Construction and Application of Nanozyme Sensor Arrays.

Compared with traditional "lock-key mode" biosensors, a sensor array consists of a series of sensing elements based on intermolecular interactions (typically hydrogen bonds, van der Waals forces, and electrostatic interactions). At the same time, sensor arrays also have the advantages of fast response, high sensitivity, low energy consumption, low cost, rich output signals, and imageability, which have attracted widespread attention from researchers. Nanozymes are nanomaterials which own enzyme-like properties. Because of the adjustable activity, high stability, and cost effectiveness of nanozymes, they are potential candidates for construction of sensor arrays to output different signals from analytes through the chemoresponse of colorants, which solves the shortcomings of traditional sensors that they cannot support multiple detection and lack universality. Recently, a sensor array based on nanozymes as nonspecific recognition receptors has attracted much more attention from researchers and has been applied to precise recognition of proteins, bacteria, and heavy metals. In this perspective, attention is given to nanozymes and the regulation of their enzyme-like activity. Particularly, the building principles and methods for sensor arrays based on nanozymes are analyzed, and the applications are summarized. Finally, the approaches to overcome the challenges and perspectives are also presented and analyzed for facilitating further research and development of nanozyme sensor arrays. This perspective should be helpful for gaining insight into research ideas within the field of nanozyme sensor arrays.

In Situ Construction of Highly Dispersed Pd on Cobalt Nanoparticle on Hollow Functional Cubic Graphene by Double Framework for ORR.

Developing advanced functional carbon materials is essential for electrocatalysis, caused by their vast merits for boosting many key energy conversion reactions. Herein, the covalent organic frameworks (COFs) is utilized on metal-organic frameworks (MOFs) as the template, under the controllable metal atoms thermal migration process successfully in situ constructs Pd-Co alloy nanoparticles on hollow cubic graphene. The electrocatalytic oxygen reduction reaction (ORR) evaluation showed excellent performances with a half-wave potential of 0.866 V, and a limited current density of 4.975 mA cm-2, that superior to the commercial Pt/C and Co nanoparticles. The contrast experiments and X-ray absorption spectrum demonstrated the aggregated electrons at highly dispersed Pd atoms on Co nanoparticle that promoted the main activities. This work not only enlightens the novel carbon materials designing strategies but also suggests heterogeneous electrocatalysis.

Memristor-Based Bionic Tactile Devices: Opening the Door for Next-Generation Artificial Intelligence.

Bioinspired tactile devices can effectively mimic and reproduce the functions of the human tactile system, presenting significant potential in the field of next-generation wearable electronics. In particular, memristor-based bionic tactile devices have attracted considerable attention due to their exceptional characteristics of high flexibility, low power consumption, and adaptability. These devices provide advanced wearability and high-precision tactile sensing capabilities, thus emerging as an important research area within bioinspired electronics. This paper delves into the integration of memristors with other sensing and controlling systems and offers a comprehensive analysis of the recent research advancements in memristor-based bionic tactile devices. These advancements incorporate artificial nociceptors and flexible electronic skin (e-skin) into the category of bio-inspired sensors equipped with capabilities for sensing, processing, and responding to stimuli, which are expected to catalyze revolutionary changes in human-computer interaction. Finally, this review discusses the challenges faced by memristor-based bionic tactile devices in terms of material selection, structural design, and sensor signal processing for the development of artificial intelligence. Additionally, it also outlines future research directions and application prospects of these devices, while proposing feasible solutions to address the identified challenges.

Electrogenerated Chemiluminescence Imaging of Single-Atom Nanocatalysts.

Single-atom catalysts (SACs), distinguished by their maximum atom efficiency and precise control over the coordination and electronic properties of individual atoms, show great promise in electrocatalysis. Gaining a comprehensive understanding of the electrochemical performance of SACs requires the screening of electron transfer process at micro/nano scale. This research pioneers the use of electrogenerated chemiluminescence microscopy (ECLM) to observe the electrocatalytic reactions at individual SACs. It boasts sensitivity at the single photon level and temporal resolution down to 100 ms, enabling real-time capture of the electrochemical behavior of individual SACs during potential sweeping. Leveraging the direct correlation between ECL emission and heterogeneous electron transfer processes, we introduced photon flux density for quantitative analysis, unveiling the electrocatalytic efficiency of individual SACs. This approach systematically reveals the relationship between SACs based on different metal atoms and their peroxidase (POD)-like activity. The outcomes contribute to a fundamental understanding of SACs and pave the way for designing SACs with diverse technological and industrial applications.

Research Progress in Iron-Based Nanozymes: Catalytic Mechanisms, Classification, and Biomedical Applications.

Natural enzymes are crucial in biological systems and widely used in biology and medicine, but their disadvantages, such as insufficient stability and high-cost, have limited their wide application. Since Fe3O4 nanoparticles were found to show peroxidase-like activity, researchers have designed and developed a growing number of nanozymes that mimic the activity of natural enzymes. Nanozymes can compensate for the defects of natural enzymes and show higher stability with lower cost. Iron, a nontoxic and low-cost transition metal, has been used to synthesize a variety of iron-based nanozymes with unique structural and physicochemical properties to obtain different enzymes mimicking catalytic properties. In this perspective, catalytic mechanisms, activity modulation, and their recent research progress in sensing, tumor therapy, and antibacterial and anti-inflammatory applications are systematically presented. The challenges and perspectives on the development of iron-based nanozymes are also analyzed and discussed.

Cascade Reaction Regulated Electrochemiluminescence via Dual-Atomic-Site Catalysts.

Single-atom catalysts (SACs), a novel kind of electrocatalysts with full metal utilization, have been developed as unique signal amplifiers in several sensing platforms. Herein, based on theoretical prediction of the oxygen reduction reaction (ORR) mechanism on different atom sites, we constructed dual-atomic-site catalysts (DACs), Fe/Mn-N-C, to catalyze luminol-dissolved oxygen electrochemiluminescence (ECL). Computational simulation indicated that the weak adsorption of OH* on a single Fe site was overcome by introducing Mn as the secondary metallic active site, resulting in a synergic dual-site cascade mechanism. The superior catalytic activity of Fe/Mn-N-C DACs for the ORR was proven by the highly efficient cathodic luminol ECL, surpassing the performance of single-site catalysts (SACs), Fe-N-C and Mn-N-C. Furthermore, the ECL system, enhanced by a cascade reaction, exhibited remarkable sensitivity to ascorbic acid, with a detection limit of 0.02 nM. This research opens up opportunities for enhancing both the ECL efficiency and sensing performance by employing a rational atomic-scale design for DACs.

Chevrel Phase Mo6 S8 Nanosheets Featuring Reversible Electrochemical Li-Ion Intercalation as Effective Dynamic-Phase Promoter for Advanced Lithium-Sulfur Batteries.

Modifying sulfur cathodes with lithium polysulfides (LiPSs) adsorptive and electrocatalytic host materials is regarded as one of the most effective approaches to address the challenging problems in lithium-sulfur (Li-S) batteries. However, because of the high operating voltage window of Li-S batteries from 1.7 to 2.8 V, most of the host materials cannot participate in the sulfur redox reactions within the same potential region, which exhibit fixed or single functional property, hardly fulfilling the requirement of the complex and multiphase process. Herein, Chevrel phase Mo6 S8 nanosheets with high electronic conductivity, fast ion transport capability, and strong polysulfide affinity are introduced to sulfur cathode. Unlike most previous inactive hosts with a fixed affinity or catalytic ability toward LiPSs, the reaction involving Mo6 S8 is intercalative and the adsorbability for LiPSs as well as the ionic conductivity can be dynamically enhanced via reversible electrochemical lithiation of Mo6 S8 to Li-ion intercalated Lix Mo6 S8 , thereby suppressing the shuttling effect and accelerating the conversion kinetics. Consequently, the Mo6 S8 nanosheets act as an effective dynamic-phase promoter in Li-S batteries and exhibit superior cycling stability, high-rate capability, and low-temperature performance. This study opens a new avenue for the development of advanced hosts with dynamic regulation activity for high performance Li-S batteries.

Biomineralized tetramethylpyrazine-loaded PCL/gelatin nanofibrous membrane promotes vascularization and bone regeneration of rat cranium defects.

Conventional electrospinning produces nanofibers with smooth surfaces that limit biomineralization ability. To overcome this disadvantage, we fabricated a tetramethylpyrazine (TMP)-loaded matrix-mimicking biomineralization in PCL/Gelatin composite electrospun membranes with bubble-shaped nanofibrous structures. PCL/Gelatin membranes (PG), PCL/Gelatin membranes containing biomineralized hydroxyapatite (HA) (PGH), and PCL/Gelatin membranes containing biomineralized HA and loaded TMP (PGHT) were tested. In vitro results indicated that the bubble-shaped nanofibrous surface increased the surface roughness of the nanofibers and promoted mineralization. Furthermore, sustained-release TMP had an excellent drug release efficiency. Initially released vigorously, it reached stabilization at day 7, and the slow-release rate stabilized at 61.0 ± 1.8% at 28 days. All membranes revealed an intact cytoskeleton, cell viability, and superior adhesion and proliferation when stained with Ghost Pen Cyclic Peptide, CCK-8, cell adhesion, and EdU. In PGHT membranes, the osteogenic and vascularized gene expression of BMSCs and human vascular endothelial cells was significantly upregulated compared with that in other groups, indicating the PGHT membranes exhibited an effective vascularization role. Subsequently, the membranes were implanted in a rat cranium defect model for 4 and 8 weeks. Micro-CT and histological analysis results showed that the PGHT membranes had better bone regenerative patterns. Additionally, the levels of CD31 and VEGF significantly increased in the PGHT membrane compared with those in other membranes. Thus, PGHT membranes could accelerate the repair of cranium defects in vivo via HA and TMP synergistic effects.

Perspective for Single Atom Nanozymes Based Sensors: Advanced Materials, Sensing Mechanism, Selectivity Regulation, and Applications.

Nanozymes are a kind of nanomaterial mimicking enzyme catalytic activity, which has aroused extensive interest in the fields of biosensors, biomedicine, and climate and ecosystems management. However, due to the complexity of structures and composition of nanozymes, atomic scale active centers have been extensively investigated, which helps with in-depth understanding of the nature of the biocatalysis. Single atom nanozymes (SANs) cannot only significantly enhance the activity of nanozymes but also effectively improve the selectivity of nanozymes owing to the characteristics of simple and adjustable coordination environment and have been becoming the brightest star in the nanozyme spectrum. The SANs based sensors have also been widely investigated due to their definite structural features, which can be helpful to study the catalytic mechanism and provide ways to improve catalytic activity. This perspective presents a comprehensive understanding on the advances and challenges on SANs based sensors. The catalytic mechanisms of SANs and then the sensing application from the perspectives of sensing technology and sensor construction are thoroughly analyzed. Finally, the major challenges, potential future research directions, and prospects for further research on SANs based sensors are also proposed.

Electronic whiskers for velocity sensing based on the liquid metal hysteresis effect.

The artificial biomimetic sensory hair as state-of-art electronics has drawn great attention from academic theorists of industrial production given its potential application in soft robotics, environmental exploration and health monitoring. However, it still remains a challenge to develop highly sensitive electronic sensory hair with fast response. In this study, a bio-inspired electronic whisker (e-whisker) with a hollow polymer shell and a liquid metal core was prepared by microinjection for airflow measurement and detection of obstacles. In addition, we illustrated the effect of liquid metal hysteresis on its distribution in microchannels on deformation. The difference in the deformed velocity between the selected fiber and EGaIn would result in a disturbance emerging in the liquid metal channel, which further causes a variation in resistance. Taking advantage of this phenomenon, the integrated fiber e-whisker can be employed to detect tiny airflow and disturbance. The experimental results indicate that the fiber sensor can detect the airflow velocity as low as 0.2 m s-1 within 0.1 s. The e-whisker can accurately monitor rainfall, human motion and object velocity. This work sheds light on the liquid metal viscosity-induced sensing mechanism and offers a novel strategy to fabricate high-performance velocity sensors.

Perspectives for Single-Atom Nanozymes: Advanced Synthesis, Functional Mechanisms, and Biomedical Applications.

Single-atom nanozymes (SANs) are one of the newest generations of nanozymes, which have been greatly developed in the past few years and exploited widely for many applications, such as biosensing, disease diagnosis and therapy, bioimaging, and so on. SANs, possessing dispersed single-atom structures and a well-defined coordination environment, exhibit remarkable catalytic performance with both high activity and stability. In this paper, the most recent progress in SANs is reviewed in terms of their advanced synthesis, characterization, functional mechanisms, performance validation/optimization, and biomedical applications. Several technical challenges hindering practical applications of SANs are analyzed, and possible research directions are also proposed for overcoming the challenges.

A wearable contact lens sensor for noninvasive in-situ monitoring of intraocular pressure.

Glaucoma is the second leading cause of blindness in the world. Intraocular pressure (IOP) is a primary indicator of glaucoma which can be measured for the treatment of the disease. This paper presents a piezo-resistive principle pressure sensor to monitor IOP continuously and non-invasively. The sensor is designed based on the Wheatstone bridge circuit and fabricated by the spray-coating method. The hybrid nanomaterials of graphene and carbon nanotubes are introduced as sensing layers which are embedded inside the soft contact lens substrate composed of flexible polydimethyl siloxane (PDMS) and parylene. The sensing performance is discussed followed by a brief description of our sensor design and fabrication. Tests on a PDMS eyeball model indicate that it has a high sensitivity of 36.01 µV mmHg-1. Also, the frequency response and the ability to track dynamic pressure change cycles are demonstrated in normal IOP variation range from 9 to 34 mmHg. It shows good repeatability and linearity, and can accurately track fluctuating IOP. Thus, this sensor, with its ease of fabrication and simple design, as well as allowance for continuous pressure measurement, offers a promising approach for IOP monitoring in clinical diagnosis of glaucoma.

Characterization of the inhomogeneity of Pt/CeO x /Pt resistive switching devices prepared by magnetron sputtering.

There are unrevealed factors that bring about the performance variations of resistive switching devices. In this work, Pt/CeO x /Pt devices prepared by magnetron sputtering showed rectification in their asymmetrical current-voltage (I-V) curves during voltage sweeps. X-ray photoelectron spectroscopy showed that the deposited CeO x film had an inhomogeneous composition, and more oxygen vacancies existed in CeO x near the top electrode. The asymmetrical resistance change of the Pt/CeO x /Pt devices can be explained by the presence of more charged oxygen vacancies in CeO x near the top electrode, along with the Schottky conduction mechanism. This work reveals that the compositional inhomogeneity is inevitable in the magnetron sputtering of oxide targets like CeO2 and can be an important source of device-to-device and cycle-to-cycle variations of memristors.

Monodispersed gold nanoparticles entrapped in ordered mesoporous carbon/silica nanocomposites as xanthine oxidase mimic for electrochemical sensing of xanthine.

Monodispersed Au nanoparticles in ordered mesoporous carbon/silica (Au/OMCS) nanocomposites were prepared by the solvent evaporation induced self-assembly. Au/OMCS nanocomposites were characterized through XRD, BET, and TEM. The obtained nanocomposites exhibit uniform mesopores with the size of 18 ± 2 nm. And ultrafine Au nanoparticles with the size of 3~7 nm are well dispersed in the cavities. An ultrasensitive nanoenzyme sensor was fabricated based on a Au/OMCS-modified electrode. The Au/OMCS-modified electrode displays high xanthine oxidase-like catalytic activity evaluated through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The DPV response currents are linearly dependent on concentrations of xanthine (Xa) in the range 0.10-20 µM, along with a high sensitivity of 6.84 µA µM-1 cm-2 and very low detection limit of 0.006 µM (S/N = 3) under the optimal working potential of 0.64 V vs. SCE. Interference experiments show that the nanoenzyme sensor has no obvious responses to most potentially interfering species at a potential of 0.64 V. The fabricated sensor has been applied to the determination of Xa in spiked urine samples with recoveries ranging from 98.26 to 101.4%. Graphical abstract.

Insertion/deletion polymorphism in the 3' untranslated region of COL1A2 disrupts its interaction with microRNA-382 and leads to decreased susceptibility to osteoporotic fracture.

A growing body of evidence has proved that the expression of COL1A2 is associated with a reduced risk of osteoporotic fracture. One single-nucleotide polymorphism (rs3917) located within the 3'-untranslated region of COL1A2 may "alter" binding site of miR-382 and thereby associated with the risk of osteoporotic fracture. Bioinformatic analysis, luciferase reporter assay, site-directed mutagenesis, Western blot and real-time PCR were performed in this study. In this study, we validated COL1A2 as a target of miR-382 in osteoblast. In addition, bone tissue samples were genotyped as wild-type rs3917, heterozygous rs3917, and homozygous rs3917. The expression of miR-382 was comparable between the genotype groups, whereas the expression of COL1A2 mRNA and protein was much higher in heterozygous rs3917 and homozygous rs3917 than the wild-type rs3917 group. Furthermore, we transfected the wild-type rs3917 and heterozygous rs3917 cells with miR-382 mimics or inhibitors and found that the transfection with miR-382 mimics significantly increased the level of the miR-382 in the cells of both genotypes, and the introduction of miR-382 inhibitors substantially suppressed the level of miR-382 in both cells. In wild-type rs3917 cells, transfection of miR-382 mimics and COL1A2 small interfering RNA (siRNA) similarly and substantially downregulated the expression of COL1A2, while in heterozygous rs3917 cells, only COL1A2 siRNA notably reduced the expression of COL1A2, whereas introduction of miR-382 mimics left expression of COL1A2 intact. The findings showed rs3917 polymorphism interfered with the interaction between COL1A2 mRNA and miR-382, and minor allele is associated with a reduced risk of osteoporotic fracture.

Mulberry leaf reduces inflammation and insulin resistance in type 2 diabetic mice by TLRs and insulin Signalling pathway.

BACKGROUND: It has been testified that Diabetes mellitus (DM) has a close association with chronic inflammation and Toll-like Receptors (TLRs), and DM could be prevented by mulberry leaf. Therefore, a hypothesis came into being that mulberry leaf could ameliorate proinflammation and insulin resistance (IR) through TLRs and insulin signalling pathways. METHODS: Water extracts of mulberry leaf (WEM) was given to diabetic mice by gavage for 10 weeks, and the diabetic mice was injected with low-dose streptozocin, fed with high-fat and high-sugar diet. Oral glucose tolerance tests (OGTTs) were conducted. At the same time, homeostasis model assessment of insulin (HOMA-IR) and the level of the inflammatory factor, tumour necrosis factor-α (TNF-α) was measured. The expressions of critical nodes of TLRs and insulin signalling pathway were also examined. RESULTS: WEM contributed to a significant decrease in fasting blood glucose, AUC from the investigation of OGTTs and HOMA-IR. The levels of the inflammatory factor, tumour necrosis factor-α (TNF-α) also declined. Moreover, WEM suppressed the expression of TLR2, myeloid differentiation primary-response protein 88 (MyD88), tumour-necrosis-factor receptor-associated factor 6 (TRAF6), nuclear factor kappa B (NF-κB) in the skeletal muscle. WEM could up-regulate the expression of insulin receptor (InsR) and insulin receptor substrate 1 (IRS1), and down-regulate the phosphorylation of IRS1 in adipose tissue. CONCLUSION: Through this study, a conclusion could be made that WEM mitigates hyperglycemia, IR, and inflammation through the interactions among TLR2 signalling pathway, insulin signalling pathway and TNF-α.

Effect of Osteoking on the osteogenic and adipogenic differentiation potential of rat bone marrow mesenchymal stem cells in vitro.

BACKGROUND: Bone damage is a condition that affects the quality of life of patients. Mesenchymal stem cells (MSCs) are important for bone repair. Osteoking is a natural compound in traditional Chinese Medicine used to treat bone diseases; however, the effect of Osteoking on the differentiation of MSCs has not been reported. In this study, we aimed to investigate the effect of Osteoking on the osteogenic and adipogenic differentiation potential of rat bone marrow mesenchymal stem cells (rbMSCs). METHODS: The effects of Osteoking on the proliferation and differentiation of rbMSCs were investigated. Different concentrations of Osteoking were prepared, and its cytotoxicity was evaluated by CCK-8 assay. The expression of osteogenic and adipogenic genes were determined, and several staining methods were used to reveal the osteogenic and adipogenic differentiation potential of rbMSCs. RESULTS: Our results show that appropriate concentrations of Osteoking can enhance osteogenic differentiation of rbMSCs and reduce adipogenic differentiation without any effect on proliferation. This may be related to the changes in related gene expression. CONCLUSION: Osteoking enhances osteogenic differentiation and inhibits adipogenic differentiation of rbMSCs. Therefore, Osteoking may have a therapeutic potential for treating bone disease caused by changes in differentiation function of MSCs.

Light enhanced room temperature resistive NO2 sensor based on a gold-loaded organic-inorganic hybrid perovskite incorporating tin dioxide.

A material is described for sensing NO2 in the gas phase. It has an architecture of type Au/MASnI3/SnO2 (where MA stands for methylammonium cation) and was fabricated by first synthesizing Au/MASnI3 and then crystallizing SnO2 on the surface by calcination. The physical and NO2 sensing properties of the composite were examined at room temperature without and with UV (365 nm) illumination, and the NO2-sensing mechanism was studied. The characterization demonstrated the formation of a p-n heterojunction structure between p-MASnI3 and n-SnO2. The sensor, best operated at a voltage of 1.1 V at room temperature, displays superior NO2 sensing performance. Figures of merit include (a) high response (Rg/Ra = 240 for 5 ppm NO2; where Rg stands for the resistance of a sensor in test gas, and Ra stands for the resistance of a sensor in air), (b) fast recovery (about 12 s), (c) excellent selectivity compared to sensors based on the use of SnO2 or Au/SnO2 only, both at room temperature under UV illumination; (d) a low detection limit (55 ppb), and (e) a linear response between 0.5 and 10 ppm of NO2. The enhanced sensing performance is mainly attributed to the high light absorption capacity of MASnI3, the easy generation and transfer of photo-induced electrons from MASnI3 to the conduction band of SnO2, and the catalytic effect of gold nanoparticles. Graphical abstract Schematic of the energy band diagrams of the gold-functionalized MASnI3/SnO2 system after equilibrium with UV illumination, by which the enhanced sensing performance for NO2 can be explained.

Efficient Separation of cis- and trans-1,2-Dichloroethene Isomers by Adaptive Biphen[3]arene Crystals.

Reported here is the highly efficient separation of industrially important cis- and trans-1,2-dichloroethene (cis-DCE and trans-DCE) isomers by activated crystalline 2,2',4,4'-tetramethoxyl biphen[3]arene (MeBP3) materials, MeBP3α. MeBP3 can be synthesized in excellent yield (99 %), and a cyclic pentamer is also obtained when using 1,2-dichloroethane as the solvent. The structure of MeBP3 in the CH3 CN@MeBP3 crystal displays a triangle-shape topology, forming 1D channels through window-to-window packing. Desolvated crystalline MeBP3 materials, MeBP3α, preferentially adsorb cis-DCE vapors over its trans isomer. MeBP3α is able to separate cis-DCE from a 50:50 (v/v) cis/trans-isomer mixture, yielding cis-DCE with a purity of 96.4 % in a single adsorption cycle. Single-crystal structures and powder X-ray diffraction patterns indicate that the uptake of cis-DCE triggers a solid-state structural transformation of MeBP3, suggesting the adaptivity of MeBP3α materials during the sorption process. Moreover, the separation can be performed over multiple cycles without loss of separation selectivity and capacity.

Unidirectional Droplet Transport on the Biofabricated Butterfly Wing.

Water droplet unidirectional transport on the asymmetric superhydrophobic surface has attracted much interest in theory analysis and applications, such as self-cleaning, antifogging, anti-icing, heat transfer, and so on. Different from the symmetrical performance on the uniform topographies, the droplets acting on the asymmetric surface exhibit an anisotropic state and easily roll off the surface along the special direction. This phenomenon is indicated by natural butterfly wings. The flexible asymmetrically arranged microstep induces the droplet to release along the outside radial (RO) direction and to pin against the RO direction. Here, inspired by butterfly wings, a kind of surface for superhydrophobic and unidirectional droplet transport is achieved by integrating the methods of soft lithography and enhanced crystal growth. The water droplet shows the anisotropic state on the biofabricated surface, and it rolls off easily along the step direction. The droplet is unidirectionally driven off the surface by the asymmetric surface tension force generated by the microstep topography. This experiment is significant for designing self-cleaning surfaces.