A Siloxane Homopolymer with Interacting Ferrocenes as a New Material for the Preparation of Sensors Based on the Detection of Hydrogen Peroxide

The electrochemical characterization of a hydrogen peroxide sensor based on a ferrocene‐containing polymer electrochemically deposited onto a platinum electrode is described. The redox polymer consists of a siloxane‐based homopolymer, with pendant electronically communicated ferrocenyl moieties. The electrodes were used as the transducer for glucose and lactate‐sensing enzyme sensors. Amperometric biosensors were prepared by immobilization of glucose oxidase (Gox) or lactate oxidase (Lox) onto these modified electrodes. The steady‐state amperometric response of the sensors is investigated as a function of the applied potential and substrate concentration. Interferences, sensitivity and stability of the sensors were also studied.     

A Micro Planar Ampehometric Glucose Sensor Using an Isfet as a Reference Electrode

Abstract

A very small glucose sensor has been realized, which consists of a gold working electrode with a glucose oxidase immobilized membrane on it, and a gold counter electrode, all made on a sapphire substrate. By using the pH sensitive ISFET as a reference electrode, the potential for a solution, whose pH is constant, can be measured and irreversible metal electrodes, such as gold or platinum, can be used as working electrode and counter electrode. The sensor is very suitable for miniaturizing and mass production, because the Integrated Circuit (IC) fabrication process can be applied. The glucose oxidase immobilized membrane was also deposited by a lift off method, one of the IC processes. A glucose concentration, from 1 to 100 mg/dl, was measured with good linear current output.     

Synthesis of PtxSn/MWCNTs and their Application in Non‐enzymatic Glucose and Hydrogen Peroxide Sensors

Pt_xSn/MWCNTs (x=1, 2, 3) nanocomposites were synthesized by chemical reduction. Comparing all of the materials, the results revealed that the best material was Pt₃Sn/MWCNTs. The sensor based on Pt₃Sn/MWCNTs exhibited excellent catalytic activities towards glucose and hydrogen peroxide. Sensing of glucose had a double‐linear range: one was between 50 μM and 550 μM, the other was between 1.35 mM and 16.35 mM. These were due to the fact that more and more intermediate species were adsorbed onto the electrode surface with increasing concentration of glucose, which limited the following glucose oxidation. Meanwhile, the sensor also had a linear response range between 0.05 mM and 18.95 mM for hydrogen peroxide. Furthermore, the glucose and hydrogen peroxide sensors exhibited excellent selectivity, stability, and reproducibility. Thus the sensors had potential utilities in the detection of glucose and hydrogen peroxide.     

Grape tissue-based electrochemical sensor for the determination of hydrogen peroxide

The use of grape tissue as a source of catalase for the determination of hydrogen peroxide is reported. A slice of grape tissue attached to the membrane of a Clark-type oxgen sensor was used to monitor the oxidation of hydrogen peroxide by catalase. At the steady state, the sensor responds linearly to hydrogen peroxide in the concentration range 1 × 10^?5–5 × 10^?4 M. The response time (T₉₀) was of the order of 1 min for this sensor. No interference was observed from ethanol, amino acids, glucose and lactic acid. The long-term stability of the grape tissue sensor was much better than previously reported immobilized enzyme and liver tissue-based hydrogen peroxide sensors.     

Detecting Both Physical and (Bio‐)Chemical Parameters by Means of ISFET Devices

A multi‐parameter sensor system for the detection of eight (bio‐)chemical and physical parameters (pH, potassium concentration, penicillin concentration, diffusion coefficient of H⁺‐ and OH ^–‐ions, temperature, flow velocity, flow direction and liquid level) is realized by using the same transducer principle. A Ta₂O₅‐gate ISFET (ion‐sensitive field‐effect transistor) is applied as basic transducer for all kinds of sensors. The multi‐parameter detection is achieved by means of sequentially or simultaneously scheduling of the hybride sensor modules consisting of four ISFET structures and an ion generator in different sensor arrangements and/or different operation modes. Thus, more parameters (eight) can be detected than the number of sensors (four) in the system.     

Alcohol-FET sensor based on a complex cell membrane enzyme system

An alcohol -FET sensor was developed by use of a complex enzyme system in a cell membrane and an ion-sensitive field effect transistor (ISFET). The cell membrane of Gluconobacter suboxydans IFO 12528, which converts ethanol to acetic acid, was immobilized on the gate of an ISFET with calcium alginate gel coated with nitrocellulose. This ISFET (1), a reference ISFET without the cell membrane (ISFET 2) and an Ag/AgCl reference electrode were placed in 5 mM Trismalate buffer (pH 5.5, 25°C), and the differential output between ISFETS 1 and 2 was measured. The output of the sensor was stabilized by adding pyrroloquinoline quinone. The response time was ca. 10 min., and there was a linear relationship between the differential output voltage and the ethanol concentration up to 20 mg l^?1. The output of the sensor was stable for 40 h below 30°C. The sensor responded to ethanol, propan- 1-ol and butan- 1-ol, but not to methanol, propan-2-ol and butan-2-ol. The sensor was used to determine blood ethanol.     

Electrode kinetics of amperometric hydrogen sensors for hydrogen detection at low parts per million level

Hydrogen gas detection at low parts per million concentration levels in sensors based on polymer membrane electrolytes and catalytically active electrodes, operating at room temperature, is sensitively dependent on the morphology of the electrode. This effect has been investigated using Nafion^® as polymeric proton-conducting membrane onto which a catalytic electrode was deposited by an in situ impregnation–reduction technique. In this work, Pt was selected as active catalyst for hydrogen oxidation. The deposition conditions were modified to optimise the parameters with regard to the application of the electrode in low-level hydrogen sensors in the 10–1,000 ppm range and to improve the metal utilisation for reduced electrode loading without loss of electrochemical performance. Models of electrode kinetics are proposed and compared with experimental results. Increasing porosity as a result of decreased reductant concentrations was observed by scanning electron microscopy and other surface characterisation methods. The response time of the hydrogen sensor was in the range of 10–30 s and a stable linear current output was observed under short-circuit conditions.     

Amperometric determination of glucose in undiluted food samples

Glucose oxidase is immobilized onto a cellulose acetate membrane by glutaraldehyde linkage, and the membrane is used to cover the platinum electrode of a hydrogen peroxide sensor. A silanized polycarbonate membrane then covers the enzyme layer, and extends the linear calibration range to higher concentrations. The sensor, when incorporated into a flow-injection system, allows the determination of glucose at levels up to 1 M in soft drinks at a rate of 60 samples h^?1 without sample dilution.     

Glucose and urea biosensors based on all solid-state PVC-NH2 membrane electrodes

Miniaturized urea and glucose sensors prepared by immobilization of glucose oxidase or urease directly onto all solid-state contact PVC-NH₂ membrane ammonium and hydrogen ion selective electrodes are described. The resulting biosensing membranes function equivalently to normal PVC membranes in terms of potentiometric response properties. The most important features of the glucose and urea sensors were high sensitivity, long life-time, easily built at a low cost, micro-construction and short response time. The characteristics of the glucose and urea sensors were examined in several buffer solutions at different concentrations and pH values. The influence of immobilization conditions on the dynamic response properties and life-time of the electrodes was studied. Under optimal conditions, the urea electrode showed a linear response between 5×10⁻² and 5×10⁻⁴ M urea, while the glucose electrode showed a linear response between 5×10⁻² and 1×10⁻⁴ M glucose.     

Glucose sensors based on enzyme immobilization onto biocompatible membranes obtained by radiation-induced polymerization

Amperometric glucose biosensors based on glucose oxidase immobilized onto poly(2-hydroxyethylmethacrylate) membranes obtained by γ radiation-induced polymerization were constructed. In a threeelectrode configuration, smooth or platinized platinum electrodes with different shapes were used, in order to detect the amount of hydrogen peroxide produced in the glucose oxidation. A saturated calomel electrode and a platinum foil were used as a reference and counterelectrode, respectively. The biocompatible obtained sensors were characterized as regards the temperature effect, the response, and lifetime. The determination of glucose in standard solutions was carried out, and linear calibration curves were obtained. Depending on the electrode configuration, the sensor had a response time of 1–4 min, and the measuring range extended from 5 × 10^?5 to 4 × 10^?3M.     

Disposable potentiometric enzyme sensor for direct determination of organophosphorus insecticides

A potentiometric disposable enzyme sensor for the direct and fast determination of organophosphorus (OP) insecticides was developed by using an organophosphorus hydrolase (OPH) immobilized on an ion-selective electrode. The disposable screen-printed transducer was based on double matrix membrane technology which allows easy mass production. The potentiometric device consisted of a H(+)-sensitive electrode with integrated Ag/AgCl reference electrode. The electrodes were prepared with N,N-dioctadecylmethylamine as H(+)-sensitive ionophore and pH calibration resulted in slopes of 55 mV decade-1 over a pH range from 11 to 6. OPH was isolated from recombinant Escherichia coli DH5 alpha and immobilized within poly(carbamoyl sulfonate) prepolymer on the surface of the H(+)-sensitive electrode without any further fixation membrane. OPH catalyzes the hydrolytic cleavage of OP compounds which releases protons in a concentration proportional to hydrolyzed substrate. Sensor performance was investigated with regard to enzyme load, concentration, pH and temperature of the measuring buffer using paraoxon as analyte. Best sensitivity and response time were obtained with sensors prepared with 250 U of OPH and measuring at 37 degrees C in 1.0 mM HEPES buffer, pH 9.3, containing 100 mM NaCl. The enzyme sensor exhibited a linear calibration range of 0.01-0.15 mM chlorpyrifos, 0.05-0.35 mM diazinon, 0.05-0.4 mM paraoxon and 0.007-0.05 mM parathion, respectively. For all these analytes response times to reach 95% of maximum change in potential did not exceed 5 min. Sensors stored under dry conditions at 4 degrees C still showed 60% of initial hydrolytic rate after 70 d. The sensors even when stored dry were ready for measurements after 5 min incubation in measuring buffer. A range of putative interfering substances did not influence sensor response, and suitability of measuring OPs in soil extracts was ascertained.     

A Novel Enzymatic Glucose Biosensor and Nonenzymatic Hydrogen Peroxide Sensor Based on (3‐Aminopropyl) Triethoxysilane Functionalized Reduced Graphene Oxide

In the present study, a novel enzymatic glucose biosensor using glucose oxidase (GOx) immobilized into (3‐aminopropyl) triethoxysilane (APTES) functionalized reduced graphene oxide (rGO‐APTES) and hydrogen peroxide sensor based on rGO‐APTES modified glassy carbon (GC) electrode were fabricated. Nafion (Nf) was used as a protective membrane. For the characterization of the composites, Fourier transform infrared spectroscopy (FTIR), X‐ray powder diffractometer (XRD), and transmission electron microscopy (TEM) were used. The electrochemical properties of the modified electrodes were investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and amperometry. The resulting Nf/rGO‐APTES/GOx/GC and Nf/rGO‐APTES/GC composites showed good electrocatalytical activity toward glucose and H₂O₂, respectively. The Nf/rGO‐APTES/GC electrode exhibited a linear range of H₂O₂ concentration from 0.05 to 15.25 mM with a detection limit (LOD) of 0.017 mM and sensitivity of 124.87 μA mM⁻¹ cm⁻². The Nf/rGO‐APTES/GOx/GC electrode showed a linear range of glucose from 0.02 to 4.340 mM with a LOD of 9 μM and sensitivity of 75.26 μA mM⁻¹ cm⁻². Also, the sensor and biosensor had notable selectivity, repeatability, reproducibility, and storage stability.     

Miniaturized back-side contact transducer for potentiometric sensors

A novel type of a miniature transducer for potentiometric sensors was designed and tested. The transducer is made from an ordinary printed circuit board using a typical technology. As a result, a back-side contact structure was obtained, which can be mounted in flow systems. The advantage of the fabrication process is its cheapness and flexibility in designing modified structures. The measurement properties of the transducer were tested as a chloride sensor. Then the structure was covered with polyHEMA and a potassium-selective membrane and tested as a potassium sensor. The performance and the long-term stability of the sensors with plasticized PVC and Siloprene based potassium-selective membranes were compared.     

A specific bio-electrochemical sensor for hydrogen peroxide

A bio-electrochemical sensor specific for hydrogen peroxide is described. The sensor consists of two membranes—a catalase-collagen membrane and a teflon membrane—an alkaline solution, a platinum cathode and a lead anode. The catalase-collagen membrane is prepared electrochemically, the thickness being 1 μ; the enzyme activity is similar to that of native catalase. The sensor responds to hydrogen peroxide with a response time of only 1–2 min. The calibration curve is quite linear over a concentration range of 0–1.5 mmol l^-1 for hydrogen peroxide. The utility of the sensor in continuous usage is discussed.     

Availability and development of an enzyme immunomicrosensor based on an ISFET for human immunoglobulins

A critical evaluation of the potentiometric response of an enzyme immuno-ISFET sensor has demonstrated that it is an effective, simple sensor for human immunoglobulin (IgG). The sensor was constructed using an immobilized human IgG membrane and an ISFET. The assay procedure involves the competitive immunochemical reaction of ureuse-labelled anti-human IgG with human IgG in samples and membrane-bound IgG and the electrochemical determination of membrane-bound urease activity. A linear relationship was obtained between the initial rate of response and the logarithm of IgG concentration from 0.1 to 2.0 mg ml^?1.     

Glucose sensor based on a field-effect transistor with a photolithographically patterned glucose oxidase membrane

A photopolymer solution consisting of polyvinylpyrrolidone and 2,5-bis(4′-azido-2′-sulfobenzal)cyclopentanone is used to make a patterned glucose oxidase membrane for a FET-glucose sensor by photolithography. A small patterned glucose oxidase membrane, 0.2 mm wide and 1 mm long, is made on the gate surface of an ISFET by developing a photocross-linked glucose oxidase membrane with aqueous 1–3% glutaraldehyde solution. The optimum composition of the enzyme/photopolymer solution is described. The sensor with the patterned membrane showed linear response to glucose concentration from 0.3 to 2.2 mM and useful response up to 5 mM.     

Gamma-irradiation immobilization of lactate oxidase in poly(vinyl alcohol) on platinized graphite electrodes

A novel method for enzyme immobilization in a polymer matrix was examined with lactate oxidase (LOD) to make a sensor for lactate. Poly(vinyl alcohol) (PVAL) and LOD were applied in layers on platinized graphite electrodes and cross-linked by exposure to a ⁶⁰Co gamma radiation source. When the sensor is dipped in lactate solution, the product of the enzymatic reaction, hydrogen peroxide, is detected at +300 mV vs. Ag/AgCl. The LOD-PVAL lactate sensor exhibits a fast response (10–50 s), a linear range between 26 μM and 1.7 mM, a detection limit of 13 μM and a sensitivity of 2.94 μA mmol^?1. The sensitivity and the linearity of the electrode were improved considerably by bubbling oxygen continuously through the lactate solution. Optimum response to lactate was obtained with a radiation dose of 3–10 Mrad. LOD was found to be active in the presence of the polymer under radiation doses as high as 40 Mrad. Repeated use of the sensors under various conditions showed a stable and reproducible response to lactate for over 80 days.     

Low Cost Hydrogen Peroxide Sensor from Manganese Oxides Modified Pencil Graphite Electrode

Electrodeposition of manganese oxides film onto the cheap pencil graphite electrode using potassium permanganate precursor provides the good alternative method of fabrication the low cost hydrogen peroxide sensor. Effect of deposition potential, deposition time and concentration of potassium permanganate were investigated. The modified electrode displayed electrocatalytic activity towards the oxidation of hydrogen peroxide in alkaline medium. Amperometric detection of hydrogen peroxide in ammonium buffer pH 9.0 is possible at the operation potential of +0.50V vs Ag/AgCl instead of over +0.80V vs Ag/AgCl with unmodified electrode. Linear concentration range between 0.50-138ppm of hydrogen peroxide was obtained with a detection limit of 0.28ppm.     

Electrocatalytical properties of polymethylferrocenyl dendrimers and their applications in biosensing

The electrochemical characterization of polymethylferrocenyl dendrimers deposited onto a platinum electrode and their applications as hydrogen peroxide and glucose sensor are described. The redox dendrimers consist of flexible poly(propileneimine) dendrimer cores functionalised with octamethylferrocenyl units. Amperometric biosensors for glucose were prepared by immobilization of glucose oxidase onto these modified electrodes. The influence of the dendrimer generation and the thickness of the dendrimer layer, the effect of the substrate concentration, and the interferences and reproducibility on the response of the sensors were investigated.