Zeolitic imidazolate framework-encapsulated zinc porphyrin photoresponsive nanozyme for colorimetric/fluorescent dual-mode sensing of glyphosate.

A novel zeolitic imidazolate framework-encapsulated zinc porphyrin (ZnTCPP@ZIF-90) photoresponsive nanozyme is proposed for the colorimetric/fluorescent dual-mode visual sensing of glyphosate (Gly). ZnTCPP@ZIF-90 exhibits photoresponsive oxidase-like activity and fluorescence quenching behavior. Meanwhile, the outer ZIF-90 layer can be selectively destroyed by Gly, causing the release of free ZnTCPP, resulting in the enhanced enzyme-like activity as well as fluorescence emission. The constructed ZnTCPP@ZIF-90 was successfully used for the colorimetric/fluorescent dual-mode detection of Gly. Additionally, the colorimetric and fluorescent images information captured by the smartphone were converted to color intensity (HSV/RGB values), with limits of detection of 0.27 µg/mL and 0.19 µg/mL, respectively. The proposed dual-mode sensor exhibits excellent selectivity and reliability for detecting Gly, and can be successfully applied to the analysis of real samples such as tap water, lake water, and fruit washing water. The current research efforts are expected to provide new perspectives for designing highly active photoresponsive nanozymes and their stimuli-responsive sensing systems, paving the way for their applications in portable dual-mode chemical sensing and environmental monitoring.

Zinc porphyrin/MXene hybrids with phosphate-induced stimuli-responsive behavior for dual-mode fluorescent/electrochemiluminescent ratiometric biosensing.

Highly sensitive ratiometric biosensors have attracted much attention in biomarker detection, but most rely on single-mode signals, which can affect accuracy. The development of new principles and methods for dual-mode ratiometric sensing can enhance detection accuracy. Herein, the zinc(II) meso-tetra(4-carboxyphenyl) porphyrin/MXene (ZnTCPP/Ti3C2Tx) hybrids with phosphate-induced stimuli-responsive behavior are used to develop a novel dual-mode fluorescent/electrochemiluminescent (FL/ECL) ratiometric biosensor. The composites exhibit FL quenching and enhanced ECL behavior involving dissolved O2. The FL quenching of ZnTCPP/Ti3C2Tx is caused by energy transfer (EnT) and photo-induced electron transfer (PET) from ZnTCPP to Ti3C2Tx. While the introduction of MXene compensates for the inadequate conductivity of ZnTCPP, facilitating electron transfer, which further makes the surface ZnTCPP more capable of activating O2 to produce singlet oxygen (1O2), thereby generating enhanced cathodic ECL. Furthermore, phosphate ions (PO43-) can interact with the Ti sites of ZnTCPP/Ti3C2Tx, leading to competition for coordination with ZnTCPP, which in turn detaches ZnTCPP, resulting in enhanced FL and reduced ECL. On the basis of the phosphate-induced stimuli-responsive behavior, the dual-mode FL/ECL ratiometric biosensing of alkaline phosphatase (ALP) is achieved through ALP-catalyzed production of PO43- cascade effect with ZnTCPP/Ti3C2Tx. The linear detection range for ALP is 0.1-50 mU/mL, with a detection limit as low as 0.0083 mU/mL. This proposed ZnTCPP/Ti3C2Tx composites with stimuli-responsive behavior is expected to provide new ideas for the development of high-sensitivity dual-mode ratiometric biosensors with promising applications in the precise detection of important biomarkers.

Two-Dimensional Nickel Porphyrinic Metal-Organic Framework-Modified Electrode for Electrochemical Sensing.

Due to their highly exposed active sites and high aspect ratio caused by their substantial lateral dimension and thin thickness, two-dimensional (2D) metal-organic framework (MOF) nanosheets are currently considered a potential hybrid material for electrochemical sensing. Herein, we present a nickel-based porphyrinic MOF nanosheet as a versatile and robust platform with an enhanced electrochemical detection performance. It is important to note that the nickel porphyrin ligand reacted with Cu(NO3)2·3H2O in a solvothermal process, with polyvinylpyrrolidone (PVP) acting as the surfactant to control the anisotropic development of creating a 2D Cu-TCPP(Ni) MOF nanosheet structure. To realize the exceptional selectivity, sensitivity, and stability of the synthesized 2D Cu-TCPP(Ni) MOF nanosheet, a laser-induced graphene electrode was modified with the MOF nanosheet and employed as a sensor for the detection of p-nitrophenol (p-NP). With a detection range of 0.5-200 µM for differential pulse voltammetry (DPV) and 0.9-300 µM for cyclic voltammetry (CV), the proposed sensor demonstrated enhanced electrochemical performance, with the limit of detection (LOD) for DPV and CV as 0.1 and 0.3 µM, respectively. The outstanding outcome of the sensor is attributed to the 2D Cu-TCPP(Ni) MOF nanosheet's substantial active surface area, innate catalytic activity, and superior adsorption capacity. Furthermore, it is anticipated that the proposed electrode sensor will make it possible to create high-performance electrochemical sensors for environmental point-of-care testing since it successfully detected p-NP in real sample analysis.

Two-Site Enhanced Porphyrinic Metal-Organic Framework Nanozymes and Nano-/Bioenzyme Confined Catalysis for Colorimetric/Chemiluminescent Dual-Mode Visual Biosensing.

The rational design of efficient nanozymes and the immobilization of enzymes are of great significance for the construction of high-performance biosensors based on nano-/bioenzyme catalytic systems. Herein, a novel V-TCPP(Fe) metal-organic framework nanozyme with a two-dimensional nanosheet morphology is rationally designed by using V2CTx MXene as a metal source and iron tetrakis(4-carboxyphenyl)porphine (FeTCPP) ligand as an organic linker. It exhibits enhanced peroxidase- and catalase-like activities and luminol-H2O2 chemiluminescent (CL) behavior. Based on the experimental and theoretical results, these excellent enzyme-like activities are derived from the two-site synergistic effect between V nodes and FeTCPP ligands in V-TCPP(Fe). Furthermore, a confined catalytic system is developed by zeolitic imidazole framework (ZIF) coencapsulation of the V-TCPP(Fe) nanozyme and bioenzyme. Using the acetylcholinesterase (AChE) as a model, our constructed V-TCPP(Fe)/AChE@ZIF confined catalytic system was successfully used for the colorimetric/CL dual-mode visual biosensing of organophosphorus pesticides. This work is expected to provide new insights into the design of efficient nanozymes and confined catalytic systems, encouraging applications in catalysis and biosensing.

MOF-On-MOF Dual Enzyme-Mimic Nanozyme with Enhanced Cascade Catalysis for Colorimetric/Chemiluminescent Dual-Mode Aptasensing.

A novel metal-organic framework (MOF)-on-MOF dual enzyme-mimic nanozyme was designed as enhanced cascade signal amplification for the colorimetric and chemiluminescent (CL) dual-mode aptasensing. The MOF-on-MOF hybrid is composed of MOF-818 with catechol oxidase-like activity and iron porphyrin MOF [PMOF(Fe)] with peroxidase-like activity, called MOF-818@PMOF(Fe). MOF-818 can catalyze the 3,5-di-tert-butylcatechol substrate and produce H2O2 in situ. Subsequently, PMOF(Fe) catalyzes H2O2 to produce reactive oxygen species, which oxidize 3,3',5,5'-tetramethylbenzidine or luminol to produce color or luminescence. Thanks to the nano-proximity effect and the confinement effect, the efficiency of the biomimetic cascade catalysis is greatly improved, which in turn generates enhanced colorimetric and CL signals. Taking the detection of chlopyrifos as an example, the prepared dual enzyme-mimic MOF nanozyme is combined with the aptamer with specific recognition ability to develop a colorimetric/CL dual-mode aptasensor for highly sensitive and selective detection of chlorpyrifos. The proposed MOF-on-MOF dual nanozyme-enhanced cascade system may provide a new pathway for the further development of a biomimetic cascade sensing platform.

Corrigendum: Recent advances in metal-organic framework- based electrochemical biosensing applications.

[This corrects the article DOI: 10.3389/fbioe.2021.797067.].

Corrigendum: Flexible biosensors based on colorimetry, fluorescence, and electrochemistry for point-of-care testing.

[This corrects the article DOI: 10.3389/fbioe.2021.753692.].

A Portable Electrochemical Sensor Based on Manganese Porphyrin-Functionalized Carbon Cloth for Highly Sensitive Detection of Nitroaromatics and Gaseous Phenol.

Organic pollutants (OPs) have garnered a considerable amount of attention in recent times due to their extreme toxicity toward humans and the ecosystem. The need for an inexpensive yet robust, sensitive, selective, and easy-to-operate method for detecting OPs remains a challenge. Herein, a portable electrochemical sensor is proposed based on manganese porphyrin-functionalized carbon cloth (CC). To explain the electrochemical performance of the sensor, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were employed. The presence of manganese(III) ion in the center of the porphyrin ligand acted as an agent for the transfer of electrons and enhanced sensitivity toward analyte-specific redox catalysis. Moreover, it allowed for the concurrent detection of multiple analytes in a complex environment. The modified CC electrode can selectively detect nitroaromatic and phenolic compounds with accessible data collected through wireless means onto a smartphone device. The as-synthesized electrode demonstrated a higher sensitivity toward the detection of nitrobenzene (NB) and aqueous phenol with a limit of detection (LOD) found to be 5.9268 × 10-10 M and 4.0178 × 10-10 M, respectively. Additionally, our proposed portable electrochemical sensor demonstrates a high selectivity and reproducibility toward nitroaromatic and phenolic compounds, which can be employed in real complex water samples. With regard to the sensor's remarkable electrochemical performance, it is envisaged that such a sensor could pave the way for environmental point of care (POC) testing.

Recent Advances on DNAzyme-Based Biosensors for Detection of Uranyl.

Nuclear facilities are widely used in fields such as national defense, industry, scientific research, and medicine, which play a huge role in military and civilian use. However, in the process of widespread application of nuclear technology, uranium and its compounds with high carcinogenic and biologically toxic cause a lot of environmental problems, such as pollutions of water, atmosphere, soil, or ecosystem. Bioensors with sensitivity and specificity for the detection of uranium are highly demand. Nucleic acid enzymes (DNAzyme) with merits of high sensitivity and selectivity for targets as excellent molecular recognition elements are commonly used for uranium sensor development. In this perspective review, we summarize DNAzyme-based biosensors for the quantitative detection of uranyl ions by integrating with diverse signal outputting strategies, such as fluorescent, colorimetry, surface-enhanced Raman scattering, and electrochemistry. Different design methods, limit of detection, and practical applications are fully discussed. Finally, the challenges, potential solutions, and future prospects of such DNAzyme-based sensors are also presented.

Magnetic zirconium-based Prussian blue analog nanozyme: enhanced peroxidase-mimicking activity and colorimetric sensing of phosphate ion.

A magnetic zirconium hexacyanoferrate-based Prussian blue analog (MB@ZrHCF) nanozyme was synthesized using dopamine (DA) reduction-assisted method and employed for colorimetric PO43- sensing. The MB@ZrHCF exhibits enhanced peroxidase-mimicking activity and ultrafast catalytic rate via the color reaction of 3,3',5,5'-tetramethylbenzidine (TMB) oxidized by hydrogen peroxide (H2O2). The catalytic reaction mechanism of MB@ZrHCF catalyzing H2O2 to produce hydroxyl radical (∙OH) was studied. Then, MB@ZrHCF was successfully applied to the detection of H2O2. Additionally, the catalytic activity of the nanocomposite is inhibited due to the steric hindrance effect from the coordination of PO43- and Zr(IV) node. Based on this, the MB@ZrHCF nanozyme can be used to detect PO43- in two linear ranges (10-100 µM and 100-200 µM) with a limit of detection of 2.25 µM. The proposed colorimetric sensor possesses excellent selectivity and reliability for PO43- sensing, which can be successfully applied to detect PO43- in sea and tap water samples.

Flexible Biosensors Based on Colorimetry, Fluorescence, and Electrochemistry for Point-of-Care Testing.

With the outbreak and pandemic of COVID-19, point-of-care testing (POCT) systems have been attracted much attention due to their significant advantages of small batches of samples, user-friendliness, easy-to-use and simple detection. Among them, flexible biosensors show practical significance as their outstanding properties in terms of flexibility, portability, and high efficiency, which provide great convenience for users. To construct highly functional flexible biosensors, abundant kinds of polymers substrates have been modified with sufficient properties to address certain needs. Paper-based biosensors gain considerable attention as well, owing to their foldability, lightweight and adaptability. The other important flexible biosensor employs textiles as substrate materials, which has a promising prospect in the area of intelligent wearable devices. In this feature article, we performed a comprehensive review about the applications of flexible biosensors based on the classification of substrate materials (polymers, paper and textiles), and illustrated the strategies to design effective and artificial sensing platforms, including colorimetry, fluorescence, and electrochemistry. It is demonstrated that flexible biosensors play a prominent role in medical diagnosis, prognosis, and healthcare.

Two-Dimensional Metalloporphyrinic Framework Nanosheet-Based Dual-Mechanism-Driven Ratiometric Electrochemiluminescent Biosensing of Protein Kinase Activity.

A dual-mechanism-driven ratiometric electrochemiluminescent (ECL) biosensor was developed for the ultrasensitive detection of protein kinase activity, which was based on a competitive catalytic reaction and resonance energy transfer (RET) by assembling gold nanoparticles (GNPs) on two-dimensional (2D) porphyrinic metal-organic framework (MOF) nanosheets. In this work, an ECL catalytic reaction competing for dissolved O2 proceeded between 2D copper-based zinc porphyrinic MOF (Cu-TCPP(Zn)) nanosheets and luminol. Meanwhile, the cathodic ECL of singlet oxygen (1O2), derived from the electrocatalytic reaction of 2D Cu-TCPP(Zn), would be reduced by the assembled GNPs due to RET, while the anodic emission of luminol could be enhanced by GNPs with excellent electrocatalytic activity. With the detection of protein kinase A (PKA) as an example, this dual-mechanism-driven ECL biosensor exhibited a broad linear range (0.005-5.0 U mL-1) and a sensitive detection limit (0.0037 U mL-1). Compared with the traditional single-mechanism-driven sensing strategies, the developed dual-mechanism-driven ratiometric ECL biosensor may provide an effective method for the design of green and ultrasensitive ECL sensors.

Recent Advances in Metal-Organic Framework-Based Electrochemical Biosensing Applications.

In the face of complex environments, considerable effort has been made to accomplish sensitive, accurate and highly-effective detection of target analytes. Given the versatility of metal clusters and ligands, high porosity and large specific surface area, metal-organic framework (MOF) provides researchers with prospective solutions for the construction of biosensing platforms. Combined with the benefits of electrochemistry method such as fast response, low cost and simple operation, the untapped applications of MOF for biosensors are worthy to be exploited. Therefore, this review briefly summarizes the preparation methods of electroactive MOF, including synthesize with electroactive ligands/metal ions, functionalization of MOF with biomolecules and modification for MOF composites. Moreover, recent biosensing applications are highlighted in terms of small biomolecules, biomacromolecules, and pathogenic cells. We conclude with a discussion of future challenges and prospects in the field. It aims to offer researchers inspiration to address the issues appropriately in further investigations.

Cationic metal-organic framework based mixed-matrix membrane for extraction of phenoxy carboxylic acid (PCA) herbicides from water samples followed by UHPLC-MS/MS determination.

A novel kind of cationic metal-organic framework(MOF) based mixed-matrix membrane(MMM) namely cationic MOF-MMM was firstly designed and used for simultaneous dispersive membrane extraction(DME) of six phenoxy carboxylic acid(PCA) herbicides from water samples followed by determination using ultrahigh-performance liquid chromatography tandem mass spectrometry. The cationic MOF-MMM was synthesized by soaking the zirconium-based MOFs in a polyvinylidene fluoride(PVDF) solution and further functionalization with quaternary amine groups, viz., UiO-66-NMe3+ MMM. The well-prepared UiO-66-NMe3+ MMM was characterized by FT-IR, SEM, XRD, XPS, NMR and etc. Several main variables influencing the MMM based DME efficiency were investigated and optimized in detail, such as dosage ratio of MOF/PVDF, solution pH, extraction time, coexistent anions and ionic strength. Electrostatic interactions dominated adsorption mechanism between anionic PCAs and cationic UiO-66-NMe3+ MMM, along with ππ conjugation and cation-π bonding, leading to better adsorption performance. Low limits of detection in the range of 0.03-0.59 ng/L and satisfactory recoveries within 80.06-117.40 % for all the PCAs are a reliable witness to demonstrate supreme sensitivity and the applicability of the developed method. By relying on the obtained results, the present work implied cationic MOF-MMM based DME can be a versatile and worthy utility for extraction of pollutants from different water samples with high throughput.

Zirconium-Metalloporphyrin Frameworks-Luminol Competitive Electrochemiluminescence for Ratiometric Detection of Polynucleotide Kinase Activity.

We propose a novel competitive mechanism involving the dissolved oxygen (O2) between zirconium-based porphyrinic metal-organic framework nanoparticles (NMOFs) and luminol into a ratiometric electrochemiluminescence (ECL) biosensing interface. Zinc tetrakis(carboxyphenyl)-porphyrin (ZnTCPP) in NMOFs as electron media reduce O2 into reactive oxygen species (ROS) and produce singlet oxygen (1O2), resulting in cathodic ECL. Meanwhile, ROS also react with the luminol anion radical and amplify the anodic ECL emission. Based on the competitive-mechanism-driven ECL process, taking the detection of polynucleotide kinase (PNK) as example, with assembling DNA-functionalized NMOFs on the sensing interface, a lower detection limit of 6.5 × 10-5 U mL-1 and broader linear relationship range from 0.0002 to 10 U mL-1 were obtained compared with that of single-signal-driven ECL sensors. This proposed MOFs-luminol competitive ECL mechanism involving dissolved O2 may provide a new pathway for further research of a green and highly sensitive ECL biosensing system.

Synthesis and biological evaluation of 2-epi-jaspine B analogs as selective sphingosine kinase 1 inhibitors.

2-Epi-jaspine B is an isomer of the natural product jaspine B and shows certain selectivity for SphK1 and potent antitumor activity. Based on the crystal structure of SphK1, we transformed the structure of 2-epi-jaspine B and modified the hydrophobic side chain to obtain a series of 2-epi-jaspine B analogs. The MTT assay was used to examine the antitumor activities of these analogs. We identified a novel 2-epi-jaspine B analog YHR17, which has potent antiproliferative activities for tested cell lines with IC50 values that ranged from 0.68 to 5.68 µM and inhibited the proliferation of the A375 cell line by affecting the cell cycle and apoptosis. Furthermore, YHR17 inhibited SphK1 with more than 125-fold selectivity over SphK2.

Diruthenium(ii)-NNN pincer complex catalysts for transfer hydrogenation of ketones.

Dinuclear ruthenium(ii)-NNN pincer complexes bearing a π linker-supported bis(pyrazolyl-imidazolyl-pyridine) ligand were synthesized and structurally characterized, and they exhibited excellent catalytic activity for the transfer hydrogenation of ketones in refluxing isopropanol, reaching TOF values up to 1.3 × 106 h-1. Compared with the corresponding mononuclear Ru(ii)-NNN pincer complexes, the bimetallic complexes could be applied at concentrations as low as 0.03 mol% Ru and demonstrated remarkably enhanced catalytic activity in the transfer hydrogenation reactions of ketones. The high catalytic activity of the diruthenium(ii) complexes is attributed to the excellent stability and possible cooperativity of the two coordinated Ru(ii) metal centers through the π linker. The present synthetic methodology has established an applicable strategy to construct highly active bimetallic NNN pincer complex catalysts.