Flower‐like Ni(II)‐based Metal‐organic Framework‐decorated Ag Nanoparticles: Fabrication,Characterization and Electrochemical Detection of Glucose

Glucose concentration monitoring is important for the prevention, diagnosis and treatment of diabetes. In this work, a composite material of AgNPs/MOF‐74(Ni) was prepared for electrochemical determination of glucose. AgNPs/MOF‐74(Ni) was characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X‐ray photoelectron spectroscopy (XPS). The electrochemical properties of the glassy carbon electrodes modified with the AgNPs/MOF‐74(Ni) composites were characterized by cyclic voltammetry (CV) and current‐time curve (I‐t curve) with three electrode system. The determination of glucose with the electrode modified by AgNPs/MOF‐74(Ni) has a linear range of 0.01～4 mM with the correlation coefficient (R²) of 0.994. The detection limit is 4.7 μM (S/N=3) and the sensitivity is 1.29 mA ? mM^?1 ? cm^?2. In addition, this sensing system possesses reasonable reproducibility and stability. The good performance of electrochemical determination for glucose is attributed to the concerted effect of silver nanoparticles and MOF‐74(Ni) on the promotion of glucose oxidation     

A Novel Non‐Enzymatic Glucose Sensor Based on Cobalt Nanoparticles Implantation‐Modified Indium Tin Oxide Electrode

A new type of cobalt nanoparticles modified indium tin oxide electrode (CoNPs/ITO) was fabricated using ion implantation technique. This method is low‐cost, facile and environmentally friendly without the use of any other chemicals. Electrochemical oxidation of glucose with this sensor was examined by cyclic voltammetry (CV) and chronoamperometry in alkaline aqueous solutions. The proposed sensor exhibited prominent electrocatalytic activity toward the oxidation of glucose with a low limit of detection of 0.25 µM. Furthermore, the fabricated electrode showed excellent selectivity, good reproducibility and long‐term stability. Thus CoNPs/ITO electrode is a promising candidate in the development of non‐enzymatic glucose sensors.     

Fabrication of Miniaturised Screen‐printed Glucose Biosensors,Using a Water‐based Ink,and the Evaluation of their Electrochemical Behaviour

This paper describes a simple, convenient approach to the fabrication of microband electrodes and microband biosensors based on screen printing technology. These devices were printed in a three‐electrode configuration on one strip; a silver/silver chloride electrode and carbon counter electrode served as reference and counter electrodes respectively. The working electrodes were fabricated by screen‐printing a water‐based carbon ink containing cobalt phthalocyanine for hydrogen peroxide detection. These were converted into a glucose microband biosensor by the addition of glucose oxidase into the carbon ink. In this paper, we discuss the fabrication and application of glucose microband electrodes for the determination of glucose in cell media. The dimensions (100–400 microns) of the microband electrodes result in radial diffusion, which results in steady state responses in the absence of stirring. The microband biosensors were investigated in cell media containing different concentrations of glucose using chronoamperometry. The device shows linearity for glucose determination in the range 0.5 mM to 2.5 mM in cell media. The screen‐printed microband biosensor design holds promise as a generic platform for future applications in cell toxicity studies.     

Copper‐based Metal‐organic Framework for Non‐enzymatic Electrochemical Detection of Glucose

A non‐enzymatic electrochemical glucose sensor based on a Cu‐based metal‐organic framework (Cu‐MOF) modified electrode was developed. The Cu‐MOF was prepared by a simple ionothermal synthesis, and the characterizations of the Cu‐MOF were studied by Fourier transform infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), single‐crystal X‐ray powder diffraction (SCXRD), and X‐ray powder diffraction (XRD). Electrochemical behaviors of the Cu‐MOF modified electrode to glucose were measured by differential pulse voltammetry (DPV). The electrochemical results showed that the Cu‐MOF modified electrode exhibited an excellent electro‐catalytic oxidation towards glucose in the range of 0.06 μM to 5 mM with a sensitivity of 89 μA/mM cm² and a detection limit of 10.5 nM. Moreover, the fabricated sensor showed a high selectivity to the oxidation of glucose in coexistence with other interferences. The sensor was satisfactorily applied to the determination of glucose in urine samples. With the significant electrochemical performances, MOFs may provide a suitable platform in the construction of kinds of electrochemical sensors and/or biosensors and hold a great promise for sensing applications.     

A Self‐Sampling‐and‐Flow Biosensor for Continuous Monitoring

A self‐sampling‐and‐flow biosensor was fabricated by sandwiching a nitrocellulose strip on the working electrode side of the double‐sided microporous gold electrodes and a wicking pad on the counter electrode side. The double‐sided microporous electrodes were formed by plasma sputtering of gold on a porous nylon substrate. Sample was taken up to the enzyme‐immobilized working electrode by the capillary action of the front nitrocellulose strip dipped into the sample solution, analyzed electrochemically at the enzyme‐immobilized electrode, and diffuses out to the backside wicking pad through the micropores of the electrodes, constituting a complete flow cell device with no mechanical liquid‐transporting device. Biosensor was formed by co‐immobilizing the glucose oxidase and electron transfer mediator (ferrocene acetic acid) on the thioctic acid self‐assembled monolayer‐modified working electrode. A typical response time of the biosensor was about 5 min with the sensitivity of 2.98 nA/mM glucose, providing linear response up to 22.5 mM. To demonstrate the use of self‐sampling‐and‐flow biosensor, the consumption rate of glucose in the presence of yeast was monitored for five days.     

A microfluidic glucose sensor incorporating a novel thread‐based electrode system

An electrochemical sensor for the detection of glucose using thread‐based electrodes and fabric is described. This device is relatively simple to fabricate and can be used for multiple readings after washing with ethanol. The fabrication of the chip consisted of two steps. First, three thread‐based electrodes (reference, working, and counter) were fabricated by painting pieces of nylon thread with either layered silver ink and carbon ink or silver/silver chloride ink. The threads were then woven into a fabric chip with a beeswax barrier molded around the edges in order to prevent leaks from the tested solutions. A thread‐based working electrode consisting of one layer of silver underneath two layers of carbon was selected to fabricate the final sensor system. Using the chip, a PBS solution containing glucose oxidase (GOx) (10 mg/mL), potassium ferricyanide (K₃[Fe(CN)₆]) (10 mg/mL) as mediator, and different concentrations of glucose (0‐25 mM), was measured by cyclic voltammetry (CV). It was found that the current output from the oxidation of glucose was proportional to the glucose concentrations. This thread‐based electrode system is a viable sensor platform for detecting glucose in the physiological range.     

Voltammetric Determination of Trace Amounts of 2‐Methyl‐4,6‐Dinitrophenol at a Silver Solid Amalgam Electrode

The voltammetric behavior of 2‐methyl‐4,6‐dinitrophenol was investigated by differential pulse voltammetry (DPV) at a nontoxic mercury meniscus‐modified silver solid amalgam electrode (m‐AgSAE). Conditions have been found for its determination by DPV at m‐AgSAE in the concentration range of 0.2 to 1 μmol L^?1.     

Glucose Biosensor Based on Multi‐Walled Carbon Nanotube Modified Glassy Carbon Electrode

An amperometric glucose biosensor based on multi‐walled carbon nanotube (MWCNT) modified glassy carbon electrode has been developed. MWCNT‐modified glassy carbon electrode was obtained by casting the electrode surface with multi‐walled carbon nanotube materials. Glucose oxidase was co‐immobilized on the MWCNT‐modified glassy carbon surface by electrochemical deposition of poly(o‐phenylenediamine) film. Enhanced catalytic electroreduction behavior of oxygen at MWCNT‐modified electrode surface was observed at a potential of ?0.40 V (vs. Ag|AgCl) in neutral medium. The steady‐state amperometric response to glucose was determined at a selected potential of ?0.30 V by means of the reduction of dissolved oxygen consumed by the enzymatic reaction. Common interferents such as ascorbic acid, 4‐acetamidophenol, and uric acid did not interfere in the glucose determination. The linear range for glucose determination extended to 2.0 mM and the detection limit was estimated to be about 0.03 mM.     

A Self‐contained Two‐electrode Nanosensor for Electrochemical Analysis in Aqueous Microenvironments

We describe the development, fabrication, and characterization of a novel two‐electrode nanosensor contained within the tip of a needle‐like probe. This sensor consists of two, vertically aligned, carbon structures which function as individual electrodes. One of the carbon structures was modified by silver electrodeposition and chlorination to enable it to function as a pseudo‐reference electrode. Performance of this pseudo‐reference electrode was found to be comparable to that of commercially available Ag/AgCl reference electrodes. The unmodified carbon structure was employed as a working electrode versus the silver‐plated carbon structure to form a two‐electrode sensor capable of characterizing redox‐active analytes. The nanosensor was demonstrated to be capable of electrochemically characterizing the redox behavior of para‐aminophenol (PAP) in both bulk solutions and microenvironments. PAP was also measured in cell lysate to show that the nanosensor can detect small concentrations of analyte in heterogenous environments. As the working and reference electrodes are contained within a single nanoprobe, there was no requirement to position external electrodes within the electrochemical cell enabling analysis within very small domains. Due to the low‐cost manufacturing process, this nanoprobe has the potential to become a unique and widely accessible tool for the electrochemical characterization of microenvironments.     

Voltammetric Determination of N,N‐Dimethyl‐4‐amine‐carboxyazobenzene at a Silver Solid Amalgam Electrode

The voltammetric behavior of N,N‐dimethyl‐4‐amino‐2′‐carboxyazobenzene was investigated by differential pulse voltammetry (DPV) at a mercury meniscus‐modified silver solid amalgam electrode (m‐AgSAE). Conditions have been found for its determination by DPV at m‐AgSAE in the concentration range of 0.4 to 15 μmol L^?1.     

Protein‐Directed In Situ Synthesis of Gold Nanoparticles on Reduced Graphene Oxide Modified Electrode for Nonenzymatic Glucose Sensing

A novel nonenzymatic glucose sensor was developed based on well‐dispersed gold nanoparticles, which were in situ grown under direction of protein on a reduced graphene oxide modified electrode. This electrode exhibited high electrocatalytic activity towards glucose oxidation without use of any enzyme or mediator. In application for the amperometric detection of glucose, a wide linear range of 0.02–16.6 mM, low detection limit of 5 µM and good selectivity were obtained. The attractive analytical performances of the proposed glucose sensor, coupled with the facile preparation method, provide a promising electrochemical platform for the development of effective nonenzymatic sensors.     

Differential Pulse Anodic Stripping Voltammetric Simultaneous Determination of Copper(II) and Silver(I) with Bis(2‐hydroxyacetophenone) Butane‐2,3‐dihydrazone Modified Carbon Paste Electrodes

The behavior of a modified carbon paste electrode (CPE) for simultaneous determination of copper(II) and silver(I) by anodic adsorptive stripping voltammetry (ASV) was studied. The electrode was built incorporating the bis(2‐hydroxyacetophenone) butane‐2,3‐dihydrazone (BHAB) as a complexing agent to a Nujol‐graphite base paste. The resulting electrode demonstrated linear responses over the range of Cu(II) and Ag(I) concentrations 0.1–20 and 0.01–2.0 µM respectively. The relative standard deviation (RSD) for the determination of 5.0 µM of both metal ions were 2.9 and 3.1 % for Cu(II) and Ag(I), respectively. The method has been applied to the analysis of copper in wheat and barley seed samples and silver in developed radiological film.     

Lab‐on‐a‐Chip Sensor with Evaporated Bismuth Film Electrode for Anodic Stripping Voltammetry of Zinc

In this work, we report on the development of a lab‐on‐a‐chip electrochemical sensor that uses an evaporated bismuth electrode to detect zinc using square wave anodic stripping voltammetry. The microscale electrochemical cell consists of a bismuth working electrode, an integrated silver/silver chloride reference electrode, and a gold auxiliary electrode. The sensor exhibits a linear response in 0.1 M acetate buffer at pH 6 with zinc concentrations in the 1–30 μM range and a calculated detection limit of 60 nM. The sensor successfully detected zinc in a bovine serum extract and the results were corfirmed by independent AAS measurements. Our results demonstrate the advantageous qualities of this lab‐on‐a‐chip electrochemical sensor for clinical applications, which include small sample volume (µL scale), reduced cost, short response time and high accuracy at low concentrations of analyte.     

Physicochemical Characteristics of Polypyrrole/(Glucose oxidase)/(Prussian Blue)‐based Biosensor Modified with Ni‐ and Co‐Hexacyanoferrates

In this work, three types of electrodes suitable for amperometric glucose biosensors were designed. One type of electrode was based on bio‐selective layer of polypyrrole/(glucose oxidase)/(Prussian Blue) (Ppy/GOx/PB) and it was used as a control electrode regarding to which electrochemical properties of two other types of electrodes were compared. During the formation of Prussian blue layers graphite electrodes were additionally modified by Ni‐hexacyanoferrate (NiHCF) and by Co‐hexacyanoferrate (CoHCF) in order to design Ppy/GOx/PB‐NiHCF and Ppy/GOx/PB‐CoHCF electrodes, respectively. Some physicochemical characteristics of all three types of electrodes were evaluated and compared. The Ppy/GOx/PB‐NiHCF electrode showed wider linear range of the calibration curve than Ppy/GOx/PB and Ppy/GOx/PB‐CoHCF electrodes. The effect of temperature on analytical performance of the Ppy/GOx/PB‐NiHCF based biosensor has been evaluated and activation energy of enzyme catalysed reaction has been calculated within the temperature range of 15 °C to 30 °C.     

Plasma‐functionalized Highly Aligned CNT‐based Biosensor for Point of Care Determination of Glucose in Human Blood Plasma

In this study, a new method for modification of vertically aligned carbon nanotube arrays (VACNTs) for selective detection of glucose was developed. VACNTs were grown by chemical vapor deposition method on a silicon substrate deposited with alumina as a buffer layer and iron as a catalyst using radio frequency (RF) sputtering and electron beam evaporation, respectively. The surface of the electrode was modified with electrodeposition of polyaniline (PANI) followed by covalent attachment of glucose oxidase (GOx). The electrode was characterized using field emission scanning electron microscopy (FESEM), micro‐Raman spectroscopy, and attenuated total reflectance Fourier transform infrared spectrometer (ATR‐FTIR) techniques. Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behavior of the electrode. The fabricated electrode was successfully employed as a point‐of‐care (POC) biosensor for the detection of glucose in human blood plasma. The detection limit was 1.1 μM, and the sensitivity was 620 μA mM^?1 cm^?2 at the linear range of 2–426 μM.     

An Air‐breathing Carbon Cloth‐based Screen‐printed Electrode for Applications in Enzymatic Biofuel Cells

We report a prototype air‐breathing carbon cloth‐based electrode that was fabricated starting from a commercially available screen‐printed electrode equipped with a transparent ITO working electrode (DropSens, ref. ITO10). The fabrication of the air‐breathing electrodes is straightforward, shows satisfactory reproducibility and a good electrochemical response as evaluated by means of [Fe(CN)₆]^3?/4? voltammetry. The gas‐diffusion electrodes were successfully modified with the O₂ reducing enzyme bilirubin oxidase from Myrothecium verrucaria in a direct electron transfer regime. The enzyme modified electrodes showed a remarkable high current density for O₂ reduction in passive air‐breathing mode of up to 5 mA cm^?2. Moreover, the enzyme modified electrodes were applied as O₂ reducing biocathodes in a glucose/air enzymatic biofuel cell in combination with a high current density glucose oxidase/redox polymer bioanode. The biofuel cell provides a high maximum power density of (0.34±0.02) mW cm^?2 at 0.25 V. The straightforward design, low cost and the high reproducibility of these electrodes are considered as basis for standardized measurements under gas‐breathing conditions and for high throughput screening of gas converting (bio‐)catalysts.     

Reconstituted Enzymes on Electropolymerizable FAD‐Modified Metallic Nanoparticles: Functional Units for the Assembly of Effectively “Wired” Enzyme Electrodes

Au nanoparticles are functionalized with thioaniline electropolymerizable units and mercaptophenyl boronic acid ligands. Flavin adenine dinucleotide (FAD) is linked to the boronic acid ligands and apo‐glucose oxidase, apo‐GOx, is reconstituted on the FAD cofactor units to yield enzymes in a structurally‐aligned configuration in respect to the Au NPs. Electropolymerization of the enzyme‐functionalized Au NPs on a thioaniline‐modified Au electrode yields a three‐dimensional bis‐aniline‐crosslinked Au NPs/reconstituted glucose oxidase matrix on the electrode that reveals effective electrical contacting with the electrode.     

A Mediator‐Free Bienzyme Amperometric Biosensor Based on Horseradish Peroxidase and Glucose Oxidase Immobilized on Carbon Nanotube Modified Electrode

Multiwalled carbon nanotube (CNT) modified glassy carbon electrode immobilized with horseradish peroxidase (HRP) in Nafion coating showed direct electron transfer between HRP enzyme and the CNT‐modified electrode. A mediator‐free bienzyme glucose biosensor based on horseradish peroxidase and glucose oxidase was constructed. The bienzyme biosensor exhibited a high sensitivity for glucose detection at zero applied potential.     

An Arrayed Micro‐glutamate Sensor Probe Integrated with On‐probe Ag/AgCl Reference and Counter Electrodes

Complete all‐in‐one multi‐arrayed glutamate (Glut) sensors have been constructed on a silicon‐based micromachined probe composed of micro‐platinum (Pt) working electrodes, a micro‐silver/silver chloride (Ag/AgCl) reference electrode (RE), and a micro‐Pt counter electrode (CE). The OCP shift of the electrodeposited Ag/AgCl on‐probe micro‐reference electrode compared with a Ag/AgCl wire is <0.1 mV/h. The composition ratio of Ag, Cl, and Pt on the electrodeposited on‐probe micro‐reference electrode is observed to be 1.00 : 0.48 : 0.02 analyzed by EDS. The miniaturized amperometric Glut biosensors were constructed on working electrode sites (electrode area: ∼8.5×10⁻⁵ cm²) of the microprobe modified with glutamate oxidase (GlutOx) enzyme layers for the selective, fast, and continuous detection of L‐glutamate. The sensor selectivity towards common electroactive interferents has been improved significantly by coating the electrode surface with perm‐selective polymer layers, overoxidized polypyrrole (PPY) and Nafion®. The sensitivity, detection range, and response time of the proposed all‐in‐one Glut biosensors are 204.7±5.8 nA μM⁻¹ cm⁻² (N=5), 4.99–109 μM, and 2.7±0.3 sec, respectively and no interferent signals of AA and DA were observed. The sensor can be reused over 19 times of continuous repetitive operation (total measurement time: ∼4 hours) and the sensor sensitivity can retain up to four weeks of storage.     

An Amperometric Glucose Biosensor Based on Poly (Pyrrole‐2‐Carboxylic Acid)/Glucose Oxidase Biocomposite

A newly developed amperometric glucose biosensor based on graphite rod (GR) working electrode modified with biocomposite consisting of poly (pyrrole‐2‐carboxylic acid) (PCPy) particles and enzyme glucose oxidase (GOx) was investigated. The PCPy particles were synthesized by chemical oxidative polymerization technique using H₂O₂ as initiator of polymerization reaction and modified covalently with the GOx (PCPy‐GOx) after activation of carboxyl groups located on the particles surface with a mixture of N‐(3‐dimethylaminopropyl)‐N′‐ethylcarbodiimide hydrochloride (EDC) and N‐hydroxysuccinimide (NHS). Then the PCPy‐GOx biocomposite was dispersed in a buffer solution containing a certain amount of bovine serum albumin (BSA). The resulting biocomposite suspension was adsorbed the on GR electrode surface with subsequent solvent airing and chemical cross‐linking of the proteins with glutaraldehyde vapour (GR/PCPy‐GOx). It was determined that the current response of the GR/PCPy‐GOx electrodes to glucose measured at +300 mV vs Cl reference electrode was influenced by the duration of the PCPy particles synthesis, pH of the GOx solution used for the PCPy particles modification and the amount of immobilized PCPy‐GOx biocomposite. An optimal pH of buffer solution for operation of the biosensor was found to be 8.0. Detection limit was determined as 0.039 mmol L⁻¹ according signal to noise ratio (S/N: 3). The proposed glucose biosensor was tested in human serum samples.