Triple-Emission Single Sensing Element-Enabled Ratiometric Fluorescent Array Identification of Multiple Antibiotics.

Given that intricate toxicological profiles exist among different antibiotics and pose serious threats to the environment and human health, synchronous analysis of multiple residues becomes crucial. Sensor arrays show potential to achieve the above purpose, but it is challenging to develop easy-to-use and high-sensitivity tools because the state-of-the-art arrays often require more than one recognition unit and are monosignal dependent. Here we exquisitely designed a fluorescent nanoprobe (2-aminoterephthalic acid-anchored CdTe quantum dots with Eu3+ coordination, CdTe-ATPA-Eu3+) featuring triple emissions at the same excitation as the only element to fabricate a luminescent sensor array with ratiometric calculations for identifying multiple antibiotics. By taking tetracycline, chlortetracycline, doxycycline, oxytetracycline, penicillin G, and sulfamethoxazole as models, the six species exhibited distinguishable motivation or/and quenching impacts on the three emissions of CdTe-ATPA-Eu3+, which were employed as indicators to perform the ratiometric logical operation and further combined with pattern recognition analysis for multitarget determination. Evidently, such a design exhibits two advances: (1) with the triple-emission probe as the sole receptor requiring neither internal nor external adjustments, the fabricated array acts as an extremely facile tool for multianalyte detection; (2) the ratiometric calculations offer excellent sensitivity and reliability for high-performance determination. Consequently, accurate identification and quantification of individual antibiotics and their combinations at various levels were verified in both laboratory and practical matrices. Our work provides a new tool for simultaneously detecting multiple antibiotics, and it will inspire the development of advanced sensor arrays for multitarget analysis.

MnOx In Situ Growth-Induced Luminescence and Oxidase-Like Feature Bimodulation of CePO4:Tb Nanorods: Toward Ascorbic Acid-Related Bioanalysis in a "One-Stone-Two-Birds" Manner.

Nanozyme-based multimode detection is a useful means to improve the accuracy and stability of analytical methods. However, both multifunctional nanozymes and related multimodal sensing strategies are still very scarce. Besides, they require complex processes to fabricate and operate. To fill this gap, here we propose a spontaneous interfacial in situ growth strategy to prepare a new bifunctional material (CePO4:Tb@MnOx) featuring good oxidase-like activity and green photoluminescence for the dual-mode colorimetric/luminescence determination of ascorbic acid (AA)-related biomarkers specifically. CePO4:Tb@MnOx was gained through the controllable redox reaction between KMnO4 and CePO4:Tb nanorods. It was interestingly found that MnOx in situ growth not only significantly enhanced the enzyme-like activity but also could reversibly regulate the luminescence of CePO4:Tb via a dual quenching mechanism. More interestingly, CePO4:Tb@MnOx exhibited a distinctive response toward AA against other reducing species. A double-coordination regulation mechanism was further verified to clarify the catalytic activity and luminescence switching behaviors in CePO4:Tb@MnOx. Based on these findings, a dual-mode colorimetric/luminescence approach was established for AA sensing in a "one-stone-two-birds" manner, providing excellent selectivity, sensitivity, and practicability. Furthermore, the determination of AA-related biomarkers, including acid phosphatase activity and organophosphorus residue, was also validated by the sensing principle. Our work not only deepens the understanding of the coordinated regulation of the luminescence and enzyme-like features in lanthanide-based materials but also offers a novel way to design and develop multifunctional nanozymes for advanced bioanalytical applications.

Multifunctional light-controllable nanozyme enabled bimodal fluorometric/colorimetric sensing of mercury ions at ambient pH.

Nanomaterials with enzyme-like catalytic features (nanozymes) find wide use in analytical sensing. Apart from catalytic characteristics, some other interesting functions coexist in the materials. How to combine these properties to design multifunctional nanozymes for new sensing strategy development is challenging. Besides, in nanozymes it is still a challenge to conveniently control the catalytic process, which also hinders their further applications in advanced biochemical analysis. To remove the above barriers, here we design a light-controllable multifunctional nanozyme, namely manganese-inserted cadmium telluride (Mn-CdTe) particles, that integrates oxidase-like activity with luminescence together, to achieve the fluorometric/colorimetric dual-mode detection of toxic mercury ions (Hg2+) at ambient pH. The Mn-CdTe exhibits a light-triggered oxidase-mimicking catalytic behavior to induce chromogenic reactions, thus enabling one to start or stop the catalytic progress easily via applying or withdrawing light irradiation. Meanwhile, the quantum dot material can exhibit bright photoluminescence, which provides the fluorometric channel to sense targets. When Hg2+ is introduced, it rapidly leans toward Mn-CdTe through electrostatic interaction and Te-Hg bonding and induces the aggregation of the latter. As a result, the luminescence of Mn-CdTe is dynamically quenched, and the masking of active sites in aggregated Mn-CdTe leads to the decrease of light-initiated oxidase-mimetic activity. According to this principle, a new fluorometric/colorimetric bimodal method was established for Hg2+ determination with excellent performance. A 3D-printed portable platform combining paper-based test strips and an App-equipped smartphone was further fabricated, making it possible to achieve in-field sensing of the analyte in various matrices.

Alkali-Etched Imprinted Mn-Based Prussian Blue Analogues with Superior Oxidase-Mimetic Activity and Precise Recognition for Tetracycline Colorimetric Sensing.

As a typical antibiotic pollutant, tetracycline (TC) is producing increasing threats to the ecosystem and human health, and exploring convenient means for monitoring of TC is needed. Here, we proposed alkali-etched imprinted Mn-based Prussian blue analogues featuring superior oxidase-mimetic activity and precise recognition for the colorimetric sensing of TC. Simply etching Mn-based Prussian blue analogues (Mn-PBAs) with NaOH could expose the sites and surfaces to significantly improve their catalytic activity. Density functional theory calculations were employed to screen the molecularly imprinted polymer (MIP) layer for target identification. Consequently, the designed Mn-PBANaOH@MIP possessed the rich channels for substrates to get in touch with the active Mn-PBANaOH core, showing an excellent catalytic capacity to trigger the chromogenic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) without the use of H2O2. If TC was introduced, it would be recognized selectively by the MIP shell and masked the channels for TMB access, resulting in the obstruction of the chromogenic reaction. According to this mechanism, selective optical detection of TC was achieved, and performance stability, reusability, and reliability as well as practicability were also verified, promising potential for TC monitoring in complex matrices. Our work not only presents an effective way to enhance the enzyme-like activity of Prussian blue analogues but also provides a facile approach for TC sensing. Additionally, the work will inspire the exploration of molecularly imprinted nanozymes for various applications.

Amorphous Fe-Containing Phosphotungstates Featuring Efficient Peroxidase-like Activity at Neutral pH: Toward Portable Swabs for Pesticide Detection with Tandem Catalytic Amplification.

Peroxidase-mimetic materials are intensively applied to establish multienzyme systems because of their attractive merits. However, almost all of the nanozymes explored exhibit catalytic capacity only under acidic conditions. The pH mismatch between peroxidase mimics in acidic environments and bioenzymes under neutral conditions significantly restricts the development of enzyme-nanozyme catalytic systems especially for biochemical sensing. To solve this problem, here amorphous Fe-containing phosphotungstates (Fe-PTs) featuring high peroxidase activity at neutral pH were explored to fabricate portable multienzyme biosensors for pesticide detection. The strong attraction of negatively charged Fe-PTs to positively charged substrates as well as the accelerated regeneration of Fe2+ by the Fe/W bimetallic redox couples was demonstrated to play important roles in endowing the material with peroxidase-like activity in physiological environments. Consequently, integrating the developed Fe-PTs with acetylcholinesterase and choline oxidase led to an enzyme-nanozyme tandem platform with good catalytic efficiency at neutral pH for organophosphorus pesticide response. Furthermore, they were immobilized onto common medical swabs to fabricate portable sensors for paraoxon detection conveniently based on smartphone sensing, showing excellent sensitivity, good anti-interference capacity, and low detection limit (0.28 ng/mL). Our contribution expands the horizon of acquiring peroxidase activity at neutral pH, and it will also open avenues to construct portable and effective biosensors for pesticides and other analytes.

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.

Smartphone-assisted bioenzyme-nanozyme-chromogen all-in-one test strip with enhanced cascade signal amplification for convenient paraoxon sensing.

Monitoring of pesticide residues in food and environmental matrices is undoubtedly crucial to guarantee food safety and ecological health, yet how to realize their sensitive and convenient detection is still challenging. Herein, we propose an all-in-one test strip that elaborately integrates bioenzyme, nanozyme and chromogen together, and achieve the highly sensitive and convenient sensing of pesticide residues assisted by a smartphone. A sequential self-assembly strategy was first explored to acquire an integrative bioenzyme-nanozyme-chromogen assembly, and then the assembly was confined in a biocompatible hydrogel to construct the test strip. Thanks to both the proximity and confinement effects, a ∼1.2-fold improvement of the cascade catalytic efficiency was gained to benefit high-sensitivity detection. More importantly, since all the sensing elements, including target recognition units and signal amplification modules, were rationally integrated in the test strip, detection operation was significantly simplified, making it possible for in-field rapid analysis. Besides, the microenvironment provided by the alginate hydrogel carrier endowed the test strip with an excellent sensing stability. By taking paraoxon as a typical pesticide, high-performance detection of the target was accomplished via the smartphone-assisted all-in-one test strip. Moreover, the test strip was successfully applied for paraoxon detection in various real samples and exhibited good correlations with commercial kits, demonstrating its great prospect for practical applications. Our work not only offers a new tool for the high-sensitivity and convenient monitoring of pesticide residues, but will also inspire the development of efficient multi-enzyme sensing platforms.

Nanozymes with Multiple Activities: Prospects in Analytical Sensing.

Given the superiorities in catalytic stability, production cost and performance tunability over natural bio-enzymes, artificial nanomaterials featuring enzyme-like characteristics (nanozymes) have drawn extensive attention from the academic community in the past decade. With these merits, they are intensively tested for sensing, biomedicine and environmental engineering. Especially in the analytical sensing field, enzyme mimics have found wide use for biochemical detection, environmental monitoring and food analysis. More fascinatingly, rational design enables one fabrication of enzyme-like materials with versatile activities, which show great promise for further advancement of the nanozyme-involved biochemical sensing field. To understand the progress in such an exciting field, here we offer a review of nanozymes with multiple catalytic activities and their analytical application prospects. The main types of enzyme-mimetic activities are first introduced, followed by a summary of current strategies that can be employed to design multi-activity nanozymes. In particular, typical materials with at least two enzyme-like activities are reviewed. Finally, opportunities for multi-activity nanozymes applied in the sensing field are discussed, and potential challenges are also presented, to better guide the development of analytical methods and sensors using nanozymes with different catalytic features.

Nanozyme-Participated Biosensing of Pesticides and Cholinesterases: A Critical Review.

To improve the output and quality of agricultural products, pesticides are globally utilized as an efficient tool to protect crops from insects. However, given that most pesticides used are difficult to decompose, they inevitably remain in agricultural products and are further enriched into food chains and ecosystems, posing great threats to human health and the environment. Thus, developing efficient methods and tools to monitor pesticide residues and related biomarkers (acetylcholinesterase and butylcholinesterase) became quite significant. With the advantages of excellent stability, tailorable catalytic performance, low cost, and easy mass production, nanomaterials with enzyme-like properties (nanozymes) are extensively utilized in fields ranging from biomedicine to environmental remediation. Especially, with the catalytic nature to offer amplified signals for highly sensitive detection, nanozymes were finding potential applications in the sensing of various analytes, including pesticides and their biomarkers. To highlight the progress in this field, here the sensing principles of pesticides and cholinesterases based on nanozyme catalysis are definitively summarized, and emerging detection methods and technologies with the participation of nanozymes are critically discussed. Importantly, typical examples are introduced to reveal the promising use of nanozymes. Also, some challenges in the field and future trends are proposed, with the hope of inspiring more efforts to advance nanozyme-involved sensors for pesticides and cholinesterases.