Glutathione Amperometric Enzyme Microsensor

Abstract

Glutathione micro-enzyme sensors were developed based on the immobilization of glutathione oxidase at the tip of a 25 μm Pt wire sealed in glass. An inner membrane constructed from cellulose acetate (CA) was deposited onto the tip of the Pt microelectrode prior to enzyme immobilization with glutaraldehyde. The final outer diameter of the microelectrodes is approximately 30 μm. The analytical characteristics of the microelectrodes, including calibration curves, apparent K_M′, pH response curves, stability and selectivity over enzymatic interferences were determined. The response was linear in the concentration range 1.0 × 10^?5 M - 1.9 × 10^?4 M glutathione, reaching 95% steady-state current in 15–20 seconds. The microelectrodes were useful for more than two months.     

Studies on the application of Fe-Zr mixed hydrous oxide membranes in ion-selective potentiometry

A solid membrane electrode selective to chloride ions has been prepared from Fe-Zr mixed hydrous oxide (with iron as a major constituent) with polystyrene as binder. Although the response of the electrode is non-Nernstian it can be utilized to estimate chloride in the concentration range 10(-4)-10(-1)M. The potentials generated across the membrane are reproducible within +/-0.2 mV and the response time is a few seconds. The standard deviation of the potential measurements is 0.4 mV at the 0.1M level. The useful pH range is 4-7 and the electrode can also be used in partially non-aqueous systems. The electrode exhibits fairly good selectivity for chloride.     

Novel Solid‐Contact Ion‐Selective Microelectrodes for Localized Potentiometric Measurements

The design and properties of novel type of solid‐contact ionophore‐based ion‐selective microelectrodes are reported. The microelectrode is based on an insulated needle‐shaped metallic wire with an exposed apex. The ion‐to‐electron transducer is made of poly(3‐octylthiophene‐2,5‐diyl) and placed between an ion‐selective membrane and the metallic tip. The ion‐selective polyvinyl chloride‐based membrane is deposited atop the layer of conductive polymer. The length of the ion‐sensitive part of the electrode is less than 10 μm. pH and Mg²⁺‐selective microelectrodes were constructed and tested showing stable potential and fast response that are essential properties for the practical application of microelectrodes for localized scanning measurements.     

A novel Urushi matrix chloride ion-selective field effect transistor

A durable chloride ion-selective field effect transistor (ISFET) is proposed with Urushi as the membrane matrix. The chloride ion-sensing material is a quaternary ammonium chloride: trioctylmethylammonium chloride (TOMA-Cl) or tridodecylmethylammonium chloride (TDMA-Cl). The optimum composition of the Urushi membrane was found by use of Urushi ion-selective electrodes. The mixture with the most favourable composition was coated on the gate region of the FET device. The Urushi ISFET with TDMA-Cl proved to be superior to that with TOMA-Cl, in sensitivity, linearity and selectivity. The Urushi ISFET with TDMA-Cl showed a linear response of about -51 mV per decade change of chloride ion activity in the range 10(-4)-1M. The Urushi ISFET showed excellent stability and durability for over two months, because of strong adhesion of the membrane to the Si(3)N(4) gate.     

Measurement of nitrate gradients with an ion-selective microelectrode

Nitrate-selective microelectrodes (1-μm tip diameter) with a liquid membrane ion exchanger were prepared. The response of the electrode is linear from 10^?1 to 10^?5 M nitrate and the response time is 30 s. Selectivity coefficients are of the same order as specified for macroelectrodes. Measurements in sediments of a mesotrophic lake and measurements in spherical agar gels with immobilized denitrifying bacteria are presented.     

Solvent extraction of phosphonium salts and their analytical applications : Separation and spectrophotometric determination of hexacyanoferrate(III)

The potentiometric determination of zinc in chloride solutions with a coated wire electrode is described. The electroactive membrane contains the chlorozincate(II) salt of Aliquat 336S in poly (vinyl chloride). The electrode shows a useful response over the range 10^-5 M–10^-1 M zinc(II) in 3 M total chloride solutions in the pH range 1.5–6. The electrode is more responsive to the divalent tetrachlorozincate(II) than to the monovalent trichlorozincate(II) species. Applications in compleximetric titrations, and to the analysis of zinc oxide and zinc concentrates are reported.     

A new procedure for the construction of flow-through optodes. Application to determination of copper (II)

A new procedure for constructing an optical fibre reflectance, bulk optode membrane type, sensor is presented. The optode membrane consists of a plasticized poly (vinyl chloride) membrane in which the ionophore is dissolved, entrapped in a cellulose support. The new optode with the dye indicator 1-(2-pyridylazo)-2-naphthol (PAN) was incorporated in a new flow-through cell and the injection system was optimized to determine Cu (II) at 567 nm in the range 5 x 10(-5)-10(-3) M. The response was reproducible and the optode can be regenerated using 10(-2) M EDTA followed by water. The method was applied to the determination of copper in real samples.     

Chromazurol S ion-selective electrode for chelatometric titration

A liquid membrane type Chromazurol S ion-selective electrode has been constructed and applied to chelatometric titrations. In aqueous medium, zephiramine (benzyldimethyltetradecylammonium chloride) forms with the anion of Chromazurol S an ion-pair which is easily extracted into nitrobenzene. The extract is used as the liquid ion-exchanger for the Chromazurol S ion-selective electrode. The most suitable ion-pair concentration in the liquid ion-exchanger membrane is 10(-4)M. The linear Nernstian-response range of the Chromazurol S anion in aqueous solution is 10(-2)-10(-6)M. The electrode has been successfully applied to the chelatometric titration of Cu(II), Ni(II), Fe(III) and Pb(II) with EDTA.     

亚硫酰氯阴极还原的半对数极化曲线

目前正在广泛研究的鲤/亚硫酰氯(Li/SOCl_2)电池是迄今为止比能量最高的一种新型化学电源。提高电池的性能和可靠性与电池反应的化学和电化学性质直接有关。但是,SOCl_2的还原过程相当复杂,对其反应机理迄今尚无明确的结论。由于SOCl_2还原时伴随着LiCl的沉积,当用常规电极测量时难以得到稳态极化曲线,因而至今未见报道SOCl_2还原反应的半对数极化曲线。微电极的单位表面上极限液相传质速度较高,且测量时较易得到稳态电流。因此,采用微电极方法可在一定程度上避开上述困难,研究SOCl_2还原反应的机理。     

Ion-selective electrodes for potentiometric determination of ranitidine hydrochloride, applying batch and flow injection analysis techniques.

New ranitidine hydrochloride (RaCl)-selective electrodes of the conventional polymer membrane type are described. They are based on incorporation of ranitidine-tetraphenylborate (Ra-TPB) ion-pair or ranitidine-phosphotungstate (RaPT) ion-associate in a poly(vinyl chloride) (PVC) membrane plasticized with dioctylphthalate (DOP) or dibutylphthalate (DBP). The electrodes are fully characterized in terms of the membrane composition, solution temperature, and pH. The sensors showed fast and stable responses. Nernstian response was found over the concentration range of 2.0 x 10(-5) M to 1.0 x 10(-2) M and 1.0 x 10(-5) M to 1.0 x 10(-2) M in the case of Ra-TPB electrode and over the range of 1.03 x 10(-5) M to 1.00 x 10(-2) M and 1.0 x 10(-5) M to 1.0 x 10(-2) M in the case of Ra-PT electrode for batch and FIA systems, respectively. The electrodes exhibit good selectivity for RaCl with respect to a large number of common ions, sugars, amino acids, and components other than ranitidine hydrochloride of the investigated mixed drugs. The electrodes have been applied to the potentiometric determination of RaCl in pure solutions and in pharmaceutical preparations under batch and flow injection conditions with a lower detection limit of 1.26 x 10(-5) M and 5.62 x 10(-6) M at 25 +/- 1 degrees C. An average recovery of 100.91% and 100.42% with a relative standard deviation of 0.72% and 0.53% has been achieved.     

An optode sensor for Cu2+ with high selectivity based on porphyrin derivative appended with bipyridine.

A porphyrin derivative (fluorophore) appended with bipyridine (ionophore) has been applied for preparation of a Cu2+-sensitive optical chemical sensor, which is based on fluorescence quenching of porphyrin derivative entrapped in a poly(vinyl chloride) membrane by the energy transfer process. The sensor exhibits a linear response toward Cu2+ in the concentration range 2.0 x 10(-8) - 1.0 x 10(-5) M, with a working pH range from 6.0 to 8.0 and a high selectivity. The detection limit is 5 x 10(-9) M. The response time for Cu2+ is less than 5 min with concentrations lower than 5 x 10(-6) M. The optode can be regenerated using 0.3 M EDTA (pH 9) and acetate buffer solution. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for direct determination of Cu2+ in water samples with satisfied results.     

One-pot electrosynthesis of polyglycine-like thin film on platinum electrodes as transducer for solid state pH measurements

The anodic oxidation of concentrated glycine based aqueous electrolyte on smooth platinum electrode leads to a strongly grafted polyglycine-like coating on the surface in an irreversible way. Due to the proton affinity towards amino groups of polyglycine (PG), the electrodeposited thin film was used as receptor for solid potentiometric pH sensor. In order to reach local pH measurement, we developed miniaturized microelectrodes on glass substrate thanks to photolithography process. We used silver chloride on silver as the reference electrode. The couple (silver chloride, PG based platinum electrode) of microelectrodes gives linear potentiometric response vs. pH in the range [2-12], reversibly and with a sensitivity of 52.4 mV/pH (for 1 mm electrode size). PG based pH electrode is compared to other organic polymer based pH receptor such as linear polyethylenimine (L-PEI), polyaniline (PANI) and glass membrane.     

Potentiometric measurement of ascorbate by using a solvent polymeric membrane electrode

A novel potentiometric method for the determination of ascorbate is described in this communication. It is based on ascorbate oxidation with permanganate which is continuously released from the inner reference solution of a ligand-free tridodecylmethylammonium chloride (TDMAC)-based polymeric membrane ion selective electrode (ISE). The ISE potential determined by the activity of permanganate ions released at the sample-membrane phase boundary is increased with the consumption of permanganate. The proposed membrane electrode is useful for continuous and reversible detection of ascorbate at concentrations in 0.1M NaCl ranging from 1.0 x 10(-6) to 1.0 x 10(-3)M with a detection limit of 2.2 x 10(-7)M.     

An Eu(III) sensor based on N,N-diethyl-N-(4-hydroxy-6-methylpyridin-2-yl)guanidine.

A highly selective poly(vinyl chloride)-based membrane sensor produced by using N,N-diethyl-N-(4-hydroxy-6-methylpyridin-2-yl)guanidine (GD) as active material is described. The electrode displays Nernstian behavior over the concentration range 7.0 x 10(-5) - 1.0 x 10(-1) M. The detection limit of the electrode is 5.0 x 10(-5) M. The best performance was obtained with the membrane containing 30% PVC, 55% benzyl acetate, 5% GD and 10% oleic acid. The response of the sensor is pH-independent in the range of 3.0 - 7.0. The sensor possesses satisfactory reproducibility, fast response time (< 20 s), and specially excellent discriminating ability for Eu(III) ion with respect to the alkali, alkaline earth, transition and heavy metal ions. The membrane sensor was used as an indicator electrode in potentiometric titration of Eu(III) ion with EDTA. It was also applied in determination of fluoride ions in mouth wash preparations.     

A double-membrane ephedrine selective electrode based on ephedrine-tetraphenylborate in poly (vinyl chloride) resin

The construction and performance characteristics of a double-membrane ephedrine selective electrode are described. The electrode is based on the use of an internal conducting membrane made of tetrabutylammonium bromide and another external electroactive membrane containing the ionic pair ephedrine-tetraphenylborate in a poly (vinyl chloride) resin (with some plasticizers incorporated) as an inert matrix. The ephedrine electrode exhibits linear Nernstian response within the range 10(-2)-5 x 10(-5)M of ephedrine, with a slope of 58.2 +/- 0.5 mV decade(-1) at 25 +/- 0.2 degrees . The detection limit is 10(-4.5)M. The reproducibility (coefficient of variation) was 0.54% (n = 10 determinations) and the stability of its potential is 2.3 mV/24 h. The selectivity coefficients for 15 ions were calculated. The electrode was applied to the determination of ephedrine in some pharmaceutical preparations with satisfactory results.     

Sensing of trace copper ion by a solid phase extraction-spectrophotometry using a poly(vinyl chloride) membrane containing bathocuproine

A new sensitive and selective spectrophotometric method for the determination of trace copper using a poly(vinyl chloride) membrane containing 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline (bathocuproine) and o-nitrophenyl-octylether as the solid phase extraction medium. Copper(I) in an aqueous sample solution is trapped on the membrane with an anion species, picrate ion, to form copper(I)-bathocuproine-picrate complexes, and the copper complexes,i.e. copper(I), were concentrated in the membrane. The absorbance of the orange membrane was measured at 480 nm using a spectrophotometer, and the concentration of the copper was then calculated using a calibration graph, which expressed the relationship between the copper(I) concentration and the membrane absorbance after coloring for 10 min. The detectable concentration of copper in a sample solution was in the range of 1.5 x 10(-7)-4.3 x 10(-5)M. The reproducibility of the absorbances of membranes was 0.193 +/- 9.44 x 10(-3) with a 4.9% relative standard deviation on five repeated measurements for the sample containing 1.2 x 10(-5)M of copper(II) under the same experimental conditions.     

Miniature potassium-sensitive electrodes with neutral carriers in a poly(vinyl chloride) matrix

A miniature version of the potassium ion-selective electrode with valinomycin or dimethyldibenzo-30-crown-10 in a poly(vinyl chloride) matrix is described. Electrodes having an effective membrane area of <0.2 mm(2) exhibit Nernstian behaviour within a range of activities of the potassium ion of 10(-1)-10(-5)M, a rapid response and good long-term potential stability.     

A new procedure for the construction of flow-through optodes. Application to determination of copper (II)

A new procedure for constructing an optical fibre reflectance, bulk optode membrane type, sensor is presented. The optode membrane consists of a plasticized poly (vinyl chloride) membrane in which the ionophore is dissolved, entrapped in a cellulose support. The new optode with the dye indicator 1-(2-pyridylazo)-2-naphthol (PAN) was incorporated in a new flow-through cell and the injection system was optimized to determine Cu (II) at 567 nm in the range 5 × 10^?5–10^?3 M. The response was reproducible and the optode can be regenerated using 10^?2 M EDTA followed by water. The method was applied to the determination of copper in real samples.     

Construction of a liquid-membrane type periodate ion-selective electrode and its application to the potentiometric titration of alpha-diols and alpha-amino-alcohols

The construction of a liquid-membrane type periodate ion-selective electrode and its application to the potentiometric titration of alpha-diols and alpha-amino-alcohols are described. The ion-pair of periodate anion with Capriquat (tri-n-octylmethylammonium chloride), is easily extracted into nitrobenzene, and this extract is employed as a liquid ion-exchange membrane. The calibration curve shows Nernstian response towards periodate ion over the concentration range from 10(-1)M to 10(-7)M with a slope of 60 mV/pIO(-)(4). Selectivity coefficients with respect to various ions were evaluated. The electrode potential was independent of pH in the range 2.5-7.5. Some alpha-diols and monoethanolamine were successfully titrated potentiometrically with the aid of the present electrode.