Nanostructured Iron Oxide Platform for Impedimetric Cholesterol Detection

A nanostructured iron oxide (NanoFe₃O₄, particle size ca. 25 nm and roughness ca. 21 nm) film deposited onto a hydrolyzed indium‐tin‐oxide (ITO) coated glass plate has been used to immobilize cholesterol oxidase (ChOx) to fabricate an impedimetric cholesterol sensor. Electrochemical studies reveal that surface charged Fe₃O₄ nanoparticles provide better conformation for ChOx loading resulting in enhanced electron transfer between ChOx and the electrode. Impedimetric response studies of the ChOx/NanoFe₃O₄/ITO bioelectrode exhibit improved linearity (2.5–400 mg/dL), low detection limit (0.25 mg/dL), fast response time (25 s), high sensitivity (86 Ω/mg dL^?1/cm^?2) and a low value of the Michaelis‐Menten constant (K_m, 0.8 mg/dL) with a regression coefficient of 0.997.     

Electrochemical Cholesterol Sensor Based on Tin Oxide‐Chitosan Nanobiocomposite Film

A chitosan (CS)‐tin oxide (SnO₂) nanobiocomposite film has been deposited onto an indium‐tin‐oxide glass plate to immobilize cholesterol oxidase (ChOx) for cholesterol detection. The value of the Michaelis–Menten constant (K_m) obtained as 3.8 mM for ChOx/CS‐SnO₂/ITO is lower (8 mM) than that of a ChOx/CS/ITO bioelectrode revealing enhancement in affinity and/or activity of ChOx towards cholesterol and also revealing strong binding of ChOx onto CS‐SnO₂/ITO electrode. This ChOx/CS‐SnO₂/ITO cholesterol sensor retains 95% of enzyme activity after 4–6 weeks at 4 °C with response time of 5 s, sensitivity of 34.7 μA/mg dL^?1 cm² and detection limit of 5 mg/dL.     

Chitosan-Modified Carbon Nanotubes-Based Platform for Low-Density Lipoprotein Detection

We have fabricated an immunosensor based on carbon nanotubes and chitosan (CNT-CH) composite for detection of low density lipoprotein (LDL) molecules via electrochemical impedance technique. The CNT-CH composite deposited on indium tin oxide (ITO)-coated glass electrode has been used to covalently interact with anti-apolipoprotein B (antibody: AAB) via a co-entrapment method. The biofunctionalization of AAB on carboxylated CNT-CH surface has been confirmed by Fourier transform infrared spectroscopic and electron microscopic studies. The covalent functionalization of antibody on transducer surface reveals higher stability and reproducibility of the fabricated immunosensor. Electrochemical properties of the AAB/CNT-CH/ITO electrode have been investigated using cyclic voltammetric and impedimetric techniques. The impedimetric response of the AAB/CNT-CH/ITO immunoelectrode shows a high sensitivity of 0.953?Ω/(mg/dL)/cm² in a detection range of 0–120 mg/dL and low detection limit of 12.5 mg/dL with a regression coefficient of 0.996. The observed low value of association constant (0.34 M^–1s^–1) indicates high affinity of AAB/CNT-CH/ITO immunoelectrode towards LDL molecules. This fabricated immunosensor allows quantitative estimation of LDL concentration with distinguishable variation in the impedance signal.     

Polyaniline/Single‐Walled Carbon Nanotubes Composite Based Triglyceride Biosensor

Nanocomposite film comprising of polyaniline (PANI) and single walled carbon nanotubes (SWCNT) has been fabricated onto indium‐tin‐oxide (ITO) coated glass plate using electrophoretic technique. Co‐immobilization of glycerol dehydrogenase (GDH) and lipase (LIP) has been done via N‐ethyl‐N′‐(3‐dimethylaminopropyl) carbodiimide and N‐hydroxysuccinimide chemistry to explore its application for triglyceride (tributyrin) sensing. Response studies have been done using linear sweep voltammetry revealing that LIP‐GDH/PANI‐SWCNT‐TB/ITO bioelectrode can detect tributyrin in the range of 50 to 400 mg dL^?1 with low Michaelis–Menten constant of 1.138 mM, improved response time of 12 s, high sensitivity as 4.28×10^?4 mA mg^?1 dL and storage stability of about 13 weeks.     

Electrochemical Study of Chitosan‐SiO2‐MWNT Composite Electrodes for the Fabrication of Cholesterol Biosensors

We report a novel composite electrode made of chitosan‐SiO₂‐multiwall carbon nanotube (CHIT‐SiO₂‐MWNT) composite coated on the indium‐tin oxide (ITO) glass substrate. Cholesterol oxidase (ChOx) was covalently immobilized on the CHIT‐SiO₂‐MWNT/ITO electrode that resulted in a ChOx/CHIT‐SiO₂‐MWNT/ITO cholesterolactive bioelectrode. The CHIT‐SiO₂‐MWNT/ITO and ChOx/CHIT‐SiO₂‐MWNT/ITO electrodes were characterized with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The influence of various parameters was investigated, including the applied potential, pH of the medium, and the concentration of the enzyme on the performance of the biosensor. The cholesterol bioelectrode exhibited a sensitivity of 3.4 nA/ mgdL^?1 with a response time of five seconds. The biosensor using ChOx/CHIT‐SiO₂‐MWNT/ITO as the working electrode retained its original response after being stored for six months. The biosensor using ChOx/CHIT‐SiO₂‐MWNT/ITO as the working electrode showed a linear current response to the cholesterol concentration in the range of 50–650 mg/dL.     

Rapid and Sensitive Electrochemical Detection of Carbaryl Based on Enzyme Inhibition and Thiocholine Oxidation Mediated by a Ruthenium(III) Complex

In the electrochemical detection method for pesticides that measures their inhibitory effects on acetylcholinesterases (AChEs), the direct electrooxidation of the enzyme product (thiocholine, SCh) is slow at conventional electrodes. To overcome this limitation, an electron mediator is required to lower the applied potential and facilitate the transfer of electrons between the enzyme product and electrode. In this study, [Ru(NH₃)₅py]³⁺ is introduced as an electron mediator in inhibition‐based pesticide detection. To obtain a better signal‐to‐background ratio, [Ru(NH₃)₅py]³⁺, which undergoes a fast outer‐sphere reaction, is combined with low‐electrocatalytic indium‐tin‐oxide (ITO) electrodes at which many interfering species undergo slow redox reactions. AChE is immobilized onto an avidin‐modified ITO electrode via the direct adsorption of avidin onto ITO followed by the biospecific binding of biotinylated AChE to the avidin. SCh is generated from acetylthiocholine by AChE. Subsequently, SCh converts [Ru(NH₃)₅py]³⁺ to [Ru(NH₃)₅py]²⁺, which is then oxidized at the ITO electrode. This procedure allows the sensitive detection of carbaryl at a low applied potential of 0.15 V vs Ag/AgCl. The calculated detection limit for carbaryl is approximately 0.3 pM. This simple and sensitive pesticide sensor is thus very promising and should be extendable to the onsite environmental monitoring of other pesticides.     

Peptide Nucleic Acid Immobilized Biocompatible Silane Nanocomposite Platform for Mycobacterium tuberculosis Detection

We have prepared nanocomposite films comprising of 3‐glycidoxypropyltrimethoxysilane (GOPS) and iron‐oxide (Fe₃O₄) onto indium‐tin‐oxide (ITO) glass plate for covalent immobilization of 21‐mer peptide nucleic acid (PNA). These films have been characterized using contact angle, atomic force microscopy (AFM), electrochemical techniques. The electrochemical response of the GOPS/ITO and Fe₃O₄‐GOPS/ITO electrodes has been investigated by hybridization with complementary, non‐complementary and one‐base mismatch using methylene blue as electrochemical indicator. The PNA/Fe₃O₄‐GOPS/ITO bioelectrode exhibits improved specificity and detection limit (0.1 fM) as compared to that of the PNA‐GOPS/ITO bioelectrode (0.1 pM). This PNA/Fe₃O₄‐GOPS/ITO electrode can be utilized for detection of hybridization with the complementary sequence in sonicated M. tuberculosis genomic DNA within 90 s of hybridization time.     

Supramolecular Assembly of β‐Cyclodextrin‐Capped Gold Nanoparticles on Ferrocene‐Functionalized ITO Surface for Enhanced Voltammetric Analysis of Ascorbic Acid

A supramolecular recognition functionalized electrode (βCD‐nanoAu/Fc‐ITO) which exhibits redox‐activity was prepared through supramolecular assembly of β‐cyclodextrin (βCD) capped gold nanoparticles (βCD‐nanoAu) on the ITO previously coated with a monolayer of ferrocene residues (Fc‐ITO). The immobilization of βCD‐nanoAu on Fc‐ITO was confirmed by atomic force microscopy (AFM), and the supramolecular nature of the immobilization approach was also confirmed by cyclic voltammetry. On the other hand, the electrocatalytic activity of βCD‐nanoAu/Fc‐ITO electrode was also studied. The electrocatalytic activity toward ascorbic acid (AA) was enhanced compared with that at the Fc‐ITO electrode, and a linear relationship existed between the anodic peak and the concentration of AA in the range of 5.3×10^?5 to 3.0×10^?3 M with a detection limit (S/N=3) of 4.1×10^?6 M.     

Biosensor for total cholesterol estimation using N-(2-aminoethyl)-3-aminopropyltrimethoxysilane self-assembled monolayer

Cholesterol oxidase (ChOx), cholesterol esterase (ChEt), and horseradish peroxidase (HRP) have been co-immobilized covalently on a self-assembled monolayer (SAM) of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTS) deposited on an indium–tin–oxide (ITO) glass surface. These enzyme-modified (ChOx-ChEt-HRP/AEAPTS/ITO) biosensing electrodes have been used to estimate cholesteryl oleate from 10 to 500 mg dL⁻¹. The sensitivity, K _m value, and shelf-life of these ChEt-ChOx-HRP/AEAPTS/ITO biosensing electrodes have been found to be 124 nA mg⁻¹ dL, 95.098 mg dL⁻¹ (1.46 mmol L⁻¹), and ten weeks, respectively. The ChEt-ChOx-HRP/AEAPTS/ITO bio-electrodes have been used to estimate total cholesterol in serum samples. Figure Covalent immobilization of enzymes onto AEAPTS/ITO surface using EDC/NHS chemistry Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Electrochemical Monitoring of Methotrexate Anticancer Drug in Human Blood Serum by Using in situ Solvothermal Synthesized Fe3O4/ITO Electrode

Here, we reported on a one‐step fabrication of magnetite Fe₃O₄ nanoparticles/indium tin oxide (ITO) electrode based on the direct growing of Fe₃O₄ nanoparticles on the ITO surface by using a solvothermal process. The modified electrode was used as electrochemical methotrexate (MTX) biosensor with high sensitivity based on cyclic voltammetry and square wave voltammetry techniques. The results demonstrated a linear relationship between the MTX concentration and its oxidation current peak over a wide range from 10^?5 to 10^?14 mole/L with a limit of detection of 0.4×10^?15 M based on the square wave voltammetry (SWV) technique. In addition, Fe₃O₄/ITO electrode showed a good capability for measuring very low concentrations of MTX drug dissolved in human serum solution. Also, Fe₃O₄/ITO electrode was used for detecting MTX in blood serum samples collected from patients after their treatment with MTX. The prepared electrode showed the higher sensitivity that higher than the Viva‐E instrument, which opens the door for developing a cheap, simple and higher sensitive MTX sensor.     

Electrochemical Synthesis of Chitosan‐co‐polyaniline/WO3⋅nH2O Composite Electrode for Amperometric Detection of NO2 Gas

An electrode of hydrated tungsten oxide (WO₃?nH₂O) embedded chitosan‐co‐polyaniline (CHIT‐co‐PANI) composite was electrochemically prepared on an indium tin oxide (ITO) coated glass surface using mineral acid as a supporting electrolyte. The resulting CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode was characterized using ultraviolet‐visible spectroscopy (UV‐vis), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and scanning electron microscopy (SEM). The composite electrode exhibited a three‐dimensional nanofibrous structure with the diameter of the nanofibers ranging from 20 to 100 nm. The CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode allowed for the low potential detection of NO₂ gas in acidic medium. The NO₂ gas sensing characteristics were studied by measuring change in the current with respect to concentration and time. Using the CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode, NO₂ gas was detected electrochemically without interference at pH 2.0 and 0.25 V vs. Ag/AgCl. The current of the electrochemical cell with the CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode decreased linearly with an increase in NO₂ gas concentration in a range from 100 to 500 ppb with a response time of eight seconds.     

Strategy for Low Background‐Current Levels in the Electrochemical Biosensors Using Horse‐Radish Peroxidase Labels

This article describes an electrochemical strategy to achieve low background‐current levels in horse‐radish peroxidase (HRP)‐based electrochemical immunosensors. The strategy consists of (i) the use of an HRP substrate/product redox couple whose formal potential is high and (ii) the use of an electrode that shows moderate electrocatalytic activity for the redox couple. The strategy is proved by a model biosensor using a catechol/o‐benzoquinone redox couple and an indium tin oxide (ITO) electrode. The combined effect of high formal potential and moderate electrocatalytic activity allows o‐benzoquinone electroreduction with minimal catechol electrooxidation and H₂O₂ electroreduction. The detection limit for mouse‐IgG is 100 pg/mL.     

Fabrication of a New Electrochemiluminescent Sensing Interface Based on Zinc Oxide Nanorod

A new electrochemiluminescence (ECL) sensing interface was established based on the zinc oxide nanorod in this paper. Firstly, the zinc oxide (ZnO) nanorod was prepared on an indium tin oxide (ITO) electrode surface by the method of constant current cathodic electrodeposition, on which the Nafion film was then modified, and finally ruthenium(II) tris(bipyridine) (Ru(bpy)₃²⁺) was immobilized at the ZnO nanorod/Nafion composite‐modified electrode. The sensing interface shows well ECL behaviors and perfect stability after being constant temperature treatment at 80 °C. The composite electrode was characterized by EIS, SEM and XRD. The results showed that the good stability maybe related to the water content of Nafion film.     

Molecularly imprinted orthophenylenediamine with Ti3C2TxMXene-based biosensor for sensitive detection of bilirubin

In this study, bilirubin (BR) is detected by using a novel molecularly imprinted electrochemical sensor based on a Ti₃C₂T_xMXene-modified ITO electrode. First, Ti₃C₂T_xMXene is synthesized by chemical etching and deposited at the ITO electrode surface by drop casting. After that, ortho-phenylenediamine (o-PD) as monomer is electropolymerized in the presence of a sodium acetate buffer solution containing the BR template to prepare BR-imprinted electrode. Field emission scanning electron microscopy (FESEM), x-ray diffraction and UV–visible absorption spectroscopy confirms the MXene synthesis. The molecular imprinted polymer (MIP) formation at the electrode is confirmed by electrochemical methods such as differential pulse voltammetry, electrochemical impedance spectroscopy, and cyclic voltammetry, and FESEM. The linearity range, limit of detection and the limit of quantification are calculated as 0.1 mg/dL to 20 mg/dL, 0.002 mg/dL, and 6.6 mg/dL respectively. Stability and reproducibility are also reported for the prepared MIP sensor.     

Electrocatalytic and Simultaneous Determination of Ascorbic Acid,Nicotinamide Adenine Dinucleotide and Folic Acid at Ruthenium(II) Complex‐ZnO/CNTs Nanocomposite Modified Carbon Paste Electrode

This paper describes the development a novel ruthenium(II) complex‐ZnO/CNTs modified carbon paste electrode (Ru(II)/ZnO/CNTs/CPE) for the electrocatalytic determination of ascorbic acid (AA). The objective of this novel electrode modification was to seek new electrochemical performances for the detection of AA, nicotinamide adenine dinucleotide (NADH) and folic acid (FA). The peak potentials recorded were 170, 500 and 830 mV vs. Ag/AgCl/KCl_sat for AA, NADH and FA, respectively. The peak currents were linearly dependent on AA, NADH and FA concentrations using square wave voltammetry (SWV) method at the ranges of 0.008–251, 1.0–650, and 3.0–700 µmol L^?1, with detection limits of 0.005, 0.5, and 1.0 µmol L^?1, respectively.     

Chitosan–iron oxide nanobiocomposite based immunosensor for ochratoxin-A

The rabbit immunoglobulin antibodies (IgGs) have been immobilized onto nanobiocomposite film of chitosan (CH)–iron oxide (Fe₃O₄₎ nanoparticles prepared onto indium–tin oxide (ITO) electrode for detection of ochratoxin-A (OTA). Excellent film forming ability and availability of –NH₂ group in CH and affinity of surface charged Fe₃O₄ nanoparticles for oxygen support the immobilization of IgGs. Differential pulse voltammettry (DPV) studies indicate that Fe₃O₄ nanoparticles provide increased electroactive surface area for loading of IgGs and improved electron transport between IgGs and electrode. IgGs/CH–Fe₃O₄ nanobiocomposite/ITO immunoelectrode exhibits improved characteristics such as low detection limit (0.5 ng dL⁻¹), fast response time (18 s) and high sensitivity (36 μA/ng dL⁻¹ cm⁻²) with respect to IgGs/CH/ITO immunoelectrode.     

Polyaniline nanotubes for impedimetric triglyceride detection

Polyaniline nanotubes (PANI-NT) based film electrophoretically deposited onto indium–tin–oxide (ITO) coated glass plate has been utilized for covalent immobilization of lipase (LIP), via glutaraldehyde (Glu), for triglyceride detection using impedimetric technique. It is shown that fatty acid molecules produced during triglyceride hydrolysis result in change in charge transfer resistance (R_CT) of PANI-NT film with varying triglyceride concentration. LIP/Glu/PANI-NT/ITO bioelectrode has linearity as 25–300 mg dL^?1, sensitivity as 2.59 × 10^?3 KΩ^?1 mg^?1 dL, response time as 20 s and regression coefficient as 0.99. A low value of apparent Michaelis–Menten constant (～0.62 mM) indicates high enzyme affinity to tributyrin. The LIP/Glu/PANI-NT/ITO bioelectrode has been utilized to estimate triglyceride in serum samples.     

A Glucose Biosensor Based on Immobilization of Glucose Oxidase into 3D Macroporous TiO2

3D macroporous TiO₂ inverse opals have been derived from a sol‐gel procedure using polystyrene colloidal crystals as templates. EDS and SEM showed a face‐centered cubic (FCC) structure TiO₂ inverse opal was obtained. Glucose oxidase (GOx) was successfully immobilized on the surface of indium‐tin oxide (ITO) electrode modified by TiO₂ inverse opal (TiO_2(IO)). Electrochemical properties of GOx/TiO_2(IO)/ITO electrode were characterized by using the three electrodes system. The result of cyclic voltammetry showed that a couple of stable and well‐defined redox peaks for the direct electron transfer of GOx in absence of glucose, and the redox peak height enhanced in presence of 0.1 μM glucose. Compare with the ordinary structured GOx/TiO₂/ITO electrode, inverse opal structured GOx/TiO_2(IO)/ITO electrode has a better respond to the glucose concentration change. Under optimized experimental conditions of solution pH 6.8 and detection potential at 0.30 V versus saturated calomel electrode (SCE), amperometric measurements were performed. The sensitivity and the detection limit of glucose detection was 151 μA cm^?2 mM^?1 and 0.02 μM at a signal‐to‐noise ratio of 3, respectively. The good response was due to the good biocompatibility of TiO₂ and the large effective surface of the three‐dimensionally ordered macroporous structure.     

A Novel Chemical Sensor Based on Sb2S3 Film for Highly Sensitive Detection of Hydrazine

The Sb₂S₃ film on indium‐tin oxide (ITO) substrate has been used as an efficient electron transfer mediator for the fabrication of novel chemical sensor towards hydrazine, which is a diamine known as neurotoxin and carcinogen. Sb₂S₃ film is deposited on ITO substrate by drop‐casting process using Sb₂S₃ solution as precursor and possesses reticular structure with the morphology of uniform hollow hemispheres. The fabricated chemical sensor for selective detection of hydrazine displays a high sensitivity of 106.25 μA/(mM cm²) with a low detection limit of 0.5 μM and it also exhibits excellent reproducibility and stability in hydrazine detection.     

Electrocatalysis of Horseradish Peroxidase Immobilized on Cobalt Nanoparticles Modified ITO Electrode

Abstract

It is the first time that Horseradish peroxidase (HRP) was successively immobilized on the magnetic cobalt nanoparticles modified ITO (indium tin oxide) electrode. Morphologies of electrode surface were featured by the field emission‐scanning electron microscope (FSEM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize the modified process of electrode. Direct electrochemistry and electrocatalysis of HRP immobilized on nano‐Co/ITO were investigated. The biosensor exhibited high sensitivity, good stability, and excellent electrocatalytic activity to the reduction of H₂O₂. Under the optimized experimental conditions, a calibration curve over 2.0×10^?9～2.0×10^?8 mol l^?1 and 2.0×10^?7～2.0×10^?6 mol l^?1, with a limit of detection of 1.9×10^?9 mol l^?1 was obtained. The apparent Michaelis‐Menten constant (K _M ^app ) for HRP/nano‐Co/ITO electrode was calculated to be 0.79 mmol l^?1, indicating a higher affinity of HRP attached on the modified electrode.