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Multivariate analysis and electrochemical detection of uric acid using a novel Fe–Ni-MOF/RGO nanosheet-based uricase biosensor on glassy carbon electrode

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We report the development of a highly innovative and selective biosensor for uric acid (UA) detection in plasma and urine samples, integrating bimetallic Fe–Ni-MOF nanoparticles with reduced graphene oxide (RGO) nanosheets and immobilized uricase (UOx) on a glassy carbon electrode (GCE). Unlike previously reported MOF- or RGO-based sensors, our design exploits the synergistic electro catalytic activity of Fe–Ni bimetallic centers and the high conductivity of RGO, coupled with an optimized enzyme loading, to achieve superior analytical performance. Critical experimental parameters—including Fe–Ni-MOF and RGO concentrations, enzyme volume, and pulse potential—were systematically optimized using central composite design (CCD) and response surface methodology, ensuring a statistically validated model confirmed by ANOVA. Under optimal conditions (Fe–Ni-MOF: 5.00 mg/mL; RGO: 1.91 mg/mL; UOx: 3.00 U/mL; pulse potential: 0.007 V), the biosensor exhibited a sharp anodic response at 0.31 V in phosphate buffer (pH 7.4). A broad linear range (0.005–5000 μM) with an ultralow detection limit of 0.21 µM was achieved, outperforming most state-of-the-art UA sensors. The sensor demonstrated excellent recoveries (99.1–101.7%) in real human plasma and urine samples, highlighting its accuracy, reproducibility, and strong potential for clinical diagnostics.

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Highly Specific Non-Enzymatic Electrochemical Sensor for the Detection of Uric Acid Using Carboxylated Multiwalled Carbon Nanotubes Intertwined with GdS-Gd2O3 Nanoplates in Human Urine and Serum.
  • Oct 2, 2024
  • Langmuir : the ACS journal of surfaces and colloids
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Herein, the electrochemical sensing efficacy of carboxylic acid functionalized multiwalled carbon nanotubes (C-MWCNT) intertwined with coexisting phases of gadolinium monosulfide (GdS) and gadolinium oxide (Gd2O3) nanosheets is explored for the first time. The nanocomposite demonstrated splendid specificity for nonenzymatic electrochemical detection of uric acid (UA) in biological samples. It was synthesized using the coprecipitation method and thoroughly characterized. The presence of functional groups and disorder in the as-synthesized nanocomposite are confirmed using Fourier transform infrared spectroscopy and Raman spectroscopy. Furthermore, field emission scanning electron microscopy, high-resolution transmission electron microscope, X-ray powder diffraction, and X-ray photoelectron spectroscopy provides a clear understanding of the morphology, coexisting phases, and elemental composition of the as-synthesized nanocomposites. The differential pulse voltammetry technique was utilized to elaborate the electrochemical sensing of UA using a GdS-Gd2O3/C-MWCNT modified glassy carbon electrode (GCE), The sensor showed an enhanced current response by more than 2-fold compared to bare GCE. Also, the sensor's performance was further improved by dispersing the nanocomposite in an ionic liquid with the exceptional reproducibility (SD = 0.0025, n = 3). The fabricated UA sensor GdS-Gd2O3/C-MWCNT/IL/GCE demonstrated a wide linear detection range from 0.5-30 μM and 30-2000 μM, effectively covering the entire physiological range of UA in biological fluids with a limit of detection (LOD) of 0.380 μM (+3SD of blank) and a sensitivity of 356.125 μA mM-1 cm-2. Moreover, the electrodes exhibited storage stability for 2 weeks with decrease in zero-day current by only 4.5%. The sensor was validated by quantifying UA in 12 unprocessed clinical human urine and serum samples, and its comparison with the gold standard test yielded remarkable results (p < 0.05). Hence, the proposed nonenzymatic electrochemical UA sensor is selective, sensitive, reproducible, and stable, making it reliable for point-of-care diagnostics.

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  • 10.1039/d4ra05537c
Electrochemical sensors based on the composite of reduced graphene oxide and a multiwalled carbon nanotube-modified glassy carbon electrode for simultaneous detection of hydroquinone, dopamine, and uric acid.
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Using a simple drop-casting technique, we successfully fabricated a sensitive electrochemical sensor based on the composite of reduced graphene oxide (RGO) and multiwalled carbon nanotubes (MWCNT) deposited on the surface of a glassy carbon electrode (GCE) for individual and simultaneous measurements of hydroquinone (HQ), dopamine (DA), and uric acid (UA). The nanocomposite of RGO/MWCNT was further characterized in terms of its structural properties, surface morphology, and topography using Raman, FT-IR spectroscopy, SEM, HRTEM, and AFM. Then, the proposed sensor for simultaneous measurement of HQ, DA, and UA based on RGO/MWCNT-modified GCE was investigated for its electrochemical behavior and electroanalytical performances using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). In addition, the composition ratio between RGO and MWCT was 1 : 1 showing the highest electrochemical response for simultaneous detection of HQ, DA, and UA. Owing to the synergistic effect between RGO and MWCNT leading to excellent conductivity properties, the proposed sensor exhibited improved electrochemical response at pH 7 toward the oxidation processes of HQ, DA, and UA on the surface of modified electrode. The proposed sensor demonstrated three well-defined anodic peaks of these analytes with their linear concentrations ranges of 3.0-150.0 μM for HQ, 4.0-100.0 μM for DA, and 2.0-70.0 μM for UA. The limit of detection values for the simultaneous detection of HQ, DA, and UA were found as follows 0.400 ± 0.014, 0.500 ± 0.006, and 0.300 ± 0.016 μM, respectively. The additional features of this proposed sensor are high reproducibility and stability for the simultaneous detection of HQ, DA, and UA with negligible interference effect from interferents such as Mg2+, K+, Cl-, ascorbic acid, and glucose. An acceptable percentage of recovery was also shown by this sensor for simultaneous measurements of HQ, DA, and UA using 6 samples of human urine. In summary, the RGO/MWCNT nanocomposite has been shown to be a promising platform for rapid, simple, and reliable determination of simultaneous measurements of HQ, DA, and UA in practical applications.

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  • Research Article
  • Cite Count Icon 79
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Electrochemical Detection of Uric Acid on Exfoliated Nanosheets of Graphitic-Like Carbon Nitride (g-C3N4) Based Sensor
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Electrode fouling is a daunting challenge during the electrochemical detection of uric acid (UA), particularly in complex biological environments. Herein, silanized reduced graphene oxide was explored as an antifouling platform to modify glassy carbon electrode (GCE) for the electrochemical detection of UA. Silanization imparts less polarity to the rGO surface upon introducing bulky siloxane groups that effectively minimizes non-specific adsorption of biomolecules. In order to evaluate the impact of different silane molecules on the antifouling performance, three different silanes, namely, triethoxymethylsilane (TEMS), dodecyltrimethoxysilane (DTMS), and trimethoxyphenylsilane (TMPS), were employed individually for rGO functionalization. Of these modified electrodes, rGO-TEMS/GCE and rGO-TMPS/GCE showed superior electrochemical responses toward UA, with rGO-TMPS/GCE exhibiting enhanced resistance to both electrochemical fouling and biofouling. rGO-TMPS/GCE maintained a stable current response after 1 h of incubation in a solution containing effective foulants such as bovine serum albumin (BSA) and cytochrome c (Cyt c). As a result, rGO-TMPS/GCE was further employed for the detection of UA by differential pulse voltammetry (DPV). The modified electrode exhibited a limit of detection of 0.76 μM ± 0.14 (N = 3), with a sensitivity of 1.04 μA μM-1 cm-2. These results emphasize the usefulness of rGO-TMPS/GCE as an effective antifouling electrode material for the stable and sensitive detection of UA.

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A Nicotinamide Adenine Dinucleotide Dispersed Multi-walled Carbon Nanotubes Electrode for Direct and Selective Electrochemical Detection of Uric Acid.
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A nanocomposite platform built with multi-walled carbon nanotubes (MWCNTs) and nicotinamide adenine dinucleotide (NAD(+)) via a noncovalent interaction between the large π systems in NAD(+) molecules and MWCNTs on a glassy carbon substrate was successfully developed for the sensitive and selective detection of uric acid (UA) in the presence of ascorbic acid (AA), dopamine (DA). NAD(+) has an adenine subunit and a nicotinamide subunit, which enabled interaction with the purine subunit of UA through a strong π-π interaction to enhance the specificity of UA. Compared with a bare glassy carbon electrode (GCE) and MWCNTs/GCE, the MWCNTs-NAD(+)/GCE showed a low background current and a remarkable enhancement of the oxidation peak current of UA. Using differential pulse voltammetry (DPV), a high sensitivity for the determination of UA was explored for the MWCNTs-NAD(+) modified electrode. A linear relationship between the DPV peak current of UA and its concentration could be obtained in the range of 0.05 - 10 μM with the detection limit as low as 10 nM (S/N = 3). This present strategy provides a novel and promising platform for the detection of UA in human urine and serum samples.

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A selective determination of levodopa (LD) in the presence of ascorbic acid (AA) and uric acid (UA) has been investigated at a glassy carbon electrode modified with reduced graphene oxide (rGO). The graphene oxide was synthesized chemically by Hummers method and characterized by energy-filtered transmission electron microscopy (EF-TEM). The reduced graphene oxide modified glassy carbon electrode (rGO/GCE) showed excellent electrochemical performance in the simultaneous electrochemical detection of LD, AA, and UA due to the unique properties of graphene, such as large surface area, facile electronic transport and high electrocatalytic activity. The redox characteristics of rGO/GCE were investigated with cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Well-resolved oxidation peak potentials, corresponding to the oxidation of AA, LD, and UA, were observed from their mixture solution at 0.098, 0.285, and 0.423 V, respectively. The rGO/GCE showed that LD can be detected without the interference of AA and UA. Under the optimized conditions, the oxidation peak current of LD is linear with the concentration of LD from 2.0 to 100 μM with the detection limit of 1.13 μM (S/N = 3). The present electrode system was also successfully applied to direct determination of LD in commercially available tablets and urine samples.

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An electrochemical sensor is described for determination of uric acid (UA). Carbon-enwrapped nickel nanoparticles (Ni@BC) were coated with polydopamine (PDA) that was molecularly imprinted with UA. The biomass carbon (BC) was synthesized by one-step solid-state pyrolysis from leaves of Firmiana platanifolia. The imprinted polymer was obtained by electrodeposition of DA as the monomer. The amount of monomer, the scan cycles, pH value and adsorption time were optimized. Furthermore, the selectivity of the MIP for UA on a glassy carbon electrode (GCE) was evaluated by selectivity tests. The differential pulse voltammetric responses to UA with and without interferents were consistent. The modified GCE has a linear response in the 0.01-30μM UA concentration range, and the limit of detection is 8nM. The MIP electrode was applied to the analysis of UA in urine for which the initial concentrations were determined by the phosphotungstic acid kit. Recoveries ranged from 91.3 to 113.4%, with relative standard deviations between 1.3 and 9.7% (n= 3). Graphical abstract Schematic presentation of electrochemical detection of uric acid by molecularly imprinted polydopamine modified with nickel nanoparticles wrapped with carbon (Ni@BC-MIP).

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Non-Enzymatic Electrochemical Detection for Uric Acid Based on a Glassy Carbon Electrode Modified With MOF-71
  • Jan 1, 2020
  • IEEE Sensors Journal
  • Syauqi Abdurrahman Abrori + 7 more

The development of non-noble-metal sensing material for sensitive and selective detection of uric acid with a simple material synthesis technique has not been frequently reported in recent years. Taking advantage of the unique properties of highly porous materials of Metal-Organic Frameworks, which incomparable in their structural diversity and tunability as well as their range of chemical and physical properties, open up a chance for developing novel nanomaterial for electrochemical sensor applications. In this article, we evaluated MOF-71 as a sensing material on a glassy carbon electrode (GCE) in a three-electrode system for electrochemical detection of uric acid. The MOF-71 was synthesized by a simple solvothermal method. Its structural characteristics that are examined by scanning electron microscopy and X-ray diffraction confirmed the successful formation of MOF-71. Cyclic voltammetry (CV) and differential pulse voltammetry DPV) analysis showed the successful uric acid detection in a phosphate buffer solution and showed good electrochemicalcatalytic activity toward uric acid. DPV was selected for the determination of uric acid with a sensitivity of 0.4811 mA.mM <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-1.</sup> cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-2</sup> , the detection range of 50.0-1000 μM, and detection limit of 15.61 μM at an S/N = 3.

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