Non-enzymatic Sensor Research Articles

A Multi-Channel Handheld Diagnostic Device Based on Green Biomimetic Material for Point-of-Care Testing of Vitamin C in Human Fluids.

In the era of "Great Health", maintaining an appropriate level of vitamin C is crucial for human health as it directly impacts the proper functioning of the immune system. In this study, a handheld nonenzymatic electrochemical sensor based on biomimetic material prussian blue functionalized polydopamine is proposed for point-of-care testing (POCT) of vitamin C in human fluids. Particularly, Prussian blue, known as a bio-antidote, and polydopamine, a main component of cuttlefish ink, ensure the safety and reliability of home testing. The experimental results quantitatively demonstrate that this electrochemical POCT sensor enables rapid and accurate determination of vitamin C with a wide linear detection range from 0.2 to 200µm, a low limit of detection at 0.03µm, and high sensitivity at 0.33µAµm-1cm-2. More importantly, the performance evaluation using human urine and saliva samples confirms satisfactory accuracy and recovery rates for vitamin C determination by this electrochemical POCT sensor. Thus, the proposed handheld electrochemical POCT sensor holds potential utility as an affordable tool for VC determination and home-based healthcare.

Flexible Non-Enzymatic Glucose Sensors: One-Step Green Synthesis of NiO Nanoporous Films via an Electro-Exploding Wire Technique.

In this study, we successfully synthesized nickel oxide (NiO) nanoparticles (NPs), i.e., samples NiO 24V, NiO 36V, and NiO 48V, via an environmentally friendly one-step electro-exploding wire technique by employing three distinct voltage levels of 24, 36, and 48 V, respectively. Sample NiO 48V showed the most rugged surface and smallest particle size, which helped to enhance electrocatalytic properties. The highest Ni3+ content of sample NiO 48V contributed to the increasing redox current and rendering highly enhanced chemical reactions and thereby improving their electrochemical properties and electrocatalytic performance in the glucose oxidation processes in alkaline (0.1 M NaOH, pH = 13) media. The NiO 48V electrode showcased an excellent linear detection range spanning from 0.1 to 1 mM, featuring a remarkable sensitivity of 1202 μA mM-1 cm-2 and an exceptionally low limit of detection (LOD) value of 0.25 μM. Remarkably, NiO NPs exhibited exceptional long-term stability, commendable reproducibility, favorable repeatability, and outstanding selectivity. This study also highlights the excellent operational performance of the NiO 48V electrode in real-world samples, such as commercially available beverages and human urine, highlighting the practical nature of these nonenzymatic sensors in real-life scenarios for the food industries, clinical diagnostics, and biotechnology applications.

An Enzyme-Free Impedimetric Sensor Based on Flower-like NiO/Carbon Microspheres for L-Glutamic Acid Assay

This research introduces a non-enzymatic electrochemical sensor utilizing flower-like nickel oxide/carbon (fl-NiO/C) microspheres for the precise detection of L-glutamic acid (LGA), a crucial neurotransmitter in the field of healthcare and a frequently utilized food additive and flavor enhancer. The fl-NiO/C were synthesized with controllable microstructures using metal–organic frameworks (MOFs) as precursors followed by a simple calcination process. The uniformly synthesized fl-NiO/C microspheres were further characterized using Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), and field emission scanning electron microscopy (FE-SEM). The fl-NiO/C was utilized as a modifier on the surface of a glassy carbon electrode, and an impedimetric sensor based on electrochemical impedance spectroscopy (EIS) was developed for the detection of LGA. The proposed sensor demonstrated excellent catalytic activity and selectivity towards LGA across a broad concentration range of 10–800 μM with a sensitivity of 486.9 µA.mM−1.cm−2 and a detection limit of 1.28 µM (S/N = 3). The sensor was also employed to identify LGA in blood plasma samples, yielding results that align with those obtained through HPLC. This achievement highlights the potential of fl-NiO/C microspheres in advancing cutting-edge biosensing applications.

In-situ Electrochemical Synthesis of Ni/Ni(OH)2/Molecularly Imprinted Polymer Nanocomposite for High-Performance Glucose Detection

This study presents a novel non-enzymatic glucose sensor that synergistically combines the high catalytic activity of nickel hydroxide (Ni(OH)2) with the selective recognition of molecularly imprinted polymers (MIPs). The sensors were fabricated through an entirely in-situ synthesis directly on the electrode, comprising electrodeposition and oxidation of Ni/Ni(OH)2 nanoparticles and electropolymerization of a glucose-imprinted MIP layer using pyrrole and 3-aminophenyl boronic acid. The integrated MIP layer significantly enhanced selectivity against common interferents while amplifying glucose sensitivity. The resulting sensor demonstrated a high sensitivity of 1802 μA mM-1 cm-2 with a linear range from 0.04 to 2.6mM. Notably, the sensor exhibited remarkable stability, retaining 97.2% of its original sensitivity after 6 months of room-temperature storage. To extend the linear range, Nafion coatings at two concentrations were applied, achieving ranges up to 0.04 – 11.6mM with adjusted sensitivities. This innovative approach, leveraging MIPs to provide selectivity to electrocatalytic nanomaterials, offers a promising strategy for developing high-performance non-enzymatic sensors for glucose and other biomolecules in diabetes monitoring and beyond.

Ruthenium(II) N-heterocyclic carbene polymer based sensors for detection of predatory drugs like ketamine and scopolamine.

The current demand in the field of abusive drug research is to have a highly sensitive and rapid method for detecting ketamine and scopolamine, which are frequently used in drug-facilitated sexual assaults administered via beverages and food. We report here the first electrochemical sensors of N-heterocyclic carbene (NHC) coordinated ruthenium organometallic 1-dimensional polymers and their multi-walled carbon nano tube (MWCNT)-based composite for detecting ketamine and scopolamine. The preparation of ruthenium NHC organometallics and the MWCNT composite as sensors offers significant advantages for electrochemical applications, with enhanced sensitivities of 121.979 and 3.273 μA μM-1 cm-2 for ketamine and scopolamine, respectively, and selectivity in sensing applications. The complex-carbon composite sensor has a low limit of detection i.e., 0.194 and 3.18 nM for ketamine and scopolamine identification, respectively. Alongside, the selectivity of the composite sensor was evaluated in the presence of other blood constituents, and the study evidenced remarkable discernment towards the title drugs. Furthermore, real-time analyses using the composite sensor demonstrated quantitative identification of ketamine and scopolamine. Therefore, this innovation has the potential to provide valuable tools for forensic investigations and address the urgent need for real-time detection of date rape drugs. This contribution demonstrates a robust proof-of-concept that emphasizes the importance of creating non-enzymatic, environmentally friendly, and cost-effective sensors for on-site sensing applications as point-of-care devices.

An electrochemical sensor for simultaneous voltammetric detection of ascorbic acid and dopamine enabled by higher electrocatalytic activity of co-modified MCM-41 mesoporous molecular sieve

It is of great value to develop effective methods for accurately and simultaneously detecting ascorbic acid (AA) and dopamine (DA) in the field of biochemistry. This work reports a nonenzymatic electrochemical sensor for the simultaneous detection of AA and DA by employing a Co-modified MCM-41 (CoMCM-41) mesoporous molecular sieve as an efficient electrocatalytic material, which was synthesized by a two-step hydrothermal method. Subsequently, the high structural organization of the CoMCM-41 mesoporous structure was characterized, and the electrocatalytic performance of CoMCM-41 toward AA and DA oxidation was then evidenced by the catalytic effect of different electrodes modified with or without CoMCM-41. By virtue of the superior electrocatalytic activity of the CoMCM-41, a much wider peak potential difference (ΔEpa) of 310 mV was obtained for the oxidation of AA and DA in their mixture solution, and the parameters that influenced the electrochemical signals of the modified electrode were also optimized. Under optimal conditions, a good linear response to AA and DA was observed on the CoMCM-41 modified electrode. For individual detection of AA and DA, the linear ranges were 7 ~ 105 μM and 5 ~ 110 μM respectively, while the linear response range was 20 ~ 100 μM for simultaneous detection of AA and DA. Satisfactory recovery results were obtained when the fabricated sensor was applied to determine AA in orange juice and DA in madopar pill samples.

Polymer organic framework-based ratiometric fluorescent probe for non-enzymatic glucose detection

Fluorescent pyrene-based polymer organic frameworks (POFs) PY-POFs were designed and synthesized by a facile solvothermal route for glucose detection, employing melamine, aromatic dialdehydes, 1-pyrenecarboxaldehyde, and phenylboronic acid as building blocks. The structure and photophysical properties of as-prepared POFs were systematically characterized via Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, N2 adsorption isotherms and fluorescence spectroscopy. The PY-POFs possessed intrinsic microporosity derived from extensively interlinked aminal structures, boasting specific surface areas reaching 192 m²/g, pore volumes extending to 0.8079 cm³/g, pore diameters of up to 17 nm, and an average particle dimension of ∼ 31 nm. In addition, the PY-POFs exhibited a dual-wavelength emission of pyrene excimer (λem = 472 nm) and monomer (λem = 382, 400, and 422 nm). When exposed to glucose, the former emission decreased while the latter increased, corresponding to the conformational transition of pyrene molecule from excimer to monomer. The non-enzymatic ratiometric fluorescent sensor displayed remarkable sensitivity towards glucose within 10−200 μM range, with a limit of detection (LOD) of 5.6 µM. Moreover, the glucose detection ability of PY-POFs was also in vivo demonstrated within zebrafish. Application of this sensor to real samples such as human saliva and DMEM biological matrix presented satisfactory results and good reproducibility. These results indicate that the fluorescent glucose sensor PY-POFs have broader prospects for utilization within biological studies.

Non-enzymatic electrochemical detection of sarcosine in serum of prostate cancer patients by CoNiWBO/rGO nanocomposite

Selective and sensitive sarcosine detection is crucial due to its recent endorsement as a prostate cancer (PCa) biomarker in clinical diagnosis. The reduced graphene oxide-cobalt nickel tungsten boron oxides (CoNiWBO/rGO) nanocomposite is developed as a non-enzymatic electrochemical sensor for sarcosine detection in PCa patients’ serum. CoNiWBO/rGO is synthesized by the chemical reduction method via a one-pot reduction method followed by calcination at 500 °C under a nitrogen environment for 2 h and characterized by UV-Vis, XRD, TGA, and SEM. CoNiWBO/rGO is then deposited on a glassy carbon electrode, and sarcosine sensing parameters are optimized, including concentration and pH. This non-enzymatic sensor is employed to directly determine sarcosine in serum samples. Differential pulse voltammetry (DPV) and linear sweep voltammetry (LSV) are employed to monitor the electrochemical behavior where sarcosine binding leads to oxidation. Chronoamperometric studies show the stability of the developed sensor. The results demonstrate a wide linear range from 0.1 to 50 µM and low limits of detection, i.e., 0.04 µM and 0.07 µM using DPV and LSV respectivel. Moreover, the calculated recovery of sarcosine in human serum of prostate cancer patients is 78–96%. The developed electrochemical sensor for sarcosine detection can have potential applications in clinical diagnosis.

Gold Nanoparticle-Embedded Thiol-Functionalized Ti3C2Tx MXene for Sensitive Electrochemical Sensing of Ciprofloxacin.

The unregulated use of ciprofloxacin (CIPF) has led to increased resistance in patients and has threatened human health with issues such as digestive disorders, kidney disorders, and liver complications. In order to overcome these concerns, this work introduces a portable electrochemical sensor based on a disposable integrated screen-printed carbon electrode (SPCE) coated with gold nanoparticle-embedded thiol-functionalized Ti3C2Tx MXene (AuNPs-S-Ti3C2Tx MXene) for simple, rapid, precise, and sensitive quantification of CIPF in milk and water samples. The high surface area and electrical conductivity of AuNPs are maximized thanks to the strong interaction between AuNPs and SH-Ti3C2Tx MXene, which can prevent the aggregation of AuNPs and endow larger electroactive areas. Ti3C2Tx MXene was synthesized from Ti3AlC2 MAX phases, and its thiol functionalization was achieved using 3-mercaptopropyl trimethoxysilane. The prepared AuNPs-S-Ti3C2Tx MXene nanocomposite was characterized using FESEM, EDS, XRD, XPS, FTIR, and UV-visible spectroscopy. The electrochemical behavior of the nanocomposite was examined using CV, EIS, DPV, and LSV. The AuNPs-S-Ti3C2Tx MXene/SPCE showed higher electrochemical performances towards CIPF oxidation than a conventional AuNPs-Ti3C2Tx MXene/SPCE. Under the optimized DPV and LSV conditions, the developed nonenzymatic CIPF sensor displayed a wide range of detection concentrations from 0.50 to 143 μM (DPV) and from 0.99 to 206 μM (LSV) with low detection limits of 0.124 μM (DPV) and 0.171 μM (LSV), and high sensitivities of 0.0863 μA/μM (DPV) and 0.2182 μA/μM (LSV).

ZnFe(PBA)@Ti3C2Tx nanohybrid-based highly sensitive non-enzymatic electrochemical sensor for the detection of glucose in human sweat

The ZnFe prussian blue analogue [ZnFe(PBA)] was infused with Ti3C2Tx (MXene) denoted as ZnFe(PBA)@Ti3C2Tx and was prepared by an in-situ sonication method to use as a non-enzymatic screen printed electrode sensor. The advantage of non-enzymatic sensors is their excellent sensitivity, rapid detection, low cost and simple design. The synthesized ZnFe(PBA)@Ti3C2Tx was characterized for its physical and chemical characterization by XRD, Raman, XPS, EDAX, and FESEM analysis. It possessed multiple functionalized layers and a cubic structure in the nanohybrid. Further, the sensor was investigated by using electroanalytical studies such as cyclic voltammetry and chronoamperometry analysis. The enhanced surface area with a cubic structure of ZnFe(PBA) and the excellent electrical response of Ti3C2 nanosheet support the advancement of a non-enzymatic electrochemical glucose sensor with improved sensitivity of 973.42 µA mM−1 cm−2 with the limit of detection (LOD) of 3.036 µM (S/N = 3) and linear detection range (LDR) from 0.01 to 1 mM.

Fabrication of a novel non-enzymatic glucose sensor based on ruthenium supported by a combination of PBA nanocubes and MOF nanosheets

The development of novel catalysts with high catalytic activity is of high importance of electrochemical non-enzymatic glucose sensing. Herein, a sensitive non-enzymatic electrochemical sensor (Ru@NiCo-MOF/NiFe-PBA) has been synthesized using a fast, simple and eco-friendly method. The high stability of PBA and the large specific surface area (two-dimensional nanosheet structure) of MOF support the excellent electrochemical performance, while the incorporation of the highly active metal Ru enhances the electrochemical activity even more. The results reveal that the sensitivities of the sensor are 1070.77 and 487.62 μA mM−1 cm−2, corresponding to linear ranges of 0.01–0.67 mM and 0.67–5.07 mM, respectively. Meanwhile, the sensor has a low detection limit (0.446 μM) and a short response time (2 s), making it a strong candidate for non-enzymatic glucose sensors. The successful detection of glucose in saliva further demonstrates its potential for practical applications. Therefore, Ru@NiCo-MOF/NiFe-PBA will make an impact in the field of glucose monitoring and detection.

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.

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.

Evaluation of electrodeposition synthesis of gold nanodendrite on screen-printed carbon electrode for nonenzymatic ascorbic acid sensor

Gold nanodendrite (AuND) is a type of gold nanoparticles with dendritic or branching structures that offers advantages such as large surface area and high conductivity to improve electrocatalytic performance of electrochemical sensors. AuND structures can be synthesized using electrodeposition method utilizing cysteine as growth directing agent. This method can simultaneously synthesize and integrate the gold nanostructures on the surface of the electrode. We conducted a comprehensive study on the synthesis of AuND on screen-printed carbon electrode (SPCE)-based working electrode, focusing on the optimization of electrodeposition parameters, such as applied potential, precursor solution concentration, and deposition time. The measured surface oxide reduction peak current and electrochemical surface area from cyclic voltammogram were used as the optimization indicators. We confirmed the growth of dendritic gold nanostructures across the carbon electrode surface based on FESEM, EDS, and XRD characterizations. We applied the SPCE/AuND electrode as a nonenzymatic sensor on ascorbic acid (AA) and obtained detection limit of 16.8 μM, quantification limit of 51.0 μM, sensitivity of 0.0629 μA μM−1, and linear range of 180–2700 μM (R2 value = 0.9909). Selectivity test of this electrode against several interferences, such as uric acid, dopamine, glucose, and urea, also shows good response in AA detection.

Functional diversification within the heme-binding split-barrel family

Due to neofunctionalization, a single fold can be identified in multiple proteins that have distinct molecular functions. Depending on the time that has passed since gene duplication and the number of mutations, the sequence similarity between functionally divergent proteins can be relatively high, eroding the value of sequence similarity as the sole tool for accurately annotating the function of uncharacterized homologs. Here, we combine bioinformatic approaches with targeted experimentation to reveal a large multi-functional family of putative enzymatic and non-enzymatic proteins involved in heme metabolism. This family (homolog of HugZ (HOZ)) is embedded in the “FMN-binding split barrel” superfamily and contains separate groups of proteins from prokaryotes, plants, and algae, which bind heme and either catalyze its degradation or function as non-enzymatic heme sensors. In prokaryotes these proteins are often involved in iron assimilation, whereas several plant and algal homologs are predicted to degrade heme in the plastid or regulate heme biosynthesis. In the plant Arabidopsis thaliana, which contains two HOZ subfamilies that can degrade heme in vitro (HOZ1 and HOZ2), disruption of AtHOZ1 (AT3G03890) or AtHOZ2A (AT1G51560) causes developmental delays, pointing to important biological roles in the plastid. In the tree Populus trichocarpa, a recent duplication event of a HOZ1 ancestor has resulted in localization of a paralog to the cytosol. Structural characterization of this cytosolic paralog and comparison to published homologous structures suggests conservation of heme-binding sites. This study unifies our understanding of the sequence-structure-function relationships within this multi-lineage family of heme-binding proteins and presents new molecular players in plant and bacterial heme metabolism.

Dibenzosuberenone-based non-enzymatic electrochemical sensors

Dibenzosuberenone-based non-enzymatic electrochemical sensors

Study on the performance of MoS2/Au composites for non-enzymatic electrochemical glucose detection

Abstract Glucose concentration is considered an indicator for the diagnosis of diabetes, highlighting the importance of accurate glucose detection. Non-enzymatic electrochemical sensors have been extensively studied for glucose detection applications, with nanocomposites composed of molybdenum disulfide (MoS2) and gold nanoparticles (Au NPs) demonstrating high catalytic activity. In this study, a nanocomposite material composed of MoS2 and Au NPs (MoS2/Au) was synthesized and employed to construct a non-enzymatic electrochemical glucose biosensor. The detection limit of this sensor was explored, reaching as low as 1 mM. Additionally, compared to MoS2, the MoS2/Au nanocomposite exhibited a higher linear correlation coefficient and sensitivity, with a linear range of 1–25 mM and a sensitivity of 417.556 μA mM−1 cm−2. The sensor demonstrated excellent performance within the range of human blood glucose concentrations, showing potential for real-time monitoring and precise measurement of glucose levels. Furthermore, it exhibited good stability and reproducibility. These findings indicate the potential applications of MoS2/Au in biosensors and immunoassays.

Corrigendum to “Surface modification of transition metals (TM: Mn, Fe, Co) decorated Pt-doped carbon quantum dots (Pt@CQDs) nanostructure as nonenzymatic sensors for nitrotyrosine (a biomarker for Alzheimer): Perspective from density functional theory” [Mater. Sci. Semicond. Process. 174 (2024) 108245]

Corrigendum to “Surface modification of transition metals (TM: Mn, Fe, Co) decorated Pt-doped carbon quantum dots (Pt@CQDs) nanostructure as nonenzymatic sensors for nitrotyrosine (a biomarker for Alzheimer): Perspective from density functional theory” [Mater. Sci. Semicond. Process. 174 (2024) 108245]

Template-synthesizing hollow cubic CeO2/Co3O4 heterostructure as electrocatalysts for sensing hydrogen peroxide

H2O2 as an important intermediary is becoming more widely acknowledged, and interest in its detection has increased significantly. Herein, we developed a hollow cubic CeO2/Co3O4 heterostructure and further employed as non-enzymatic H2O2 detection sensor through a series of facile synthesis strategies using cobalt-based zeolitic imidazolate framework as a template. The synthesized CeO2/Co3O4 with huge cavity structure offers numerous electrocatalytic active sites for the target analyte, thus endowing its high sensitivity (60.5 μA. mM−1cm−2), excellent selectivity, broad detection range for H2O2 (10 μM -1 mM), and favorable working potential (-0.45 V). Not only that the CeO2/Co3O4 sensor achieved satisfactory recovery and accuracy in real lake-water samples.

ZnO/NiFe2O4 heterostructure on nickel foam for the electrochemical detection of uric acid

In this study, heterostructures containing hydrothermally derived ZnO and combustion derived NiFe2O4 were co-deposited on nickel foam (NF) substrate. The modification of NF based substrate with the synthesised electrocatalysts is capable of increasing the electrochemically active surface area (ECSA) due to its porous network. The fabricated ZnO@NF, NiFe2O4@NF and ZnO/NiFe2O4@NF electrodes were tested in phosphate buffer saline (PBS) (pH = 7.4 ± 0.2) to understand their chemical kinetics which reveals a diffusion-controlled process. A comparative study reveals that the presence of surface charges on ZnO/NiFe2O4@NF electrode, influences the selectivity by enhancing the sensitivity towards UA which is attributed to the low charge transfer resistance and its higher ECSA of 1.487 cm2. The linear response current was observed between 0.52 mM and 1.48 mM with a detection limit (LOD) of 8.22 μM and limit of quantification (LOQ) of 27.4 μM. The sensitivity was found to be 2.31 mA.mM−1cm−2. The main advantages of ZnO/NiFe2O4@NF electrode is its simple fabrication technique which is inexpensive, stability over a period of 13 days with current loss of ∼19.2 %. The proposed ZnO/NiFe2O4 based non-enzymatic UA sensor is capable of selectively detecting UA in the presence of various interferents. UA acts as a biomarker for the diagnosis of different stages of chronic kidney disease (CKD). Hence, the validity of the developed heterostructure was investigated for real time UA sensing using spot urine samples. The recovery percentage was found to be between 95.7 % and 103.5 % further paving way for the use of this electrode for diagnosis of CKD.

Biosensor Based on ZIF-67-HRP and MWCNTs Nanocomposite Modified Glass Carbon Electrode for the Detection of Luteolin in Vegetables.

Luteolin has various pharmacological properties, including anti-inflammatory, antioxidant, and antitumor characteristics. Due to its potential value in drugs and functional foods, it is important to develop an efficient method for detecting luteolin. In this work, the poor selectivity of existing luteolin nonenzymatic sensors was solved by translating the enzyme-catalyzed reaction from bulk solution to the surface of a horseradish peroxidase (HRP) modified electrode through an electrocatalytic oxidation process. Here, we modified the surface of a glassy carbon electrode (GCE) with metal-organic frameworks (MOFs; ZIF-67 here, abbreviated as ZIF), functional nanomaterials, and HRP and finally covered it with Nafion (NF). In this case, luteolin acts as a hydrogen donor, and the electrode acts as a hydrogen acceptor; the oxidation reaction occurs on the electrode surface. The use of ZIF-67 ensured the conformational stability of HRP to ensure the selectivity and anti-interference property, and SDS-dispersed multiwalled carbon nanotubes (MWCNTs) enhanced the electrode conductivity. The use of NF avoids shedding of the electrode material during the testing process. A UV-vis spectrophotometer was used to study the selectivity of luteolin by HRP and the compatibility between HRP and ZIF. The materials were characterized and analyzed by scanning electron microscopy and transmission electron microscopy. Due to the synergistic effect of these nanomaterials, the linear range of NF/ZIF-HRP/MWCNTs-SDS/GCE was 1.0 × 10-2 to 6.0 μM, with detection limits of 25.3 nM (S/N = 3). The biosensor showed long-term stability and reproducibility, with a relative standard deviation of 4.2% for the peak current (n = 5). Finally, the biosensor was successfully used to detect luteolin in carrots, celery, and cauliflower.