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Continuous monitoring of anthraquinone-based anticancer drugs by amperometric technique
Skalová, Štěpánka ; Fischer, J. ; Barek, J. ; Navrátil, Tomáš ; Krejčí, J. ; Kučerová, R. ; Vyskočil, V.
This contribution is focused on the development of electroanalytical methods for the monitoring of anthraquinone-based anticancer drugs in physiological solution by combination of liquid-flow system and dialysis catheter, possibly inserted into blood circulation of patients. For this purpose, amperometric detection with dual glassy carbon electrode was developed and derivate of these drugs, anthraquinone-2-sulphonate, was used as a model compound. Two different flow rates of carrier solution (physiological solution) were tested (specifically, 1 and 5 mu L min(-1)) and the dependence of peak currents of anthraquinone-2-sulphonate on its concentration was verified
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Electrochemical Enzymatic Biosensors for Determination of Catecholamines in Flow Systems
Josypčuk, Bohdan ; Barek, J. ; Josypčuk, Oksana
Several biosensors (BS) based on flow enzymatic mini-reactors containing a mesoporous silica powder covered by enzyme laccase or tyrosinase were used for determination of L-DOPA, dopamine, noradrenaline, and adrenaline. The silica powder of MCM-41 with covalently bonded laccase was found to be the best reactor filling for the detection of catecholamines. Relative current response of such BS was 100 % for dopamine, 32.1 % for L-DOPA, 26.2 % for noradrenaline, and 0.71 % for adrenaline. The practical applicability of Lac-MCM41 biosensor was successfully verified by the determination of dopamine and noradrenaline in medical solutions for infusions.
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Voltammetry at Silica Gel-Modified Carbon Paste Electrode
Šestáková, Ivana ; Navrátil, Tomáš
Voltammetry using silica gel modified carbon paste electrode (SiO2-CPE) for oxidation of selected flavonoid showed better sensitivity and reproducibility than oxidation using glassy carbon or unmodified carbon paste electrode. Only SiO2-CPE is useful for study of cadmium complexation with cysteine containing ligand as phytochelatin or metallothionein. Voltammetry on boron doped diamond electrode showed only peak of sulfur compound oxidation, which decreased with the addition of cadmium ions.
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Voltammetric Determination of Chili Peppers Pungency using Phospholipid Modified Glassy Carbon Electrode\n
Skopalová, J. ; Rajcová, A. ; Vokounová, D. ; Navrátil, Tomáš
The aim of this study was to develop a simple method for evaluation of the pungency in chili peppers with a glassy carbon electrode modified using phospholipid membrane prepared from asolectin. For these purposes cyclic voltammetry (CV) and differential pulse voltammetry (DPV) have been used. A few different methods have been tested: direct method, transfer method on unmodified and modified electrode, using standard addition method as well as calibration curve method. A statistically significant correlations with the results of the reference HPLC method have been found in case of voltammetric methods, especially in DPV with asolectin modified electrode.
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HPLC-ED/UV for determination of vanillylmandelic acid in human urine after solid phase extraction
Němečková-Makrlíková, Anna ; Dejmková, H. ; Navrátil, Tomáš ; Barek, J. ; Vyskočil, V.
HPLC with electrochemical and spectrophotometric detection (ED/UV) after solid phase extraction (SPE) was used for determination of vanillylmandelic acid in human urine. HPLC-ED was performed at a glassy carbon electrode in a “wall-jet” arrangement in acetate-phosphate buffer at pH = 2.5 and gradient elution (increasing content of\nacetonitrile from 5 to 25% in 10 minutes) was used. Optimized parameters were following: flow rate of mobile phase 1 mL min−1, detection potential +1.1 V, detection wavelength 279 nm, injected volume 20 μL. Dependence of the peak current on the analyte concentration was linear in the concentration range from 10 to 150 μmol L−1, with obtained limits of detection 2.6 μmol L−1 (calculated from peak height) and 1.9 μmol L−1 (calculated from peak area) for HPLC-ED, and 11.0 μmol L−1 (calculated from peak height) and 9.8 μmol L−1 (calculated from peak area) for HPLC-UV.
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Hollow-fibre Based Microextraction and Voltammetric Determination of Vanillylmandelic Acid
Hrdlička, Vojtěch ; Barek, J. ; Navrátil, Tomáš
New method of liquid/liquid/liquid hollow fibre based microextraction of vanillylmandelic acid coupled with voltammetric determination is being developed. Selected liquid membranes based on alcohols, aliphatic hydrocarbons and esters were tested. Highest enrichment factor of 2.52 after 30 minutes of extraction was obtained using propyl benzoate, RSD = 18.2 % (n=5). Mechanically and cathodically pretreated (-1000 mV vs. Ag/AgCl/3M KCl, 15 s) boron doped diamond electrode in a miniaturized arrangement was used for DPV determination. LOD = 1.2 micromol/l, RSD = 5.9% (n=10) for a 10 microl extract.
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Differences in Oxidation Mechanism of Selected Bioflavonoids, UV-Vis and IR Spectroelectrochemical Study
Sokolová, Romana ; Fiedler, Jan ; Ramešová, Šárka ; Kocábová, Jana ; Degano, I. ; Quinto, A. ; Křen, Vladimír
The oxidation of selected bioflavonoids (quercetin, rhamnazin, fisetin, rhamnetin, taxifolin, luteolin, silybin and 2,3-dehydrosilybin) was studied by electrochemical and spectroscopic methods. The oxidation mechanism and formation of oxidation products depends on the chemical structure. Only small differences in the chemical structure of compounds with flavone, flavanone and flavonol motif result in extremely variable oxidation pathways and products. Products of oxidation and further decomposition were determined by HPLC-ESIMS/MS and HPLC-DAD.
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Behavior of Metallothioneins and Phytochelatins at Mercury and Amalgam Electrodes
Šestáková, Ivana ; Navrátil, Tomáš ; Josypčuk, Bohdan
The presence of cysteine residues in molecules of metallothioneins or phytochelatins is crucial for their electrochemical behavior. At mercury electrodes, the reduction of\ntetracoordinated Cd and Zn in molecule of mamamalian MT is observed in solution of pH 8- 8.5, whereas with lowering pH or at presence of excessive ions, signals of differently coordinated or free metal ions appear. Such changes were confirmed on model complexes with phytochelatin PC2 .Using amalgam electrodes CuSAE or AgSAE for voltammetry of metallothioneins or phytochelatins, their Cu or Ag complexes are formed on the electrode surface, which could be with limitations - employed for the analytical purposes.
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HPLC-ED/UV with Solid Phase Extraction for the Determination of 5-Hydroxyindole-3-acetic Acid
Němečková-Makrlíková, Anna ; Dejmková, H. ; Navrátil, Tomáš ; Barek, J. ; Vyskočil, V.
Determination of 5-HIAA in human urine was successfully performed using HPLC-ED/UV with SPE. HPLC-ED is a very sensitive technique, presented method does not need any sample pre-treatment apart from SPE procedure, which replaced filtration of samples of human urine to avoid problems with clogging a HPLC column. The found native\nconcentrations of 5-HIAA in human urine using HPLC-ED with SPE fully corresponds with published normal concentrations in urine (17.8 - 58.3 micromol l-1). The found native concentrations of 5-HIAA were 18.4 micromol L-1 (calculated from peak height). The presented method is fast and could be used for simple\nscreening of human urine, because HPLC-ED/UV allows simultaneous determination of 5-HIAA, HVA, and VMA as important tumour biomarkers.
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