Application of flow-injection potentiometric system for determination of total concentration of aliphatic carboxylic acids.

In this work, flow-injection system with potentiometric detection was tested for determination of total carboxylic acid concentration. Detection part of the examined system consists of ion-selective electrodes (ISEs) with polymer membranes of different compositions. First electrode is based on Zr(IV)-tetraphenylporphyrin as ionophore selective towards carboxylic acid anions, the membrane of second one contains only liphophilic anion exchanger - tridodecylmethylammonium chloride. Final response of the system is a result of combination of EMF signals from both electrodes. Combination of two detectors enables significant decrease of differences between potentiometric signals induced by mixtures of studied anions of various concentrations as compared to results obtained only with metalloporphyrin-based ISE. The use of anion-exchanger based detector allows for elimination of the influence of aliphatic carboxylic acids lipophilicity. Proposed potentiometric flow-injection system was employed for determination of short-chain aliphatic carboxylic acids (so-called VFA - volatile fatty acids) in samples originating from an anaerobic digester. Results obtained for these relatively complicated samples are in good agreement with results obtained with the use of reference colorimetric method. Linear response towards carboxylic acids was observed in the concentration range of 10(-4) to 10(-2)mold m(-3), with the slopes in the range of -110 to -150 mV dec(-1) (for acetate(-) and butyrate(-), respectively). System enables for determination of about 6 samples per hour. Life time of ISEs average about 2 months.

Optical acetylcholine sensor based on free base porphyrin as a chromoionophore.

In this work, the possibility of application of free base porphyrin as a lipophilic pH chromoionophore for the preparation of optical cation-selective sensors was investigated. The properties of polymeric membranes, containing porphyrins of different structures, namely tetraphenylporphyrin (TPP) and octaethylporphyrin (OEP), were compared. Changes in equilibrium between protonated and deprotonated form of porphyrin, resulting from variations in ACh concentration, were evaluated. The influence of various factors (kind and quantity of anionic additive and porphyrin in the membrane phase, pH of sample solution) on initial equilibrium was studied. The best membrane composition was chosen as: TPP 3 wt.%, KTFPB 175 mol.% relative to ionophore, PVC:o-NPOE (1 : 4) and measuring buffer solution: 0.05 M MES, pH 4.5. Selectivity, response stability, reversibility and repeatability tests were carried out for chosen sensor. Developed sensor allowed for the determination of a model analyte, acetylcholine, at the concentration range of 10(-5) to 10(-2) M, both in stationary and flow-injection system. Sensor response was reversible and repeatable in the mentioned concentration range.

Metalloporphyrin-based acetate-selective electrodes as detectors for enzymatic acetylcholine determination in flow-injection analysis system.

In this work two Zr(IV)-porphyrins were tested as potential acetate-selective ionophores. It is shown that these compounds show increased selectivity towards acetate ion, with selectivity sequence: Cl- < NO3- < SCN- < ClO4- < acetate- < F-, when incorporated into polymeric ion-selective membranes. Among tested ionophores, Zr(IV)-tetra(tert-butylphenyl)porphyrin was found to be the best in terms of response time (20 s) and lower detection limit (2 x 10(-4) M acetate-). Designed electrodes were used as detectors in flow-injection analysis system for acetylcholine determination. Enzymatic hydrolysis was used to generate acetate ions from acetylcholine, employing acetylcholinesterase immobilized on Amberlite. The optimization of enzymatic reactions and flow-injection analysis system configuration were performed and enzyme immobilization procedures have been evaluated. It is shown that resulting flow-injection system exhibits good working parameters, such as reproducibility (standard deviation < or = 3.5%), sampling rate (60 samples per hour) and lifetime (over a week).

Complexes of tetra-tert-butyl-tetraazaporphine with Al(III) and Zr(IV) cations as fluoride selective ionophores.

In this work, complexes of Zr(IV) and Al(III) cations with 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraazaporphine (TAP) were tested as ionophores in plasticized PVC membranes of ion-selective electrodes. It was found that both tested ionophores show enhanced affinity towards fluoride anion. High fluoride selectivity was observed in the presence of anionic or cationic additives in the membrane, which indicates that proposed compounds work according to charged or neutral carrier mechanism, depending on membrane composition and pretreatment. tert-Butyl substituents, present in the structure of tested compounds, were supposed to prevent formation of ionophore dimers within the membrane phase. This process was found to be responsible for some unfavorable potentiometric properties of electrodes based on complexes of Zr(IV) and Al(III) cations with porphyrins (compounds closely related to tetra-tert-butyl-5,10,15,20-tetraazaporphine). As it was shown using spectrophotometrical measurements, Al(III)-TAP was not susceptible to dimerization, while dimer formation was observed for Zr(IV)-TAP. In full agreement with these observations, electrodes with membranes containing Al(III)-TAP responded in near-Nernstian and fast manner towards fluoride anion, while the employment of Zr(IV)-TAP as ionophore resulted in super-Nernstian and sluggish response. Plasticized PVC membranes doped with Al(III)-TAP and 20mol% of lipophilic anionic additives shown remarkable F(-) selectivity, with selectivity coefficients, logK(F-pot.).(Y-), as follows: -4.4 (Y(-)Br(-)), -4.3 (Cl(-)), -4.2 (NO(3)(-)), -3.6 (SCN(-)), -2.9 (ClO(4)(-)).