Discrimination of apple juice and herbal liqueur brands with solid-state electrodes covered with polyaniline and thiacalixarenes.

Solid-contact ion-selective electrodes based on glassy carbon electrode covered with electropolymerized polyaniline and tetrasubstituted thiacalix[4]arene ionophores with hexyl and o-pyridylamido functional groups at the lower rim have been developed and examined in the discrimination of the brands of apple juices and herbal liqueurs. For this purpose, the liquids tested were diluted and spiked with a constant amount of Fe(3+) ions. The variation of the signal toward Fe(3+) ions was achieved due to their involvement in the reactions with the organic ligands and the antioxidants present. As was shown, the combination of the three electrodes with various receptors makes it possible to predict the brand of apple juices and herbal liqueurs using linear discriminant analysis in 95-100% cases. The discrimination procedure makes it possible to discriminate liquids within 20 min. Besides, the electrodes developed make it possible to detect individual antioxidants (ascorbic, malic, oxalic acids, hydroquinone, and quercetin) in the range from 5.0x10(-6) to 1.0x10(-2) M in direct potentiometric measurements and redox titration.

Selectivity of solid-contact Ag potentiometric sensors based on thiacalix[4]arene derivatives.

Potentiometric sensors based on glassy carbon electrode covered with polyaniline and thiacalix[4]arenes containing amidopyridine, morpholide, pyrrolidide and hydrazide functional groups in cone, partial cone and 1,3-alternate conformations have been developed and applied for determination of Ag(+) ions in the range from 1.0 x 10(-2) to 4.0 x 10(-7)M and limits of detection from 1 x 10(-7) to 3.5 x 10(-8)M. The sensitivity of Ag(+) detection decreases in the following range of thiacalix[4]arene substituents: morpholide>pyrrolidide>amidopyridine>hydrazide. Potentiometric selectivity coefficients predominantly showed binding of Ag(+), Hg(II) and Fe(III) ions over other transient and alkali metals. The influence of functional groups and conformation of receptor on the selectivity of the sensor response was investigated. As shown, selectivity and sensitivity of Ag(+) determination depends on the steric accessibility of the binding site and flexibility of the receptor structure. For Fe(III) ions, changes of the sensor potential are also determined by their implementation in redox reactions of polyaniline.

Ag selective electrode based on glassy carbon electrode covered with polyaniline and thiacalix[4]arene as neutral carrier.

Potentiometric sensor based on glassy carbon electrode covered with polyaniline and neutral carrier, e.g. thiacalix[4]arene containing pyridine fragments in the substituents in the lower rim has been developed and applied for determination of Ag(+) ions in the range from 1.0x10(-2) to 5.0x10(-7)M with the response time of 12s. The presence of thiacalixarene in the surface layer improves the reversibility and selectivity of the signal towards transient metal ions. The potentiometric selectivity coefficients were determined for various measurement conditions. As shown, the pH control and the use of NaF as a masking agent fully eliminate the interfering effect of Hg(2+) and Fe(3+) ions, respectively. The reaction of Ag(+) with thiacalixarene was proved by the investigation of the extraction of picrate complexes of transient metals in the organic phase. The potentiometric sensor developed was successfully used for the potentiometric determination of silver sulfathiazole (Argosulfantrade mark).

Amperometric immunosensor for nonylphenol determination based on peroxidase indicating reaction.

Novel immunosensor for nonylphenol (NP) determination has been developed by immobilization of specific antibodies together with horseradish peroxidase on the surface of carbon screen-printed electrode. The signal of the immunosensor is generated by the involvement of NP accumulated in the peroxidase oxidation of mediator (Methylene Blue, hydroquinone or iodide). This results in the increase of the signal recorded by linear-sweep voltammetry. The sensitivity of the detection depends on the nature of mediator, its concentration and incubation period. Cross-selectivity of the response toward readily oxidized phenolic compounds has been determined. The immunosensor developed makes it possible to detect from 20 microgL(-1) to 44 mgL(-1) of NP with detection limit 10 microgL(-1) of NP.

Electrochemical determination of the total antioxidant capacity of human plasma.

Electrochemical reduction of oxygen at a glassy carbon electrode in a 0.05 mol L(-1) solution of (C2H5)4NI in dimethylformamide leads to generation of the superoxide anion-radical. This product of reversible one-electron oxygen reduction reacts with antioxidants, a process which is based on protonation of the anion-radical by the antioxidant. Rate constants of this interaction have been calculated. Human plasma antioxidants also react with electrochemically generated superoxide anion-radical. A voltammetric method is proposed for estimation of the total antioxidant capacity (TAC) of plasma on the basis of on this reaction. The TAC of plasma was also determined using constant-current coulometry with electro-generated bromine as the active species. A correlation was observed between TAC data obtained by voltammetry (O2*-, in alpha-tocopherol units) and coulometry (Br2 as titrant). TAC of plasma from patients with purulent infections was determined. Statistically significant differences were found between TAC of patients and control group. Treatment of purulent infections increases the TAC of plasma. So, use of electrochemical methods (voltammetry and coulometry) for determination of TAC can be used for estimation of the effectiveness of treatment.

Bi-enzyme sensor based on thick-film carbon electrode modified with electropolymerized tyramine.

Bi-enzyme sensor based on thick-film epoxy-carbon electrode modified with polytyramine has been developed and examined for the determination of peroxidase substrates and cholinesterase inhibitors. Polytyramine was obtained on the electrode surface by repeated scanning of the potential from +600 to +1800 mV vs. Ag/AgCl in tyramine solution. The enzymes were immobilized in the polytyramine matrix by cross-linking with glutaraldehyde. The biosensor developed provides a reliable and inexpensive way for preliminary testing of common environmental pollutants with a single sensor in accordance with assumed toxic effect by the choice of appropriate substrate and measurement conditions. The bi-enzyme sensor makes it possible to determine substituted phenols and aromatic amines in the micromolar range of their concentrations and anticholinesterase pesticides with detection limits of 0.1 (Coumaphos) and 0.03 micromol l(-1) (Chloropyrifos-methyl).

Polyaniline-modified cholinesterase sensor for pesticide determination.

Cholinesterase sensors based on glassy carbon and planar epoxy graphite electrodes modified with processed polyaniline have been developed and examined for pesticide detection. The modification of electrode surface with polyaniline provides high operational stability and sensitivity towards the pesticides investigated. The detection limits found (coumaphos, 0.002, trichlorfon, 0.04, aldicarb, 0.03, methiocarb, 0.08 mg l(-1)) make it possible to detect the pollutants in the waters on the level of limited threshold levels without sample preconcentration.

Amperometric biosensors based on nafion coated screen-printed electrodes for the determination of cholinesterase inhibitors.

Screen-printed electrodes coated with the nafion layer have been investigated for cholinesterase biosensor design. The butyrylcholinesterase (ChE) from horse serum was immobilised onto the nafion layer by cross-linking with glutaraldehyde vapours. The biosensors obtained showed better long-term stability and lower working potential in comparison to those obtained with no nafion coating. The sensitivity of a biosensor toward organophosphate pesticides is not affected by the nafion coating. The detection limits were found to be 3.5x10(-7) M for trichlorfon and 1.5x10(-7) M for coumaphos.

Sensitivity and selectivity of electrochemical enzyme sensors for inhibitor determination.

The performance of electrochemical biosensors developed for the determination of inhibiting species is considered. The role of various factors affecting the analytical characteristics of biosensors, their selectivity toward inhibitors to be tested as well as operational characteristics is discussed. The choice of enzyme-inhibitor system, the influence of enzyme immobilization on the behaviour of a biosensor, the modes of the optimization of working conditions are discussed. Most conclusions are illustrated with the models of the application of biosensors for monitoring environmental pollutants.

Influence of surface-active compounds on the response and sensitivity of cholinesterase biosensors for inhibitor determination.

The influence of non-ionogenic surfactants, i.e., Tween-20, Triton X-100 and PEG-10,000, on the response of cholinesterase-based potentiometric biosensors and their sensitivity towards reversible and irreversible inhibitors were investigated. Acetyl- and butyrylcholinesterases were immobilized on nylon, cellulose nitrate films and tracing paper and were introduced into an assembly of potentiometric biosensors. The effect of surface-active compounds depends on the hydrophilic properties and porosity of the enzyme support material and the inhibition mechanism. In the range 0.002-0.3% m/v the surfactants show a reversible inhibiting effect on biosensor response. At lower concentrations (down to 10(-4)% m/v) the surfactants alter the analytical characteristics of reversible and irreversible inhibitor determination. The use of surface-active additives improves the biosensor selectivity in multi-component media.

New variants of enzyme immunoassay of antibodies to DNA.

A method of DNA immobilization on cellulose nitrate films has been developed. Modified films of uniform and stable surface have been used to devise two variants of solid-phase enzyme immunoassays of antibodies. The co-immobilization of enzyme label (cholinesterase) and the DNA molecules makes it possible to carry out the procedure of solid-phase enzyme immunoassay without any separation of components. Thus, it takes only 15 min to diagnose an autoimmune disease (Aleutian disease of minks) with the immunoenzyme amperometric sensor, with a lower detection limit for antibodies of 0.5 x 10(-10) M. For scaled diagnosing, solid-phase enzyme immunoassay on DNA-modified films with prior separation of components and spectrophotometric registration of peroxidase activity has been developed. The time for determination was 30 min, with a lower detection limit of 7.4 x 10(-12) M.

Determination of hydrazine derivatives by flow-injection analysis with spectrophotometric detection.

Flow-injection analysis for the determination of hydrazine derivatives based on their nucleophilic substitution reaction with 4-chloro-5,7-dinitrobenzofurazan in aqueous medium, and spectrophotometric detection has been described. The calibration graphs were linear in the range from 0.15 to 4.0 mug ml(-1) of hydrazine derivatives, with sampling rates of up to 28-32 samples h(-1). Interferences from amino compounds, benzoic acids, aliphatic amines and ammonia have been evaluated. The procedure has been applied to the determination of hydrazine derivatives in serum, urine, appressin drugs and artificial mixtures.

Electrochemical investigation of palladium complexes with organic sulphides and their use in extraction differential pulse polarography.

Dialkyl-, amino-, keto- and ketoaminosulphide complexes of palladium(II) are shown to undergo one- or two-step reduction in a mixed acetonitrile-toluene solvent containing Bu(4)NClO(4) at 0.1 M concentration. The half-wave potentials of the complexes show a certain dependence on the ligand structure, a positive shift of the potentials being caused by an increase in the pi-acceptor ability of the ligands. The limiting currents are proportional to the concentration of the complex, according to the Ilkovic equation. Fast-scan differential pulse polarography was applied to the determination of palladium(II) in the organic phase after extraction of its complex with dihexylsulphide.

The stability of metal complexes with 8-mercaptoquinoline and alkyl-substituted 8-mercaptoquinolines in dimethylformamide.

The stoichiometry and stability constants of 8-mercaptoquinoline and alkyl-8-mercaptoquinoline complexes of Zn(II), Cd(II), Pb(II), Ni(II), Bi(III) and Ag(I) were determined potentiometrically in dimethylformamide. The stability of the 8-mercaptoquinolinates decreases in the order Ag(I) Bi(III) Ni(II) Pb(II) Cd(II) Zn(II). Metal 7-methyl-8-mercaptoquinolinates are the most stable. The presence of the alkyl group in the 2-position (which has a steric effect) lowers the strength of metal-ligand bonding.