Electron Transfer Rate Research Articles

Powering Hydrogen Evolution Reaction by Precise Control Over A Cu‐Ni Bimetallic Electrocatalyst

ABSTRACTPrecious metals are effective catalysts for the hydrogen evolution reaction, but their high cost with complicated operation steps drives people to search for non–noble‐metal alternatives. Building rational design concept for efficient electrocatalyst relies on the capability to control the structure and composition. Herein, a Ni/Cu bimetallic mesoporous MOFs with 4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid as the robust ligand has been assembled via a one‐step solvothermal method. Due to the extensive conjugate plane and high nitrogen content, the catalyst possesses large pore size of 17 nm and fast electron transfer rate, which favors hydrogen bubble overflow and exposes more active sites to solid–liquid interfaces. The bimetallic interaction between highly conductive Cu ions and Ni ions allows it to improve charge migration and realize excellent conductivity. The functionalized electrode requires an overpotential of 132 mV to achieve 10 mA current density with a small Tafel slope (87.7 mV·dec−1) and continuous electrolysis for 24 h.

Detection of Tert-Butylhydroquinone in Edible Oils Using an Electrochemical Sensor Based on a Nickel-Aluminum Layered Double Hydroxide@Carbon Spheres-Derived Carbon Composite.

Phenolic antioxidants such as tert-butylhydroquinone (TBHQ) can prolong the shelf life of edible oils by delaying the oxidation process. The excessive use of TBHQ can damage food quality and public health, so it is necessary to develop an efficient TBHQ detection technique. In this work, nickel-aluminum double hydroxide (NiAl-LDH) was grown on glucose carbon spheres (GC), which formed porous carbon nanomaterials (named NiAl-LDH@GC-800) after pyrolysis at 800 °C. The successful synthesis of the material was verified by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The obtained NiAl-LDH@GC-800 was dopped onto a glass carbon electrode to prepare an electrochemical sensor for TBHQ. The synergistic effect of porous carbon and Ni metal reduced from NiAl-LDH by high-temperature calcination accelerated the electron transfer rate and improved the sensitivity of the sensor. The prepared sensor showed a low limit of detection (LOD) of 8.2 nM, a high sensitivity (4.2 A·M-1), and a good linear range (20~300 µM) in detecting TBHQ. The sensor was also successfully used for TBHQ detection in edible oils, including chili oil, peanut oil, and rapeseed oil.

Nanobioengineered Al2O3 Core-Shell Nanoparticle Preparation Using Bauhinia Variegate Plant Extract for Efficient Photocatalysis and Electrochemical Sensing.

Core-shell-based nanomaterials have garnered considerable attention in the recent past not only in catalytic applications but also in their potentiality in selective and efficient sensing. Present research reports the first and successful biosynthesis of the core (c-Al2O3)-shell nanoparticles (NPs) using Bauhinia variegate blossom extract as reducing and capping agents. The synthesized c-Al2O3 NPs were characterized and utilized to fabricate nanobioengineered electrodes on indium tin oxide (ITO) substrates via electrophoretic deposition. Electrochemical analysis, including cyclic voltammetry and differential pulse voltammetry, revealed quasi-reversible processes with high electron-transfer rates (Ks = 0.66 s-1) and a diffusion coefficient (D = 5.84 × 10-2 cm2 s-1). The electrode exhibited a very high sensitivity (23.44 μA μM-1 cm-2) and a low detection limit (0.463 μM) for sodium azide (NaN3) over two linear ranges of 1-6 and 8-20 μM. Additionally, c-Al2O3 NPs demonstrated the effective photocatalytic degradation of crystal violet dye under visible light, following pseudo-first-order kinetics. The fabricated electrode showed excellent selectivity, stability, and reproducibility, highlighting its potential for environmental monitoring and clinical diagnostics.

Leveraging leaf spectroscopy to identify drought-tolerant soybean cultivars

Understanding cultivars' physiological traits variations under abiotic stresses is critical to improve phenotyping and selections of resistant crop varieties. Traditional methods of accessing physiological traits in plants are costly and time consuming, which prevents their use in breeding programs. Spectroscopy data and statistical approaches such as partial least square regression could be applied to rapidly collect and predict several physiological parameters at leaf-level, allowing phenotyping several genotypes in a high-throughput manner. We collected spectroscopy data of twenty soybean cultivars planted under well-watered and drought conditions during the reproductive phase. At 20 days after drought was imposed, we measured leaf pigments content (chlorophyll a and b, and carotenoids), specific leaf area, electrons transfer rate, and photosynthetic active radiation. At 28 days after drought imposition, we measured leaf pigments content, specific leaf area, relative water content, and leaf temperature. Partial least square regression models accurately predicted leaf pigments content, specific leaf area, and leaf temperature (cross-validation R2 ranging from 0.56 to 0.84). Discriminant analysis using 54 wavelengths was able to select the best-performance cultivars regarding all evaluated physiological traits. We showed the great potential of using spectroscopy as a feasible, non-destructive, and accurate method to estimate physiological traits and screening of superior genotypes.

The influence of Rh-doped SnO2 microspheres on the sensitivity of benzene detection

In this article, Rh-doped SnO2 microspheres were prepared by a convenient hydrothermal treatment. Compared with the non-doped SnO2 microspheres, the Rh-doped SnO2 microspheres had larger specific surface area, faster electron transfer rate and increased oxygen vacancies, which is beneficial to improve the gas sensitivity of the material. The optimal sensitivity was observed of Rh-0.1 at 250 °C, and the response-recovery time of Rh-0.1 were 46 and 25 s, respectively. Besides, the Rh-doped SnO2 microspheres exhibited excellent gas selectivity and stability to benzene vapor. The novel Rh-doped SnO2 microspheres are potential gas detection materials for accessing benzene vapor.

The Hidden Mechanism: Excited‐State Proton‐Electron Pair Transfer in Metal Nanocluster Emission

Comprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate the critical role of excited‐state proton‐coupled electron transfer in the emission of metal NCs. Our findings demonstrate that hydronium ion (H3O+) binding can trigger a nonlinear, pH‐dependent excited‐state concerted electron proton transfer (CEPT) reaction. This involves simultaneous electron transfer from the Au(0) core to the Au(I)‐ATT (ATT denotes 6‐aza‐2‐thiothymidine) surface and proton transfer from H3O+ to the ATT ligand in a single step, greatly promoting vibrations and rotations of the Au(I)‐ATT surface, resulting in substantial PL quenching of Au10(ATT)6 NCs. Further analyses show that the unique CEPT dynamics are strongly influenced by the opposing effects of increased reorganization energy and a larger pre‐exponential factor on the electron transfer rate. Moreover, the proposed excited‐state CEPT process is found to be prevalent in core‐shell relaxation metal NCs, such as Au25(SR)18 (SR denotes thiolate) NCs, and serves as an important factor in limiting their PL emission. By simply controlling the pKa of the ligands, the emission performance of Au25(SR)18 can be easily regulated in physiological environments.

Homojunction-Incorporated Oxygen Vacancy Functionalized Spherical TiO2 Nanocrystals for the Electrochemical Detection of Chemical Oxygen Demand.

Chemical oxygen demand (COD) is a critical criterion for the analytical assessment of the degree of organic contaminants in an aqueous system. Typically, toxic and expensive reagents are employed in standardized COD analysis methods, leading to secondary pollution. In this work, we developed a rapid electrochemical method for COD detection based on the oxidation of hydroxyl radicals for organics in water by using oxygen vacancy doped anatase/rutile-TiO2 nanoparticles as electrooxidation catalysts. Homojunction interface generated increasing oxygen vacancies for enhancing electron-transfer rate and accelerating H2O oxidation to substantially improve ·OH yield. Oxygen vacancy further increased the oxygen evolution potential of the material. Initially, glucose was chosen as a standard analyte to evaluate electrochemical responses, and water from urban wastewater treatment plants was assessed as real samples subsequently. Excellent analytical characteristics were achieved with the A/R-TiO2 sensor under the optimal conditions, exhibiting a linear range from 1 to 300 mg L-1 and detection limit of 0.1 mg L-1 COD. The estimated COD values obtained from the samples were highly consistent with those determined using the conventional standard dichromate method. We have presented a fast, cost-effective, and ecologically sustainable method that outperforms the standard COD analysis method and holds great potential for the accurate determination of COD and boasts high detection sensitivity and a broad linear range.

Novel strategies for enhancing energy metabolism and wastewater treatment in algae-bacteria symbiotic system through carbon dots-induced photogenerated electrons: The definitive role of accelerated electron transport

The nitrogen removal efficiency of the algae-bacteria symbiotic system (ABSS) remains challenging due to competition for light capture and insufficient electron donors in aquaculture wastewater. To overcome this bottleneck issue, we first identified and reported the introduction of photogenerated electrons into ABSS by coupling them with carbon dots (CDs). The energy metabolism (21.52 %-56.25 %) and pollutant degradation efficiency (89.36 %-96.42 %) of ABSS/CDs surpassed the biochemical limit observed in traditional ABSS. Notably, the addtion of CDs facilitated an opening of the plastoquinone-pool (PQ-pool) valve and accelerated electron transfer rates, enabling photogenerated electrons to selectively target light-harvesting complexs as activation sites, thereby mobilizing photosynthesis and respiratory system activity to enhance nicotinamide adenine dinucleotide reduced (NADH) and adenosine triphosphate (ATP) production while promoting tricarboxylic acid (TCA) and Calvin cycle processes. In simulated swine wastewater treatment, ABSS/CDs achieved higher removal rates for the chemical oxygen demand (COD), total nitrogen (TN) and ammonium-nitrogen (NH4+-N) (100 %, 99.23 % and 98.62 % respectively) compared to pure culture systems alone. Network-based analysis revealed that ABSS/CDs improved microbial community structure stability within the photobioreactor while demonstrating efficient coupling between fungi, nitrifying bacteria, and denitrifying bacteria for enhanced performance in nitrogen removal processes. The upregulation of nitrogen metabolism and PQ-pool genes maintains efficient electron transport rates and contributes to nitrogen removal. This study expands our understanding of the physiological aptitudes of ABSS and provides valuable insights into applying CDs photoelectrons for enhanced wastewater treatment.

Free-standing medium-entropy porous needle-like FeCoCuNi phosphide nanowires-formed flower clusters/carbon fiber anode with high capacity and long durability for sodium-ion batteries

The drastic volume expansion and slow sodium-ion kinetics hinder the practical application of phosphides with high specific capacity and low discharge voltage in sodium-ion batteries (SIBs). Herein, we introduced entropy configuration into nanostructures and prepared a novel free-standing, three-dimensional, porous needle-like medium-entropy Fe, Co, Cu, Ni phosphide (ME-FCCNP) nanowires-formed flower clusters/carbon fiber cloth (CFC) anode (ME-FCCNP@CFC) for SIBs. The distorted lattices caused by medium-entropy configuration provide abundant sites for sodium-ion reactions and improve the electron transfer rate. The medium-entropy effects improve the mechanical stability, while the three-dimensional networks and porous needle-like nanowires provide sufficient space for the volume expansion. These combined properties enable the ME-FCCNP@CFC electrode to exhibit a high-rate capability of 170.8 mAh g−1 at 5.0 A g−1 and deliver a specific capacity of 325.8 mAh g−1 after 2000 cycles at 2.0 A g−1, far surpassing most of reported transition-metal phosphides. Moreover, the Na3V2(PO4)3 || ME-FCCNP@CFC full cell showcases a high-energy density of 256.8 Wh kg−1 and a long cycling life (267.8 mAh g−1 at 2.0 A g−1 with a capacity retention of 83.2 % after 1000 cycles). These results provide significantly promising implications for the anode design of SIBs by employing self-supporting and medium-entropy structures.

Effect of Tungsten Doping on the Properties of Titanium Dioxide Dye-Sensitized Solar Cells

Tungsten-doped TiO2 thin films were prepared by sol–gel method on fluorine-doped tin oxide-coated substrates as working electrodes of dye-sensitized solar cells. The influences of different W doping (0, 2, 4, 6, and 8 at%) on the microstructure, optical, and photovoltaic properties of the W-TiO2 thin-film DSSCs were studied by the measurement of X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) analysis, and electrochemical impedance spectroscopy (EIS). An optimal DSSCs performance was observed with a 6 at% W-doped TiO2 thin film, resulting in a Voc of 0.68 V, a Jsc of 20.2 mA/cm2, an FF of 68.6%, and an efficiency (η) of 9.42%. The efficiency of DSSCs with 6 at% W-doped TiO2 photoanode improved by 75%. This is because the 6 at% W-doped TiO2 thin film increases the specific surface area and electron transfer rate.

Self-Assembled Blossom-Shaped NiCo2S4 Nanosheets In Situ Deposited Electrodes: Possessing High Reactivity and Selectivity for Bromine-Based Flow Batteries.

Bromine-based flow batteries (Br-FBs) are emerging rapidly due to their high energy density and wide potential window for renewable energy storage systems. Nevertheless, the sluggish kinetics of the Br2/Br- reaction on the electrode is considered to be the main challenge contributing to the poor performance of Br-FBs. Herein, we report self-assembled blossom-shaped NiCo2S4 nanosheets, enabling in situ growth on graphite felt (GF) via a one-step hydrothermal method. In the prepared NiCo2S4-GF, the gaps formed by the nanosheets restrict bromine diffusion, the sulfuretted blossom-shaped structure provides active sites with bromine adsorption capacity, and the synergistic effect of Ni and Co accelerates the electron transfer rate, which allow the electrode to exhibit excellent electrocatalytic activity compared to commercial GF, CoS-GF, and NiS-GF. Moreover, NiCo2S4-GF demonstrates unique selectivity for enhancing the Br2/Br- redox reaction compared to the bimetallic oxide of NiCo2O4-GF. Consequently, the zinc-bromine flow battery (ZBFB) with NiCo2S4-GF achieves an energy efficiency of 80.16%, which is 16.18% higher than that of the battery with commercialized GF at a current density of 60 mA cm-2, as well as a maximum power density of 260.75 mW cm-2 at 280 mA cm-2. The effective enhancement of the performance of ZBFB suggests that NiCo2S4-GF possesses great application potential in Br-FBs.

Parkinson biomarker determination with an Au microflower-enhanced electrochemical immunosensor using non-Faradaic capacitancemeasurements.

This work comprehends the development and characterization of a carbon black-based electrode modified with Au microflowers to increase its effect as a capacitance biosensor for the determination of PARK7/DJ-1. Due to its high surface-to-volume ratio and biocompatibility, Au particles are suitable for antibody binding, and by monitoring surface capacitance, it is possible to identify the immune-pair interaction. Au microflowers allowed the adequate immobilization of Parkinsonian-related proteins: PARK7/DJ-1 and its antibody. The protein is associated with several antioxidant mechanisms, but its abnormal concentrations or mutations can be the cause of the loss of dopaminergic neurons, leading to Parkinson's disease. The device was characterized by scanning electron microscopy and cyclic voltammetry, revealing the flower-like structures and the electrochemically-interest enhancements they provide, such as increased heterogeneous electron transfer rate coefficient and electroactive area. The self-assembled monolayers of different molecules were optimized with the aid of 22 central composite experiments and a linear calibration curve was obtained between 0.700 and 120ngmL-1 of PARK7/DJ-1, with a limit of detection of 0.207ngmL-1. The data confirms that the addition of Au microflowers enhanced the electrochemical signal of the device, as well as allowed for the determination of an early stage Parkinson's disease biomarker with appreciable analytical performance.

Recent Advances in Bonding Regulation of Metalloporphyrin-Modified Carbon-Based Catalysts for Accelerating Energy Electrocatalytic Applications.

Metalloporphyrins modified carbon-based materials, owing to the excellent acid-base resistance, optimal electron transfer rates, and superior catalytic performance, have shown great potential in energy electrocatalysis. Recently, numerous efforts have concentrated on employing carbon-based substrates as platforms to anchor metalloporphyrins, thereby fabricating a diverse array of composite catalysts tailored for assorted electrocatalytic processes. However, the interplay through bonding regulation of metalloporphyrins with carbon materials and the resultant enhancement in catalyst performance remains inadequately elucidated. Gaining an in-depth comprehension of the synergistic interactions between metalloporphyrins and carbon-based materials within the realm of electrocatalysis is imperative for advancing the development of innovative composite catalysts. Herein, the review systematically classifies the binding modes (i.e., covalent grafting and non-covalent interactions) between carbon-based materials and metalloporphyrins, followed by a discussion on the structural characteristics and applications of metalloporphyrins supported on various carbon-based substrates, categorized according to their binding modes. Additionally, this review underscores the principal challenges and emerging opportunities for carbon-supported metalloporphyrin composite catalysts, offering both inspiration and methodological insights for researchers involved in the design and application of these advanced catalytic systems.

Flower-like SnS2/rGO composites with efficient iodide-triiodide redox performance for counter electrodes in Pt-free dye-sensitized solar cells

The work function (WF) of the counter electrode (CE) predominantly determines the device performance of dye sensitized solar cells (DSSCs) as it controls the electron transfer rate for dye regeneration. Hence in this work, tin disulphide/reduced graphene oxide (SnS2/rGO) composites were synthesized with different wt.% of rGO (3, 5, 7, 10 %) and investigated their performance in DSSCs applications. At the outset, the formation of pristine SnS2 and SnS2/rGO composites were confirmed through X-ray diffraction and Raman spectral analysis. The morphological imaging revealed the micro flower-like structure of SnS2 with cross-sectional width of 5 ± 0.2 μm, and petal thickness ranges from 30.7 nm to 46.4 nm. The binding energy spectra confirms the 4+ oxidation state of Sn in both SnS2 and 7 wt% SnS2/rGO, suggesting that the rGO does not alter the chemical states of SnS2. Further, the peak-to-peak separation values obtained from Cylic-Voltammetry analysis were found to be 0.37 and 0.57 V for S7 and Pt CE respectively, indicating the rapid electrolyte reduction of 7 wt% SnS2/rGO. Finally, a photo conversion efficiency (PCE) of 7.3 % has been achieved with 7 wt% SnS2/rGO CE which is greater than that of the PCE with Pt CE (6.5 %) and also higher than that of pristine SnS2 with 4.7 %. The improved PCE is attributed to the reduced WF of the 7 wt% SnS2/rGO composite as measured from the Kelvin probe force microscopy analysis, enabling the rapid redox reaction towards triiodide reduction.

Addition of CuO to form CuO/TiO2 and CuO/ZnO heterojunctions for photocatalytic CO2 conversion to methanol

Photocatalytic conversion of carbon dioxide (CO2) to value-added products is a promising route towards sustainability. In this work, gas phase CO2 in presence of water vapor and UV irradiation source was converted to methanol using TiO2, ZnO, CuO/TiO2 and CuO/ZnO photocatalysts. Characterization by physico-chemical, optical and First-principle based techniques revealed that CuO/TiO2 possessed increased oxygen vacancy, highest average electron lifetime, transfer rate, injection efficiency and highest separation efficiency. The maximum methanol (∼28 %) yield of CuO/TiO2 is ascribed due to combined effect of heterojunction formation and increment in surface oxygen vacancies by doping with CuO, acted as electron-trapping cocatalyst.

Development of a MOF-5/g-C3N4 nanocomposite: an effective type 2 heterojunction photocatalyst for rhodamine B dye degradation.

The field of environmental and water remediation faces a significant challenge in removing organic dyes from wastewater, particularly Rhodamine B (RhB), a stubborn dye used in various industries. Traditional treatment methods struggle with its resistance to decomposition, posing risks to water quality, human health, and aquatic life. This study demonstrates a novel approach to enhance photocatalytic efficiency for RhB degradation by constructing a MOF-5/g-C3N4 composite through a facile mechanical grinding method, which is unprecedented. The composite addresses the limitations of g-C3N4, such as rapid recombination of electron-hole pairs, low electron transfer rates, and small surface area, by forming a heterojunction with MOF-5. The composite exhibits enhanced photocatalytic efficiency for the degradation of RhB under sunlight, with a degradation of 91.5% achieved within 90min. Optimization studies highlight the importance of pH and catalyst dosage in the degradation process. The reusability test shows consistent performance over five successive cycles, maintaining a degradation efficiency of over 90%. Total organic carbon (TOC) analyses confirm the mineralization of the dye solution to 82.05% after 90min of irradiation, demonstrating the environmental benignity of the composite. Trapping experiments suggest the involvement of superoxide radicals, electrons, and holes in the photocatalytic mechanism. This study introduces a promising strategy for addressing challenges in dye degradation through innovative composite materials.

CeO2 anchored in VO2@C rambutan-like microsphere achieving advanced zinc storage

Low-cost and high-safety aqueous zinc ion batteries (AZIBs) show great potential in energy storage for the grid. We propose a strategy to construct the self-assembled microspheres with the cerium oxide nanocrystals anchored on B-phase vanadium dioxide nanobelts, which are encapsulated by carbon (CVC), as cathode for high capacity and cycle stability of AZIBs. The rambutan-like structure with large specific surface area provides more active sites for the overall improvement of reaction kinetics; the carbon layer relieves vanadium dioxide from dissolving in the electrolyte while enhancing electron transfer rate; and electrocatalytic activity of cerium oxide accelerates redox reaction to enhance the performance of the cells. Consequently, the CVC electrode exhibits excellent electrochemical properties, including a reversible specific capacity (490 mAh g−1 at 0.1 A g−1), incredible cycle (84 % capacity retention after 1000 cycles at 5 A g−1). The excellent performance demonstrates the correctness of the combined internal and external modification strategy, while the simple hydrothermal method and inexpensive raw materials point to a new direction for the large-scale preparation of high-performance aqueous zinc ion batteries.

Electrochemical immunosensor based on gold nanoparticles for the detection of creatine kinase as a cardiac marker

This study presents the development of an electrochemical immunosensor utilizing gold nanoparticles for the detection of creatine kinase (CK), a crucial cardiac marker. Gold nanoparticles with an average diameter of 18.3 ± 2.1 nm were synthesized and characterized, exhibiting a characteristic surface plasmon resonance peak at 520 nm. The construction of the immunosensor was observed through cyclic voltammetry and electrochemical impedance spectroscopy, showing notable alterations in electron transfer rates during each step of the assembly process. Optimal performance was achieved at pH 7.4, with an antibody concentration of 100 μg/mL and an incubation time of 45 minutes. The sensor demonstrated a sensitivity of 152.6 Ω/(ng/mL) and maintained its response in the presence of common interfering substances, with maximum signal deviation of 7.2 %. Testing with spiked human serum samples yielded recovery rates between 96.5 % and 103.8 %. Comparison with ELISA using clinical samples further validated the sensor's accuracy. This AuNP-based immunosensor offers a promising platform for rapid and sensitive CK detection in cardiac health assessment.

Sinusoidal LED light recipes can improve rocket edible biomass and reduce electricity costs in indoor growth environments.

Accumulation of edible biomass by crop plants relies on maintenance of a high photosynthetic rates across the photoperiod, with assimilation rate (A) generally responding to increasing light intensity in a hyperbolic fashion. In natural environments light fluctuates greatly over the course of the day, however in Controlled Environmental Agricultural (CEA) systems, light intensity can be supplemented or precisely controlled using LEDs to create near optimum conditions. In such indoor growth environments light is often delivered as a square wave and recommendations to horticulturalists are given in the form of Daily Light Integrals (DLI). However, this does not take into account the slow photosynthetic induction at the start of the photoperiod and the decline of A towards the end of the photoperiod, which has been demonstrated by several previous studies. Square wave light regimes therefore potentially cause suboptimal photosynthetic utilization of the applied lighting and waste electricity. Here we have adapted light recipes to gradually increase and decrease in intensity to take account of these findings. We demonstrate that, utilising a sinusoidal light regime capped at 250 μmol m-2 s-1, it is possible to increase edible biomass of rocket (by ca. 20%) compared to square wave delivered at 250 at the same DLI. Additionally, this can be achieved using less electricity (0.6%), therefore reducing energy costs and improving profitability. We suggest that capping maximum light intensity at 250 µmol m-2 s-1 improves the operating efficiency of PSII photochemistry (Fq'/Fm') also known as the photosynthetic efficiency by maintaining A later in the photoperiod. We show that a higher electron transfer rate (ETR) is maintained in these treatments over the photoperiod compared to higher light intensity caps, resulting in a greater Daily Photochemical Integral (DPI). We attribute this to less NPQ due to a greater sink capacity for the end products of electron transport, ATP and NADPH, as A is kept high for longer.

Novel dopamine-derived carbon modified fe-based metal–organic framework enhanced aptasensor rendering ultrasensitive electrochemical detection of oxytetracycline

In the present work, an aptasensor with dual binding sites based on Au NPs modified with self-polymerized polydopamine (PDA) and Fe-MOF is successfully constructed. In terms of standard electron transfer, the cyclic voltammetry (CV) analysis showcases a rate constant (ks) of 96.0 s−1, signifying an exceptional electron transfer rate of oxytetracycline at the sensor interface of Apt/Au@PDA@NH2-MIL-101(Fe)/GCE. Further deepening the investigation into electrochemical kinetics using chronoamperometry (CA), we investigated the electrocatalytic parameters (Kcat) of Au@PDA@NH2-MIL-101(Fe) in relation to oxytetracycline. The results divulged an impressive average Kcat value of 3.06 × 105 M−1 S-1. This evidence robustly suggests the superior electrocatalytic activity of Au@PDA@NH2-MIL-101(Fe) when it comes to oxytetracycline oxidation. A custom-designed portable rapid detection platform was developed, achieving detection limits of 6.88 nM under static water flow conditions and 5.56 nM under dynamic conditions. Remarkably, the self-polymerization of PDA on Au NPs not only refines their size but also boosts their interaction with biomolecules, thereby promising excellent biocompatibility. Moreover, the abundance of –COOH groups and unsaturated Fe3+ sites on the NH2-MIL-101(Fe) surface furnishes a considerable number of grafting sites for the aptamer. More importantly, the redox interplay between Au@PDA and NH2-MIL-101(Fe) accelerates electron movement, thus amplifying the electrochemical signal and the detection sensitivity for oxytetracycline.