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1.
Anal Methods ; 16(28): 4827-4834, 2024 Jul 18.
Article in English | MEDLINE | ID: mdl-38967314

ABSTRACT

A cloud point method was developed and applied for the first time to extract and preconcentrate thiabendazole (TBZ) from commercial whole grape juice samples, with determination by high performance liquid chromatography coupled to electrochemical detection (HPLC/EC), using a cathodically pretreated boron-doped diamond electrode (BDD). The best conditions for extraction and preconcentration of TBZ by cloud point extraction (CPE) were performed at pH 6.0, by adding 1 mL of the surfactant Tergitol TMN-6 at 10% (mass-to-mass ratio), without heating (at 27 °C) and ultrasonic stirring time of (20 kHz) for 60 min. The HPLC/EC determination was duly validated in a C8 column, in mobile phase with a 69 : 31 ratio (V/V) of phosphate buffer (pH 7.0):ACN, at a flow rate of 1.2 mL min-1 and electrochemical detection with BDD electrode by applying 1.40 V × Ag/AgCl (3.0 mol L-1). Under these conditions, the procedure showed a preconcentration factor (FC) of 21.7, and limits of detection (LOD) and quantification (LOQ) of 6.64 × 10-9 mol L-1 (or 1.33 µg L-1) and 1.66 × 10-8 mol L-1 (or 3.34 µg L-1), respectively. The method provided a percent recovery of 81% to 98%, with a coefficient of variation between 3% and 15%.


Subject(s)
Electrochemical Techniques , Fruit and Vegetable Juices , Thiabendazole , Vitis , Chromatography, High Pressure Liquid/methods , Thiabendazole/analysis , Thiabendazole/isolation & purification , Fruit and Vegetable Juices/analysis , Vitis/chemistry , Electrochemical Techniques/methods , Limit of Detection , Electrodes , Pesticides/analysis , Food Contamination/analysis
2.
Anal Methods ; 16(28): 4691-4699, 2024 Jul 18.
Article in English | MEDLINE | ID: mdl-38973362

ABSTRACT

Herein, a new dual-model photoelectrochemical (PEC)/electrochemical (EC) sensor based on Z-scheme titanium dioxide (TiO2) disk/methylene blue (MB) sensibilization for the detection of kanamycin (Kana) was developed. Metal-organic framework-derived porous TiO2 disks were synthesized and exhibited excellent anodic photocurrent under visible light excitation. Subsequently, amino-labeled double-stranded DNA (dsDNA) was introduced into the modified electrode. Photocurrent was enhanced with MB embedded in dsDNA to form Z-scheme TiO2/MB sensibilization. When the target, Kana, was present, it specifically bound to the aptamer in the dsDNA, leading to the disruption of the dsDNA structure and the release of MB. This release of MB and the increase in target spatial resistance resulted in a significant weakening of PEC signal and a decreased oxidation peak current of MB. The PEC sensor successfully detected Kana in the range of 2-1000 pM with an LOD of 0.17 pM. Meanwhile, the EC sensor for Kana detection showed a linear range of 5-500 pM with an LOD of 1.8 pM. Additionally, the sensor exhibited excellent selectivity, reproducibility, stability, and good recoveries when applied to milk and honey samples. As a result, this method has the potential for application in ensuring food safety through the rapid determination of antibiotics in food.


Subject(s)
Electrochemical Techniques , Kanamycin , Methylene Blue , Milk , Titanium , Titanium/chemistry , Kanamycin/analysis , Kanamycin/chemistry , Methylene Blue/chemistry , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Milk/chemistry , Animals , Limit of Detection , Biosensing Techniques/methods , Honey/analysis , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/chemistry , Photochemical Processes , Reproducibility of Results , Electrodes
3.
Sci Rep ; 14(1): 16424, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-39013935

ABSTRACT

Lately, children's daily consumption of some products, such as cereals and candies, has been rising, which provides a compelling rationale for determining any metallic substances that may be present. Monitoring the concentration of certain metals, like nickel, in these products is necessary due to medical issues in humans when consumed regularly. So, in this work, a novel and highly selective carbon paste as a Ni(II) ion-selective sensor was prepared and investigated using ceramic magnesium aluminum spinel nanoparticles as the ionophore and tritolyl phosphate (TOCP) as a plasticizer. A modified co-precipitation method was used to synthesize the spinel nanoparticles. X-ray diffraction, scanning electron microscope with EDAX, transmission electron microscope, and BET surface area were used to determine the phase composition, microstructure, pores size, particle size, and surface area of the synthesized nanoparticles. The spinel nanoparticle was found to have a nano crystallite size with a cubic crystal system, a particle size ranging from 17.2 to 51.52 nm, mesoporous nature (average pore size = 8.72 nm), and a large surface area (61.75 m2/g). The composition ratio of graphite carbon as a base: TOCP as binder: spinal as ionophore was 67.3:30.0:2.7 (wt%) based on potentiometric detections over concentrations from 5.0 × 10-8 to 1.0 × 10-2 mol L-1 with LOD of 5.0 × 10-8 mol L-1. A measurement of 29.22 ± 0.12 mV decade-1 over pH 2.0-7.0 was made for the Nernstian slope. This sensor demonstrated good repeatability over nine weeks and a rapid response of 8 s. A good selectivity was shown for Ni(II) ions across many interferents, tri-, di-, and monovalent cations. The Ni(II) content in spiked real samples, including cocaine, sweets, coca, chocolate, carbonated drinks, cereals, and packages, were measured. The results obtained indicated no significant difference between the proposed potentiometric method and the officially reported ICP method according to the F- and t-test data. In addition to utilizing ANOVA statistical analysis, validation procedures have been implemented, and the results exceed the ICP-MS methodology.


Subject(s)
Nickel , Nickel/analysis , Nickel/chemistry , Humans , Child , Magnesium Oxide/chemistry , Electrochemical Techniques/methods , Aluminum Oxide/chemistry , Nanoparticles/chemistry , Magnesium/chemistry , Magnesium/analysis , Ions/analysis , X-Ray Diffraction , Ionophores/chemistry
4.
Chem Commun (Camb) ; 60(59): 7630-7633, 2024 Jul 18.
Article in English | MEDLINE | ID: mdl-38958176

ABSTRACT

A W-doped Pt modified graphene oxide (Pt-W-GO) electrochemical microelectrode was developed to detect hydrogen peroxide (H2O2) in real time at a subcellular scale. Interestingly, results showed that the concentration of H2O2 in the nucleus of HeLa cells was 2.68 times and 0.51 times that in the extracellular membrane and cytoplasm, respectively.


Subject(s)
Electrochemical Techniques , Graphite , Hydrogen Peroxide , Microelectrodes , Platinum , Hydrogen Peroxide/analysis , Hydrogen Peroxide/chemistry , Humans , HeLa Cells , Platinum/chemistry , Graphite/chemistry
5.
ACS Appl Mater Interfaces ; 16(28): 37087-37099, 2024 Jul 17.
Article in English | MEDLINE | ID: mdl-38958653

ABSTRACT

Hydrogels, as flexible materials, have been widely used in the field of flexible sensors. Human sweat contains a variety of biomarkers that can reflect the physiological state of the human body. Therefore, it is of great practical significance and application value to realize the detection of sweat composition and combine it with human motion sensing through a hydrogel. Based on mussel-inspired chemistry, polydopamine (PDA) and gold nanoparticles (AuNPs) were coated on the surface of cellulose nanocrystals (CNCs) to obtain CNC-based nanocomposites (CNCs@PDA-Au), which could simultaneously enhance the mechanical, electrochemical, and self-healing properties of hydrogels. The CNCs@PDA-Au was composited with poly(vinyl alcohol) (PVA) hydrogel to obtain the nanocomposite hydrogel (PVA/CNCs@PDA-Au) by freeze-thaw cycles. The PVA/CNCs@PDA-Au has excellent mechanical strength (7.2 MPa) and self-healing properties (88.3%). The motion sensors designed with PVA/CNCs@PDA-Au exhibited a fast response time (122.9 ms), wide strain sensing range (0-600.0%), excellent stability, and fatigue resistance. With the unique electrochemical redox properties of uric acid, the designed hydrogel sensor successfully realized the detection of uric acid in sweat with a wide detection range (1.0-100.0 µmol/L) and low detection limit (0.42 µmol/L). In this study, the dual detection of human motion and uric acid in sweat was successfully realized by the designed PVA/CNCs@PDA-Au nanocomposite hydrogel.


Subject(s)
Cellulose , Gold , Hydrogels , Nanocomposites , Polymers , Sweat , Cellulose/chemistry , Nanocomposites/chemistry , Humans , Hydrogels/chemistry , Gold/chemistry , Sweat/chemistry , Polymers/chemistry , Metal Nanoparticles/chemistry , Polyvinyl Alcohol/chemistry , Nanoparticles/chemistry , Indoles/chemistry , Biosensing Techniques/methods , Electrochemical Techniques/methods , Limit of Detection , Motion
6.
ACS Appl Mater Interfaces ; 16(28): 36194-36203, 2024 Jul 17.
Article in English | MEDLINE | ID: mdl-38952261

ABSTRACT

The occurrence of cancer is often closely related to multiple tumor markers, so it is important to develop multitarget detection methods. By the proper design of the input signals and logical operations of DNA logic gates, detection and diagnosis of cancer at different stages can be achieved. For example, in the early stages, specific input signals can be designed to correspond to early specific tumor markers, thereby achieving early cancer detection. In the late stage, logic gates for multitarget detection can be designed to simultaneously detect multiple biomarkers to improve diagnostic accuracy and comprehensiveness. In this work, we constructed a dual-target-triggered DNA logic gate for anchoring DNA tetrahedra, where methylene blue was embedded in the DNA tetrahedra to sensitize ZnO@CdS@Au, achieving ultrasensitive detection of the target substance. We tested the response of AND and OR logic gates to the platform. For AND logic gates, the sensing platform only responds when both miRNAs are present. In the concentration range of 10 aM to 10 nM, the photoelectric signal gradually increases with an increase of the target concentration. Subsequently, we used OR logic gates for miRNA detection. Even if only one target exists, the sensing platform exhibits excellent performance. Similarly, within the concentration range of 10 aM to 10 nM, the photoelectric signal gradually increases with an increase of the target concentration. The minimum detection limit is 1.10 aM. Whether it is the need to detect multiple targets simultaneously or only one of them, we can achieve it by selecting the appropriate logic gate. This strategy holds promising application prospects in fields such as biosensing, medical diagnosis, and environmental monitoring.


Subject(s)
Biosensing Techniques , Cadmium Compounds , Electrochemical Techniques , Gold , Methylene Blue , MicroRNAs , Nanotubes , Sulfides , Zinc Oxide , Methylene Blue/chemistry , Zinc Oxide/chemistry , Biosensing Techniques/methods , Gold/chemistry , Nanotubes/chemistry , Cadmium Compounds/chemistry , Electrochemical Techniques/methods , MicroRNAs/analysis , Sulfides/chemistry , Humans , Limit of Detection , Logic
7.
J Mol Model ; 30(8): 245, 2024 Jul 03.
Article in English | MEDLINE | ID: mdl-38960925

ABSTRACT

CONTEXT: For the first time, the use of monocyclic rings C18 and B9N9 as sensors for the sensing of carbazole-based anti-cancer drugs, such as tetrahydrocarbazole (THC), mukonal (MKN), murrayanine (MRY), and ellipticine (EPT), is described using DFT simulations and computational characterization. The geometries, electronic properties, stability studies, sensitivity, and adsorption capabilities of C18 and B9N9 counterparts towards the selected compounds confirm that the analytes interact through active cavities of the C18 and B9N9 rings of the complexes. METHODS: Based on the interaction energies, the sensitivity of surfaces towards EPT, MKN, MRY, and THC analytes is observed. The interaction energy of EPT@B9N9, MKN@B9N9, MRY@B9N9, and THC@B9N9 complexes are observed - 20.40, - 19.49, - 20.07, and - 18.27 kcal/mol respectively which is more exothermic than EPT@C18, MKN@C18, MRY@C18, and THC@C18 complexes are - 16.37, - 13.97, - 13.96, and - 11.39 kcal/mol respectively. According to findings from the quantum theory of atoms in molecules (QTAIM) and the reduced density gradient (RDG), dispersion forces play a significant role in maintaining the stability of these complexes. The electronic properties including FMOs, density of states (DOS), natural bond orbitals (NBO), charge transfer, and absorption studies are carried out. In comparison of B9N9 and C18, the analyte recovery time for C18 is much shorter (9.91 × 10-11 for THC@C18) than that for B9N9 shorter recovery time value of 3.75 × 10-9 for EPT@B9N9. These results suggest that our reported sensors B9N9 and C18 make it faster to detect adsorbed molecules at room temperature. The sensor response is more prominent in B9N9 due to its fine energy gap and high adsorption energy. Consequently, it is possible to think of these monocyclic systems as a potential material for sensor applications.


Subject(s)
Antineoplastic Agents , Carbazoles , Density Functional Theory , Carbazoles/chemistry , Antineoplastic Agents/chemistry , Adsorption , Electrochemical Techniques/methods , Models, Molecular , Molecular Structure
8.
Luminescence ; 39(7): e4825, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38961763

ABSTRACT

Herein, we have reported a red-emitting 4-methyl coumarin fused barbituric acid azo dye (4-MCBA) synthesized by conventional method. Density functional theory (DFT) studies of tautomer compounds were done using (B3LYP) with a basis set of 6-31G(d,p). NLO analysis has shown that tautomer has mean first-order hyperpolarisabilities (ß) value of 1.8188 × 10-30 esu and 1.0470 × 10-30 esu for azo and hydrazone forms, respectively, which is approximately nine and five times greater than the magnitude of urea. 4-MCBA exhibited two absorption peaks in the range of 290-317 and 379-394 nm, and emission spectra were observed at 536 nm. CV study demonstrated that the modified 4-MCBA/MGC electrode exhibited excellent electrochemical sensitivity towards the detection of catechol and the detection limit is 9.39 µM under optimum conditions. The 4-MCBA employed as a fluorescent probe for the visualisation of LFPs on various surfaces exhibited Level-I to level-II LFPs, with low background interference.


Subject(s)
Barbiturates , Catechols , Coumarins , Electrochemical Techniques , Barbiturates/chemistry , Catechols/chemistry , Catechols/analysis , Electrochemical Techniques/instrumentation , Coumarins/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Molecular Structure , Density Functional Theory , Electrodes
9.
Mikrochim Acta ; 191(8): 460, 2024 07 10.
Article in English | MEDLINE | ID: mdl-38987355

ABSTRACT

The facile sonochemical synthesis is reported of zinc cobalt oxide (ZnCo2O4) composited with carbon nanofiber (CNF). Structural, chemical, and morphological were characterized by X-ray diffraction (XRD), X-ray photoluminescent spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and transmittance electron microscopy (TEM), respectively. ZnCo2O4/CNF-modified GCE was applied to the detection of bisphenol A (BPA). The modified GCE shows enhanced sensing performance towards BPA, which includes a linear range (0.2 to 120 µM L-1) alongside a low limit of detection (38.2 nM L-1), low interference, and good stability. Detection of lower concentrations of BPA enables real sample analysis in the food industries (milk, orange juice, yogurt, tap water, and baby feeding bottles). Surprisingly, the BPA was detected in milk 510 nM L-1, orange juice 340 nM L-1, yogurt 1050 nM L-1, and tap water 140 nM L-1. Moreover, an interaction mechanism between the BPA analyte and ZnCo2O4 was discussed.


Subject(s)
Benzhydryl Compounds , Carbon , Cobalt , Milk , Nanofibers , Phenols , Benzhydryl Compounds/analysis , Phenols/analysis , Phenols/chemistry , Cobalt/chemistry , Carbon/chemistry , Milk/chemistry , Nanofibers/chemistry , Food Contamination/analysis , Animals , Oxides/chemistry , Limit of Detection , Electrochemical Techniques/methods , Fruit and Vegetable Juices/analysis , Green Chemistry Technology/methods , Yogurt/analysis
10.
Int J Mol Sci ; 25(13)2024 Jun 28.
Article in English | MEDLINE | ID: mdl-39000196

ABSTRACT

The green and sustainable electrocatalytic conversion of nitrogen-containing compounds to ammonia is currently in high demand in order to replace the eco-unfriendly Haber-Bosch process. Model catalysts for the nitrate reduction reaction were obtained by electrodeposition of metal Co, Fe, and bimetallic Fe/Co nanoparticles from aqueous solutions onto a graphite substrate. The samples were characterized by the following methods: SEM, XRD, XPS, UV-vis spectroscopy, cyclic (and linear) voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. In addition, the determination of the electrochemically active surface was also performed for all electrocatalysts. The best electrocatalyst was a sample containing Fe-nanoparticles on the layer of Co-nanoparticles, which showed a Faradaic efficiency of 58.2% (E = -0.785 V vs. RHE) at an ammonia yield rate of 14.6 µmol h-1 cm-2 (at ambient condition). An opinion was expressed to elucidate the mechanism of coordinated electrocatalytic action of a bimetallic electrocatalyst. This work can serve primarily as a starting point for future investigations on electrocatalytic conversion reactions to ammonia using model catalysts of the proposed type.


Subject(s)
Ammonia , Cobalt , Iron , Metal Nanoparticles , Nitrates , Oxidation-Reduction , Ammonia/chemistry , Catalysis , Iron/chemistry , Metal Nanoparticles/chemistry , Nitrates/chemistry , Cobalt/chemistry , Electrochemical Techniques/methods
11.
Molecules ; 29(13)2024 Jun 26.
Article in English | MEDLINE | ID: mdl-38998990

ABSTRACT

The tractable preparation of Phase I drug metabolites is a critical step to understand the first-pass behaviour of novel chemical entities (NCEs) in drug discovery. In this study, we have developed a structure-electroactivity relationship (SeAR)-informed electrochemical reaction of the parent 2-chlorophenothiazine and the antipsychotic medication, chlorpromazine. With the ability to dial-in under current controlled conditions, the formation of S-oxide and novel S,S-dioxide metabolites has been achieved for the first time on a multi-milligram scale using a direct batch electrode platform. A potential rationale for the electrochemical formation of these metabolites in situ is proposed using molecular docking to a cytochrome P450 enzyme.


Subject(s)
Antipsychotic Agents , Molecular Docking Simulation , Phenothiazines , Antipsychotic Agents/chemistry , Phenothiazines/chemistry , Humans , Electrochemical Techniques , Chlorpromazine/chemistry , Oxides/chemistry , Cytochrome P-450 Enzyme System/metabolism , Molecular Structure
12.
Molecules ; 29(13)2024 Jul 02.
Article in English | MEDLINE | ID: mdl-38999110

ABSTRACT

Electrochemical biosensors have emerged as powerful tools for the ultrasensitive detection of lung cancer biomarkers like carcinoembryonic antigen (CEA), neuron-specific enolase (NSE), and alpha fetoprotein (AFP). This review comprehensively discusses the progress and potential of nanocomposite-based electrochemical biosensors for early lung cancer diagnosis and prognosis. By integrating nanomaterials like graphene, metal nanoparticles, and conducting polymers, these sensors have achieved clinically relevant detection limits in the fg/mL to pg/mL range. We highlight the key role of nanomaterial functionalization in enhancing sensitivity, specificity, and antifouling properties. This review also examines challenges related to reproducibility and clinical translation, emphasizing the need for standardization of fabrication protocols and robust validation studies. With the rapid growth in understanding lung cancer biomarkers and innovations in sensor design, nanocomposite electrochemical biosensors hold immense potential for point-of-care lung cancer screening and personalized therapy guidance. Realizing this goal will require strategic collaboration among material scientists, engineers, and clinicians to address technical and practical hurdles. Overall, this work provides valuable insight for developing next-generation smart diagnostic devices to combat the high mortality of lung cancer.


Subject(s)
Biomarkers, Tumor , Biosensing Techniques , Electrochemical Techniques , Lung Neoplasms , Humans , Biomarkers, Tumor/analysis , Lung Neoplasms/diagnosis , Biosensing Techniques/methods , Electrochemical Techniques/methods , Carcinoembryonic Antigen/analysis , Carcinoembryonic Antigen/blood , Nanocomposites/chemistry , Graphite/chemistry
13.
Water Sci Technol ; 90(1): 225-237, 2024 Jul.
Article in English | MEDLINE | ID: mdl-39007316

ABSTRACT

To solve the problem of low removal rate and poor N2 selectivity in direct electrochemical ammonia oxidation (EAO), commercial Ni foam and Cu foam were used as anode and cathode of the EAO system, respectively. The coupling effect between the cathode and anode promoted nitrogen cycling during the reaction process, which improved N2 selectivity of the reaction system and promoted it to achieve a high ammonia removal rate. This study showed that the thin Ni(OH)2 with oxygen vacancy formed on the surface of Ni foam anode played an effective role in the dimerization of intermediate products in ammonia oxidation to form N2. This electrochemical system was used to treat real goose wastewater containing 422.5 mg/L NH4+-N and 94.5 mg/L total organic carbon (TOC). After treatment, this electrochemical system achieved good performance with an ammonia removal rate of 87%, N2 selectivity of 77%, and TOC removal rate of 72%. Therefore, this simple and efficient system with Ni foam anode and Cu foam cathode is a promising method for treating ammonia nitrogen wastewater.


Subject(s)
Ammonia , Copper , Electrodes , Hydroxides , Nickel , Nitrogen , Oxidation-Reduction , Ammonia/chemistry , Nitrogen/chemistry , Nickel/chemistry , Copper/chemistry , Hydroxides/chemistry , Waste Disposal, Fluid/methods , Wastewater/chemistry , Electrochemical Techniques/methods , Water Pollutants, Chemical/chemistry
14.
Anal Chem ; 96(28): 11299-11308, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38953225

ABSTRACT

Measuring neuronal electrical activity, such as action potential propagation in cells, requires the sensitive detection of the weak electrical signal with high spatial and temporal resolution. None of the existing tools can fulfill this need. Recently, plasmonic-based electrochemical impedance microscopy (P-EIM) was demonstrated for the label-free mapping of the ignition and propagation of action potentials in neuron cells with subcellular resolution. However, limited by the signal-to-noise ratio in the high-speed P-EIM video, action potential mapping was achieved by averaging 90 cycles of signals. Such extensive averaging is not desired and may not always be feasible due to factors such as neuronal desensitization. In this study, we utilized advanced signal processing techniques to detect action potentials in P-EIM extracted signals with fewer averaged cycles. Matched filtering successfully detected action potential signals with as few as averaging five cycles of signals. Long short-term memory (LSTM) recurrent neural network achieved the best performance and was able to detect single-cycle stimulated action potential successfully [satisfactory area under the receiver operating characteristic curve (AUC) equal to 0.855]. Therefore, we show that deep learning-based signal processing can dramatically improve the usability of P-EIM mapping of neuronal electrical signals.


Subject(s)
Action Potentials , Deep Learning , Electric Impedance , Electrochemical Techniques , Microscopy , Microscopy/methods , Animals , Electrochemical Techniques/methods , Neurons/physiology
15.
Mikrochim Acta ; 191(8): 463, 2024 07 12.
Article in English | MEDLINE | ID: mdl-38995455

ABSTRACT

The intensifying global opioid crisis, majorly attributed to fentanyl (FT) and its analogs, has necessitated the development of rapid and ultrasensitive remote/on-site FT sensing modalities. However, current approaches for tracking FT exposure through wastewater-based epidemiology (WBE) are unadaptable, time-consuming, and require trained professionals. Toward developing an extended in situ wastewater opioid monitoring system, we have developed a screen-printed electrochemical FT sensor and integrated it with a customized submersible remote sensing probe. The sensor composition and design have been optimized to address the challenges for extended in situ FT monitoring. Specifically, ZIF-8 metal-organic framework (MOF)-derived mesoporous carbon (MPC) nanoparticles (NPs) are incorporated in the screen-printed carbon electrode (SPCE) transducer to improve FT accumulation and its electrocatalytic oxidation. A rapid (10 s) and sensitive square wave voltammetric (SWV) FT detection down to 9.9 µgL-1 is thus achieved in aqueous buffer solution. A protective mixed-matrix membrane (MMM) has been optimized as the anti-fouling sensor coating to mitigate electrode passivation by FT oxidation products and enable long-term, intermittent FT monitoring. The unique MMM, comprising an insulating polyvinyl chloride (PVC) matrix and carboxyl-functionalized multi-walled carbon nanotubes (CNT-COOH) as semiconductive fillers, yielded highly stable FT sensor operation (> 95% normalized response) up to 10 h in domestic wastewater, and up to 4 h in untreated river water. This sensing platform enables wireless data acquisition on a smartphone via Bluetooth. Such effective remote operation of submersible opioid sensing probes could enable stricter surveillance of community water systems toward timely alerts, countermeasures, and legal enforcement.


Subject(s)
Analgesics, Opioid , Electrochemical Techniques , Fentanyl , Metal-Organic Frameworks , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Fentanyl/analysis , Fentanyl/blood , Analgesics, Opioid/analysis , Metal-Organic Frameworks/chemistry , Electrodes , Wastewater/analysis , Environmental Monitoring/methods , Limit of Detection , Carbon/chemistry , Nanoparticles/chemistry , Remote Sensing Technology/methods
16.
Anal Chem ; 96(28): 11383-11389, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38946419

ABSTRACT

Apurinic/apyrimidinic endonuclease 1 (APE1), as a vital base excision repair enzyme, is essential for maintaining genomic integrity and stability, and its abnormal expression is closely associated with malignant tumors. Herein, we constructed an electrochemiluminescence (ECL) biosensor for detecting APE1 activity by combining nanoconfined ECL silver nanoclusters (Ag NCs) with X-shaped DNA recognizer-triggered cascade amplification. Specifically, the Ag NCs were prepared and confined in the glutaraldehyde-cross-linked chitosan hydrogel network using the one-pot method, resulting in a strong ECL response and exceptional stability in comparison with discrete Ag NCs. Furthermore, the self-assembled X-shaped DNA recognizers were designed for APE1 detection, which not only improved reaction kinetics due to the ordered arrangement of recognition sites but also achieved high sensitivity by utilizing the recognizer-triggered cascade amplification of strand displacement amplification (SDA) and DNAzyme catalysis. As expected, this biosensor achieved sensitive ECL detection of APE1 in the range of 1.0 × 10-3 U·µL-1 to 1.0 × 10-10 U·µL-1 with the detection limit of 2.21 × 10-11 U·µL-1, rendering it a desirable approach for biomarker detection.


Subject(s)
Biosensing Techniques , DNA-(Apurinic or Apyrimidinic Site) Lyase , Electrochemical Techniques , Luminescent Measurements , Metal Nanoparticles , Silver , DNA-(Apurinic or Apyrimidinic Site) Lyase/metabolism , DNA-(Apurinic or Apyrimidinic Site) Lyase/analysis , Silver/chemistry , Humans , Metal Nanoparticles/chemistry , Electrochemical Techniques/methods , Luminescent Measurements/methods , Biosensing Techniques/methods , Nucleic Acid Amplification Techniques/methods , DNA/chemistry , Limit of Detection , DNA, Catalytic/chemistry , DNA, Catalytic/metabolism
17.
Anal Chem ; 96(28): 11326-11333, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38953527

ABSTRACT

Herein, the aptamer-antibody sandwich module was first introduced to accurately recognize a low molecular weight compound (mycotoxin). Impressively, compared with the large steric hindrance of a traditional dual-antibody module, the aptamer-antibody sandwich with low Gibbs free energy and a low dissociation constant has high recognition efficiency; thus, it could reduce false positives and false negatives caused by a dual-antibody module. As a proof of concept, a sensitive electrochemiluminescence (ECL) biosensor was constructed for detecting mycotoxin zearalenone (ZEN) based on an aptamer-antibody sandwich as a biological recognition element and porous ZnO nanosheets (Zn NSs) supported Cu nanoclusters (Cu NCs) as the signal transduction element, in which the antibody was modified on the vertex of a tetrahedral DNA nanostructure (TDN) with a rigid structure to increase the kinetics of target recognition for promoting the detection sensitivity. Moreover, the Cu NCs/Zn NSs exhibited an excellent ECL response that was attributed to the aggregation-induced ECL enhancement through electrostatic interactions. The sensing platform achieved trace detection of ZEN with a low detection limit of 0.31 fg/mL, far beyond that of the enzyme-linked immunosorbent assay (ELISA, the current rapid detection method) and high-performance liquid chromatography (HPLC, the national standard detection method). The strategy has great application potential in food analysis, environmental monitoring, and clinical diagnosis.


Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , Electrochemical Techniques , Zearalenone , Aptamers, Nucleotide/chemistry , Biosensing Techniques/methods , Zearalenone/analysis , Zearalenone/immunology , Electrochemical Techniques/methods , Copper/chemistry , Limit of Detection , Antibodies/chemistry , Antibodies/immunology , Luminescent Measurements/methods , Zinc Oxide/chemistry , Molecular Weight
18.
Environ Sci Technol ; 58(28): 12708-12718, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38953681

ABSTRACT

Electroreduction of nitrate (NO3RR) to ammonia in membraneless electrolyzers is of great significance for reducing the cost and saving energy consumption. However, severe chemical crossover with side reactions makes it challenging to achieve ideal electrolysis. Herein, we propose a general strategy for efficient membraneless ammonia synthesis by screening NO3RR catalysts with inferior oxygen reduction activity and matching the counter electrode (CE) with good oxygen evolution activity while blocking anodic ammonia oxidation. Consequently, screening the available Co-Co system, the membraneless NO3--to-NH3 conversion performance was significantly higher than H-type cells using costly proton-exchange membranes. At 200 mA cm-2, the full-cell voltage of the membraneless system (∼2.5 V) is 4 V lower than that of the membrane system (∼6.5 V), and the savings are 61.4 kW h (or 56.9%) per 1 kg NH3 produced. A well-designed pulse process, inducing reversible surface reconstruction that in situ generates and restores the active Co(III) species at the working electrode and forms favorable Co3O4/CoOOH at the CE, further significantly improves NO3--to-NH3 conversion and blocks side reactions. A maximum NH3 yield rate of 1500.9 µmol cm-2 h-1 was achieved at -0.9 V (Faraday efficiency 92.6%). This pulse-coupled membraneless strategy provides new insights into design complex electrochemical synthesis.


Subject(s)
Ammonia , Nitrates , Ammonia/chemistry , Electrodes , Oxidation-Reduction , Electrochemical Techniques , Electrolysis , Catalysis
19.
Anal Chem ; 96(28): 11280-11289, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38954610

ABSTRACT

Here, ultrasmall SiO2 nanoparticles (u-SiO2 NPs, <5 nm) with obvious electrochemiluminescence (ECL) phenomenon, which was absent for conventional silica nanoparticles (c-SiO2 NPs), were reported. In a finite ultrasmall volume, the u-SiO2 NPs exhibited increasing ground state energy and higher optical absorption strength due to the electron-hole confinement model and favored catalyzing the reaction through the rapid diffusion of bulk charge, resulting in apparent ECL emission. Then, Zn2+-induced u-SiO2 nanoaggregates (Zn/u-SiO2-Ov nAGG) were synthesized and exhibited improved ECL performance via multipath surface state adjustment of u-SiO2 from several aspects, including aggregation-induced ECL, the generation of oxygen vacancy (Ov), and more positive surface charge. In addition, an ECL biosensor was constructed for ultrasensitive human immunodeficiency virus-related deoxyribonucleic acid detection from 100 aM to 1 nM with a low limit of 50.48 aM, combining the ECL luminescence of Zn/u-SiO2-Ov nAGG with three-dimensional DNA nanomachine-mediated multioutput amplification for enhanced accuracy and sensitivity compared to the single-output method. Therefore, exploring the ECL of ultrasmall nanoparticles via the adjustment of size and surface state provided a valuable indication to a wider investigation and application of novel ECL materials for clinical diagnostic.


Subject(s)
DNA, Viral , Electrochemical Techniques , Luminescent Measurements , Nanoparticles , Silicon Dioxide , Surface Properties , Silicon Dioxide/chemistry , Nanoparticles/chemistry , Electrochemical Techniques/methods , Luminescent Measurements/methods , DNA, Viral/analysis , Particle Size , Biosensing Techniques/methods , HIV , Humans , Limit of Detection
20.
Mikrochim Acta ; 191(8): 443, 2024 07 02.
Article in English | MEDLINE | ID: mdl-38955844

ABSTRACT

CoFe@C was first prepared by calcining the precursor of CoFe-metal-organic framework-74 (CoFe-MOF-74), then an electrochemical sensor for the determination of neohesperidin dihydrochalcone (NHDC) was constructed, which was stemmed from the novel CoFe@C/Nafion composite film modified glassy carbon electrode (GCE). The CoFe@C/Nafion composite was verified by field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). Electrochemical impedance spectroscopy (EIS) was used to evaluate its electrical properties as a modified material for an electrochemical sensor. Compared with CoFe-MOF-74 precursor modified electrode, CoFe@C/Nafion electrode exhibited a great synergic catalytic effect and extremely increased the oxidation peak signal of NHDC. The effects of various experimental conditions on the oxidation of NHDC were investigated and the calibration plot was tested. The results bespoken that CoFe@C/Nafion GCE has good reproducibility and anti-interference under the optimal experimental conditions. In addition, the differential pulse current response of NHDC was linear with its concentration within the range 0.08 ~ 20 µmol/L, and the linear regression coefficient was 0.9957. The detection limit was as low as 14.2 nmol/L (S/N = 3). In order to further verify the feasibility of the method, it was successfully used to determine the content of NHDC in Chinese medicine, with a satisfactory result, good in accordance with that of high performance liquid chromatography (HPLC).


Subject(s)
Chalcones , Cobalt , Electrochemical Techniques , Electrodes , Limit of Detection , Metal-Organic Frameworks , Cobalt/chemistry , Metal-Organic Frameworks/chemistry , Chalcones/chemistry , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Drugs, Chinese Herbal/chemistry , Drugs, Chinese Herbal/analysis , Hesperidin/analogs & derivatives , Hesperidin/analysis , Hesperidin/chemistry , Fluorocarbon Polymers/chemistry , Oxidation-Reduction , Carbon/chemistry , Reproducibility of Results , Iron/chemistry
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