detection performance with excellent sensitivity and selectivity, a good linear range, and reproducibility. More importantly, real sample detection and the feasibility of this electrochemical sensor as a wearable biosensor were demonstrated.

New Insight into Assembled Fe3O4@PEI@Ag Structure as Acceptable Agent with Enzymatic and Photothermal Properties.

Metal-based enzyme mimics are considered to be acceptable agents in terms of their biomedical and biological properties; among them, iron oxides (Fe3O4) are treated as basement in fabricating heterogeneous composites through variable valency integrations. In this work, we have established a facile approach for constructing Fe3O4@Ag composite through assembling Fe3O4 and Ag together via polyethyleneimine ethylenediamine (PEI) linkages. The obtained Fe3O4@PEI@Ag structure conveys several hundred nanometers (~150 nm). The absorption peak at 652 nm is utilized for confirming the peroxidase-like activity of Fe3O4@PEI@Ag structure by catalyzing 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H2O2. The Michaelis–Menten parameters (Km) of 1.192 mM and 0.302 mM show the higher catalytic activity and strong affinity toward H2O2 and TMB, respectively. The maximum velocity (Vmax) value of 1.299 × 10−7 M∙s−1 and 1.163 × 10−7 M∙s−1 confirm the efficiency of Fe3O4@PEI@Ag structure. The biocompatibility illustrates almost 100% cell viability. Being treated as one simple colorimetric sensor, it shows relative selectivity and sensitivity toward the detection of glucose based on glucose oxidase. By using indocyanine green (ICG) molecule as an additional factor, a remarkable temperature elevation is observed in Fe3O4@PEI@Ag@ICG with increments of 21.6 °C, and the absorption peak is nearby 870 nm. This implies that the multifunctional Fe3O4@PEI@Ag structure could be an alternative substrate for formatting acceptable agents in biomedicine and biotechnology with enzymatic and photothermal properties.