Nature-Derived Hollow Micron-Tubular Signal Tracers Conquering the Size Limitations for Multimodal Immunochromatographic Detection of Antibiotics.

Developing signal tracers (STAs) with large size, multifunctionality, and high retention bioaffinity is believed to be a potential solution for achieving high-performance immunochromatographic assays (ICAs). However, the size limitations of STAs on strips are always a challenge because of the serious steric hindrance. Here, based on metal-quinone coordination and further metal etching, hollow micron-tubular STAs formed by natural alizarin and Fe3+ ions (named ALIFe) are produced to break through size limitations, provide more active sites, and achieve three-mode ICAs (ALIFe STAs-ICAs). Thanks to the special tubular morphology, ALIFe can successfully pass through the strip and provide an ideal signal intensity within 7 min at low mAb and probe dosages to achieve stable ICA analysis. Importantly, ALIFe shows excellent antibody enrichment and bioaffinity retention capability. With a proof-of-concept for streptomycin, the ALIFe STAs-ICAs showed the limit of detection (LOD) at 0.39 ng mL-1 for colorimetric mode, 0.32 ng mL-1 for catalytic mode, and 0.016 ng mL-1 for photothermal mode with total recoveries ranging from 80.46 to 121.59% in mike and honey samples. We anticipate that our study will help expand the ideas for the design of high-performance STAs with large size and broaden the practical application of ICA.

Engineered Collaborative Size Regulation and Shape Engineering of Tremella-Like Au-MnOx for Highly Sensitive Bimodal-Type Lateral Flow Immunoassays.

Engineered collaborative size regulation and shape engineering of multi-functional nanomaterials (NPs) offer extraordinary opportunities for improving the analysis performance. It is anticipated to address the difficulty in distinguishing color changes caused by subtle variations in target concentrations, thereby facilitating the highly sensitive analysis of lateral flow immunoassays (LFIAs). Herein, tremella-like gold-manganese oxide (Au-MnOx ) nanoparticles with precise MnCl2 regulation are synthesized as immuno signal tracers via a facile one-step redox reaction in alkaline condition at ambient temperature. Avail of the tunable elemental composition and anisotropy in morphology, black-colored tremella-like Au-MnOx exhibits superb colorimetric signal brightness, enhanced antibody coupling efficiency, marvelous photothermal performance, and unrestricted immunological recognition affinity, all of which facilitate highly sensitive multi-signal transduction patterns. In conjunction with the handheld thermal reader device, a bimodal-type LFIA that combines size-regulation- and shape-engineering-mediated colorimetric-photothermal dual-response assay (coined as the SSCPD assay) with a limit of detection of 0.012 ng mL-1 for ractopamine (RAC) monitoring is achieved by integrating Au-MnOx with the competitive-type immunoreaction. This work illustrates the effectiveness of this strategy for establishing high-performance sensing, and the SSCPD assay may be extended to a wide spectrum of future point-of-care (POC) diagnostic applications.

Integrated Design of a Dual-Mode Colorimetric Sensor Driven by Enzyme-like Activity Regulation Strategy for Ultratrace and Portable Detection of Hg2.

Colorimetric analysis for mercury detection has great application potential in the prevention of health damage caused by mercury in the environment. Sensitivity, selectivity, and portability are core competencies of sensors, and concentrating these properties in a single sensor for efficient mercury detection remains a great challenge. Herein, a hollow structure CuS@CuSe@PVP (CCP) was prepared in which the enzyme-like activities could be activated by Hg2+ due to the antagonism between Hg and Se, inspiring the establishment of a colorimetric method for Hg2+ detection. As for Hg2+ detection performance, the linear range (LR) and limit of detection (LOD) were 1-900 and 0.81 nM in the POD-like activity system, respectively. Also, 5-550 nM of LR and 2.34 nM of LOD were achieved in the OD-like activity system. Further, a smartphone-mediated portable RGB nanosensor was fabricated, with a LOD down to 6.65 nM in the POD-like system and 7.97 nM in the OD-like system. Moreover, the excellent self-calibration and satisfactory recovery of 94.77%-106.16% were shown in the application of real water samples analysis. This study represented advanced progress toward emerging applications of nanozymes with multiple enzyme-like activities in heavy metal detection and will accelerate the development of efficient and portable heavy metal sensors.

pH-responsive dual-enzyme mimics based on hollow metal organic framework-derivatives ß-Co(OH)2 for multiple colorimetric assays.

A hollow metal organic framework derivative ß-Co(OH)2 has been prepared, which possesses oxidase and peroxidase-like activities. Oxidase-like activity is derived from the generation of free radicals, and peroxidase-like activity is related to the electron transfer process. Unlike other nanozymes with dual enzyme-like activities, ß-Co(OH)2 possesses pH-responsive enzyme-like activities, among which the ß-Co(OH)2 exhibits superior oxidase and peroxidase-like activities under pH of 4 and 6, respectively, which could avoid mutual interference between multiple enzymes. Based on the phenomenon that enzyme-like activities of ß-Co(OH)2 can catalyze colorless TMB to generate blue oxidized TMB (oxTMB) with absorption peak at 652 nm, the sensors integrating total antioxidant capacity and H2O2 quantification were developed. The oxidase-like activity-based colorimetric system has a sensitive response to ascorbic acid, Trolox, and gallic acid, in which the limit of detection for those antioxidant substances was 0.54 µM, 1.26 µM, and 14.34 µM, respectively. The sensors based on peroxidase-like activity had low limit of detection of 1.42 µM for H2O2 and a linear range of 5-1000 µM. The proposed method can be well applied to the detection of the total antioxidant capacity of kiwi, Vc tables, orange and tea extract with high accuracy, and H2O2 determination in milk and glucose detection in beverages with satisfactory recovery (within 97-106%).

Portable Colorimetric Detection of Mercury(II) Based on a Non-Noble Metal Nanozyme with Tunable Activity.

The nanozyme-based strategy is currently one of the frontiers in the detection of toxic heavy metal ions. However, the utilization of noble metal free nanozymes to construct an economically and environmentally sustainable methodology remains largely unknown. Here, chitosan-functionalized molybdenum(IV) selenide nanosheets (CS-MoSe2 NS), greenly synthesized by an ionic liquid-assisted grinding method, were exploited for the colorimetric sensing of mercury ions (Hg2+). The sensing principle was based on the activating effect of Hg2+ on CS-MoSe2 NS nanozyme activities, triggered by the in situ reduction of chitosan-captured Hg2+ ions on a MoSe2 NS surface. Using 3,3',5,5'-tetramethylbenzidine (TMB) as a colorimetric indicator, the concentrations of activator-like Hg2+ ions could be quantitatively and selectively monitored, reaching a limit of detection of 3.5 nM with the ultraviolet-visible spectrophotometer. In addition, the integration system of CS-MoSe2 NS with a smartphone achieved a portable detection limit as low as 8.4 nM Hg2+ within 15 min and showed high specificity and anti-interfering ability over other ions and great practicability in real water and serum samples. The eco-friendly properties of such sensing system were also confirmed. This work emphasizes the rational portable assembly of biocompatible nanozymes like CS-MoSe2 NS for the field detection of Hg2+ in food, biological, and environmental samples.

Mixed-Valence Ce-BPyDC Metal-Organic Framework with Dual Enzyme-like Activities for Colorimetric Biosensing.

Enzyme-like metal-organic frameworks (MOFs) are currently one type of starring material in the fields of artificial enzymes and analytical sensing. However, there has been little progress in making use of the MOF structures based on the catalytically active metal center with multiple valences. Herein, we report a mixed-valence Ce-MOF (Ce-BPyDC) that can exhibit both oxidase-like and peroxidase-like activities. Ce-BPyDC was synthesized by a facile hydrothermal method, which preserves the rare coexistence of Ce(III) and Ce(IV) in the MOF structure. The enzymatic studies demonstrated the enzyme-like activities of Ce-BPyDC follow the Michaelis-Menten kinetics and are strongly dependent on temperature, pH, and reaction time. Ce-BPyDC was also revealed to exert high catalytic activity that could transcend horseradish peroxidase and other MOF nanozymes, due to the redox-active Ce(III)/Ce(IV) cycles inside. Furthermore, the simple synthesis, high nanozyme activity, and great stability of Ce-BPyDC motivated us to establish a colorimetric biosensing platform using 3,3',5,5'-tetramethylbenzidine as a color reagent. Adopting this strategy, we established a visual, sensitive, and selective colorimetric method for ascorbic acid (AA) detection, for which the linear interval and limit of detection were 1-20 and 0.28 µM, respectively. The successful AA detection in real juice samples implies the promising use of such mixed-valence MOF nanozymes in food and biomedical samples.

Metal-phenolic networks derived CN-FeC hollow nanozyme with robust peroxidase-like activity for total antioxidant capacity detection.

A tannate-iron network-derived peroxidase-like catalyst loaded with Fe ions on carbon nitride (C3N4) was reported for detection of total antioxidant capacity (TAC) in food in this study. Metal-phenolic networks (MPNs) was employed to form a low coordination compound on C3N4, and calcined catalyst formed hollow structure with abundant and uniform Fe sites and surface folds. CN-FeC exhibited significant peroxidase-like activity and high substrate affinity. The homogeneous distribution of amorphous Fe elements on the C3N4 substrate provides more active sites, resulting in provided excellent catalytic activity to activate H2O2 to ·OH, 1O2 and O2·-. The established CN-FeC/TMB/H2O2 colorimetric system can detect AA in the concentration range of 5-40 µM, with the detection limits of 1.40 µM, respectively. It has good accuracy for the detection of vitamin C tablets, beverages. Taken together, this work shows that metal-phenolic networks can be an effective way to achieve efficient utilization of metal atoms and provides a promising idea for metal-phenolic networks in nanoparticle enzyme performance enhancement.

A highly sensitive dual-mode lateral flow immunoassay based on plasmonic hollow Ag/Au nanostars enhancing light absorption.

The conventional lateral flow immunoassay (LFIA) based on gold nanoparticles (Au NPs) is limited by low sensitivity due to the insufficient brightness of Au NPs. To address this problem, noble metal nanomaterials with localized surface plasmon resonance (LSPR) and synthetic tunability are potential signal outputs for LFIA, which can achieve better optical properties by adjusting the preparation conditions. Herein, this study prepared the hollow silver/gold nano-stars (HAg/Au NSts) as LFIA signal output via the galvanic replacement method. HAg/Au NSts with anisotropic hollow alloy nanostructures exhibit a wide visible light absorption band and great NIR thermal conversion efficiency (η = 37.32 %), which endows them with enhanced colorimetric and photothermal signals. Further, we constructed a colorimetric-photothermal (CM-PT) dual-signal HAg/Au NSts-LFIA and chose staphylococcal enterotoxin B as the target analyte. The linear range of HAg/Au NSts-LFIA is 0.19-100 ng mL-1, and the limit of detection (LOD) is up to 0.29 ng mL-1 and 0.09 ng mL-1 in the colorimetric and photothermal modes respectively. Compared with the conventional Au NPs-LFIA, HAg/Au NSts-CM/PT-LFIA effectively improved the detection performance of LFIA. In addition, HAg/Au NSts-LFIA also showed satisfactory sensitivity (vLOD = 0.78 ng mL-1) and recovery (89.06-114.74 %) in milk and pork samples. Therefore, this work provides a new shape design idea for noble metal nanomaterials in biosensor applications.

Fortified Dual-Spectral Overlap with Enhanced Colorimetric/Fluorescence Dual-Response Immunochromatography for On-Site Bimodal-Type Gentamicin Monitoring.

Immunochromatography (ICA) remains untapped toward enhanced sensitivity and applicability for fulfilling the nuts and bolts of on-site food safety surveillance. Herein, we report a fortified dual-spectral overlap with enhanced colorimetric/fluorescence dual-response ICA for on-site bimodal-type gentamicin (Gen) monitoring by employing polydopamine (PDA)-coated AuNPs (APDA) simultaneously serving as a colorimetric reporter and a fluorescence quencher. Availing of the enhanced colorimetric response that originated from the PDA layer, the resultant APDA exhibits less required antibody and immunoprobes in a single immunoassay, which facilitates improved antibody utilization efficiency and immuno-recognition in APDA-ICA. Further integrated with the advantageous features of fortified excitation and emission dual-spectral overlap for the Arg/ATT-AuNCs, this APDA-ICA with a "turn on/off" pattern achieves the visual limits of detection of 1.0 and 0.5 ng mL-1 for colorimetric and fluorescence patterns (25- and 50-fold lower than standard AuNPs-ICA). Moreover, the excellent self-calibration and satisfactory recovery of 79.03-118.04% were shown in the on-site visual colorimetric-fluorescence analysis for Gen in real environmental media (including real river water, an urban aquaculture water body, an aquatic product, and an animal byproduct). This work provides the feasibility of exploiting fortified dual-spectral overlap with an enhanced colorimetric/fluorescence dual response for safeguarding food safety and public health.

Thermal-Driven Curcumin Release Film with Dual-Mode Synergistic Antibacterial Behavior for Efficient Tangerine Preservation.

Antimicrobial packing showed great potential in extending the shelf life of food. However, developing a new biocomposite film with an intelligent and efficient antimicrobial performance is still desirable. Herein, a Fe-MoOx encapsulated with curcumin (Cur) filled chitosan-based composite film (CCF films) was prepared by solvent casting method. The total color differences of the CCF films were less than 30%, and satisfactory surface color, transparency, hydrophobicity, and thermal stability were also obtained. Besides, the UV-light/water/oxygen barrier capability and mechanical properties were enhanced with the incorporation of Cur@Fe-MoOx. Moreover, CCF films showed photothermal performance and thermal-controlled curcumin release ability, which endowed the CCF0.15 film with excellent antibacterial capability toward E. coli (≥99.95%) and S. aureus (≥99.96%) due to the synergistic antibacterial effect. Fe-MoOx exhibited high cell viability and less than 5% hemolysis even under the concentration of 500 µg mL-1. Based on those unique characteristics, the CCF0.15 film was chosen for tangerine preservation. The CCF0.15 film could prolong the shelf life of tangerine by at least 9 days compared with the unpacking group, and the tangerines could maintain the freshness characteristics over a 24 day storage period. Such thermal-mediated antibacterial film proposed by our work showed promising potential in food packaging.

Transition Metal High-Entropy Nanozyme: Multi-Site Orbital Coupling Modulated High-Efficiency Peroxidase Mimics.

Strong substrate affinity and high catalytic efficiency are persistently pursued to generate high-performance nanozymes. Herein, with unique surface atomic configurations and distinct d-orbital coupling features of different metal components, a class of highly efficient MnFeCoNiCu transition metal high-entropy nanozymes (HEzymes) is prepared for the first time. Density functional theory calculations demonstrate that improved d-orbital coupling between different metals increases the electron density near the Fermi energy level (EF ) and shifts the position of the overall d-band center with respect to EF , thereby boosting the efficiency of site-to-site electron transfer while also enhancing the adsorption of oxygen intermediates during catalysis. As such, the proposed HEzymes exhibit superior substrate affinities and catalytic efficiencies comparable to that of natural horseradish peroxidase (HRP). Finally, HEzymes with superb peroxidase (POD)-like activity are used in biosensing and antibacterial applications. These results suggest that HEzymes have great potential as new-generation nanozymes.

Rational construction of a robust metal-organic framework nanozyme with dual-metal active sites for colorimetric detection of organophosphorus pesticides.

While nanomaterials with enzyme-mimicking activities are emerging as promising candidates in the colorimetric detection of organophosphorus pesticides (OPs), the catalytic activities and recognition ability to analyte of most nanozymes are inherently deficient. In this work, we introduced manganese ions into a typical iron based MOF (Fe-MIL(53)) via a one-pot hydrothermal reaction strategy, which brought out a catalytically favorable bimetallic Mn/Fe-MIL(53) MOF nanozyme. The catalytic performance of Mn/Fe-MIL(53) is superior to that of pure Fe-MIL (53) and the mechanism for superior catalytic activity of material is revealed by active species scavenging experiments and X-ray photoelectron spectroscopy (XPS). Besides, the introduction of manganese endows the material with the characteristic of being specially destroyed by choline, which motivates the establishment of a simple, selective and sensitive colorimetric strategy for OPs detection. The proposed colorimetric strategy could quantify the methyl parathion and chlorpyrifos in the concentration range of 10-120 nM and 5-50 nM, respectively. The low detection limit of 2.8 nM for methyl parathion and 0.95 nM (3 S/N) for chlorpyrifos were achieved. Good recoveries were obtained when applied in the real sample detection. Our work paves the way to boost catalytic performance of MOF nanozymes, which will be useful in biosensing.

Dextran-stabilized Fe-Mn bimetallic oxidase-like nanozyme for total antioxidant capacity assay of fruit and vegetable food.

The total antioxidant capacity (TAC) has become increasingly vital for evaluating antioxidant food quality in the field of healthcare. Herein, a convenient and sensitive method for TAC assay was proposed based on the absorbance difference of reaction systems between various antioxidants existed in food and Dex-FeMnzyme/oxTMB. Under the optimum condition, the limit of detection (LOD) of the colorimetric sensor was 1.17 µM with the linear concentration range from 1 µM to 30 µM. The analysis results demonstrated the excellent feasibility of practical application in fruit and vegetable food, which offered a new avenue for the establishment of colorimetric biosensors.

A portable dual-mode colorimetric platform for sensitive detection of Hg2+ based on NiSe2 with Hg2+-Activated oxidase-like activity.

The nanozyme-based colorimetric strategy for heavy metal detection has broad application prospects nowadays. However, the inefficient recognition capabilities of nanozyme sensors for targets hinder its further application. Herein, the authors synthesize bare nickel selenide (NiSe2) via a one-step hydrothermal reaction, in which the Se element possesses a strong binding ability with mercury (Hg). As expected, NiSe2 exhibits oxidase-like activity in the presence of Hg2+, that is, Hg2+ can enhance the oxidase-like activity of NiSe2. The enhanced mechanism is the accelerated electron transfer between NiSe2-Hg2+ and substrate caused by the formation of Hg-Se bonds. Besides, the oxidase-like activity of NiSe2 exhibits excellent selectivity, sensitivity and stability in response to Hg2+, which enables NiSe2-Hg2+ to efficiently oxidize colorless TMB to blue TMB even in harsh environments. Based on this, a dual-mode colorimetric sensor integrating solution reaction and test paper is developed for the detection of Hg2+. In the Hg2+ concentration range of 10-700 nM, the colorimetric platform presents a liner response to Hg2+, which can reach a low LOD of 5.18 nM in solution reaction and 8.42 nM in the test paper. The proposed strategy can also be applied to real water samples with good recovery and excellent self-calibration capability.

Lycium Barbarum Polysaccharide-Iron (III) Chelate as Peroxidase Mimics for Total Antioxidant Capacity Assay of Fruit and Vegetable Food.

Quantitative evaluation of the antioxidant capacity of foods is of great significance for estimating food's nutritional value and preventing oxidative changes in food. Herein, we demonstrated an easy and selective colorimetric method for the total antioxidant capacity (TAC) assay based on 3,3',5,5'-tetramethyl-benzidine (TMB), hydrogen peroxide (H2O2) and synthetic Lycium barbarum polysaccharide-iron (III) chelate (LBPIC) with high peroxidase (POD)-like activity. The results of steady-state kinetics study showed that the Km values of LBPIC toward H2O2 and TMB were 5.54 mM and 0.16 mM, respectively. The detection parameters were optimized, and the linear interval and limit of detection (LOD) were determined to be 2-100 µM and 1.51 µM, respectively. Additionally, a subsequent study of the determination of TAC in six commercial fruit and vegetable beverages using the established method was successfully carried out. The results implied an expanded application of polysaccharide-iron (III) chelates with enzymatic activity in food antioxidant analysis and other biosensing fields.

Ultrasensitive label-free immunochromatographic strip sensor for Salmonella determination based on salt-induced aggregated gold nanoparticles.

Here we present an innovative label-free immunochromatographic strip (ICTS) sensor, in which salt-induced aggregated gold nanoparticles (SIA-AuNPs) act as the signal probe, allowing in 14 min the identification and sensitive quantification of Salmonella as model targets. It has been evidenced that SIA-AuNPs could be absorbed on the surface of bacteria based on van der Waals forces. The SIA-AuNPs@Salmonella complex was captured by anti-Salmonella polyclonal antibody deposited on the test zone. With the label-free ICTS sensor, we successfully detected Salmonella in a concentration range of 103-108 CFU/mL and a visual detection limit of 1 × 103 CFU/mL. The band of test zone could be distinguished at a concentration of 103 CFU/mL by naked eye, which is 100-fold lower than the cationic AuNPs based method. The strip sensor was further validated with real samples including cabbage and drinking water with excellent precision and showed to provide excellent recovery.

Natural Products Self-Assembled Nanozyme for Cascade Detection of Glucose and Bacterial Viability in Food.

Sugar content and bacterial contamination levels are important indicators for the health and safety of food, respectively. Therefore, it is important to construct a method that can detect both glucose and bacterial activity. Herein, natural compounds (gallic acid and glucose oxidase) were assembled into nanozyme (GOx@GA-Fe (ii)) for mild cascade detection. The nanozyme catalyzes glucose to produce hydrogen peroxide, which is then converted to ·OH and oxidized colorless TMB from blue oxidized TMB. Under the optimal conditions, the method has a good linear relationship in the glucose concentration range of 1-500 µM (R2 = 0.993) with minimum detection concentration of 0.43 µM. Based on the glucose consumption of bacteria metabolism, the cascade reaction was then applied to detect the viability of 5 common bacteria. As such, a cascade method based on a natural self-assembled nanozyme was fabricated to monitor the quality of food.