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Determination of Roughness Factor and Fractal Dimension of Zirconium in its Native and Surface Modified State using Atomic Force Microscopy. Effect of the Hydrogen Evolution Reaction on the Surface Structure
Novák, M. ; Kocábová, Jana ; Kolivoška, Viliam ; Pospíšil, Lubomír ; Macák, J. ; Cichoň, Stanislav ; Cháb, Vladimír ; Hromadová, Magdaléna
Atomic force microscopy (AFM) was used to characterize surface morphology of pristine zirconium, Si modified and FeSi modified zirconium electrodes prior and after hydrogen evolution at potentials negative of the open circuit potential value. Two main characteristic parameters were obtained from the ex situ AFM height images, namely, the roughness factor and fractal dimension of the studied surface. The effect of hydrogen evolution reaction on the electrode surface morphology was discussed. Fractal dimension values were used successfully to explain the non ideality of the interfacial capacitance.
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Investigation of Single Molecule Charge Transport Properties and Geometrical Arrangement in Terpyridine Architectures Supported by the Tetraphenylmethane Tripod
Kolivoška, Viliam ; Sebechlebská, Táňa ; Šebera, Jakub ; Gasior, Jindřich ; Lindner, M. ; Lukášek, J. ; Valášek, M. ; Mayor, M. ; Mészáros, G. ; Hromadová, Magdaléna
Tripodal platforms were engineered recently to realize a well-defined directional contact between metallic electrodes and molecular architectures dedicated to serve as working elements for electronic applications. In this work we employ cyclic voltammetry, scanning tunneling microscopy break junction technique and theoretical approaches based on the combination of density functional theory and non-equilibrium Green´s function to investigate the geometrical arrangement and single molecule charge transport in terpyridine-based architectures supported by tetraphenylmethane tripod. We demonstrate that this architecture adopts a favorable geometrical arrangement capable of forming highly conductive molecular junctions and is thus suitable to serve as a basis for working molecular switches.
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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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Application of a Micro-Volume Voltammetric Cell for Determination of Doxorubicin Hydrochloride
Skalová, Štěpánka ; Navrátil, Tomáš ; Barek, J. ; Vyskočil, V.
Doxorubicin is an anticancer drug, which is used for treatment of various cancer types. It contains a quinone structure, similarly as some other drugs belonging to the same category (e.g., daunorubicin and epirubicin). Its monitoring can lead to optimization of individual patient dosages and increase chances for recovery of patients. A micro-volume voltammetric cell and differential pulse cathodic stripping voltammetry have been used for determination of doxorubicin hydrochloride. A volume of used sample was 50 microL. Limit of detection was 0.39 micromol L-1. An applicability of this method was verified on samples of drinking water and of human urine.
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Electrochemical Study of the Supported Iron Oxide Catalysts
Gál, M. ; Horváth, B. ; Navrátil, Tomáš
Propylene oxide (PO) belongs to the group of the most important chemical industrial\nintermediates. It is mainly used for polyurethanes, pharmaceuticals, textile, and detergent\nproduction. In this short contribution we tried to characterize supported iron(III) oxide\ncatalyst with different amount of Fe and to find an optimal iron(III) oxide content for the best\ncatalysts performance. The importance of phase quality on the selectivity of respective\ncatalysts samples is also discussed. Linear sweep voltammetry was chosen for this purpose.\nResults obtained by electrochemical methods are compared with efficiency (selectivity) of\nrespective catalysts.
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Electrochemical Monitoring of the Water Clusters Formation in an Organic Solvent in the Presence of Hydrated Ions
Mareček, Vladimír
An electrochemical method has been developed that makes it possible to monitor the\ndynamics of the co-extraction of water with hydrated chloride ions at the interface between\ntwo immiscible electrolyte solutions (ITIES). The interfacial potential was controlled by the\ndistribution of a common tetralkylammonium (TAA+) ion. Changes in the TAA+\nconcentration at the interface were monitored by measuring the open circuit potential (OCP).\nTransfer of hydrated chloride ions is accompanied by the transfer of TAA+, decreasing its\nconcentration on the aqueous side of the interface. This process involves the co-extraction of\nwater molecules with the hydrated chloride ions and the formation of water clusters in the\norganic solvent phase. The ability to monitor the process from the very beginning of interface\nformation allowed us to obtain important kinetic data.
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Electrochemical Measurements in Flow Systems on Silver Amalgam Tubular Detector Combined with Auxiliary Electrode
Josypčuk, Bohdan ; Barek, J. ; Josypčuk, Oksana
A new type of tubular detector (TD+AuxE) was proposed, fabricated, tested and compared\nwith a typical silver amalgam tubular detector developed earlier. Non-stop-flow differential\npulse voltammetric anodic stripping method (AS-DPV) and amperometric method in a\nglucose oxidase biosensor arrangement were tested. Both detectors were applied for AS-DPV\nmeasurements in flow systems for the first time. The proposed combination of tubular\ndetector with auxiliary electrode provides a much greater current response than the classic\narrangement with three individual electrodes. All relevant parameters (potentials of\naccumulation or detection, flow rate, analyte concentrations, shielding sleeve length, etc.)\nwere optimized for the developed TD+AuxE.
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