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Electrochemistry of Phospholes
Koláčná, Lucie ; Liška, Alan ; Ludvík, Jiří
Seventeen pentasubstituted phospholes with expected application in organic electronics were\nsynthesized and characterized electrochemically and by UV-vis spectra. Quantum chemical\ncalculations ofredox potentials and HOMO-LUMO energies were performed and experimental\nand theoretical data were successfully correlated. Tuning of redox properties can be achieved\nby combination of induction and resonance effects of substituents, extension / diminution of\nthe pi- delocalized system and by steric changes which affect intramolecular electron\ncommunication.
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Voltammetric Determination of Heavy Metals in Honeybee Venom using Hanging Mercury Drop Electrode and Carbon Conductive Filaments for 3D Printer
Navrátil, Tomáš ; Choińska-Mlynarczyk, Marta ; Šestáková, Ivana ; Hrdlička, Vojtěch
Heavy metals belong to typical contaminants of our environment. It is known that they are\nmetabolized and incorporated into bee products as honey as well as honeybee venom (apitoxin).\nIt is supposed that their composition can reflect contamination of the “bee environment” and\ncan give us information about the environment in the neighborhood of human dwellings.\nThis study aimed to develop a simple method for the determination of heavy metals in honeybee\nvenom. Due to the complicated matrix, wet microwave mineralization with sulfuric acid, nitric\nacid, under increased temperature and pressure, and repeated boiling with concentrated nitric\nacid had to be applied. Voltammetry proved to be very suitable for the determination of heavy\nmetals.\nTwo types of working electrodes have been used: pen-type hanging mercury drop electrode and\ncarbon conductive filaments for 3D printers. Results achieved using both of them and their\nadvantages and limitations have been compared.
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Metallothioneins as Biomarker of Environmental Pollution
Šestáková, Ivana ; Křivská, D. ; Navrátil, Tomáš
Small wild mammals living at contaminated soil are exploited for monitoring of their metal and\nmetallothionein (MT) levels, which can be influenced by presence of parasites. This has been\ntested in laboratory experiment with white rats (Rattus norvegicus) infected with tapeworm\nHimenolepis diminuta and given diet enriched with lead or zinc. The influence of parasite was\nconfirmed with analysis of samples, where metal concentrations in infected groups were\nlowered in comparison with the uninfected rats. Within infected groups, tapeworms MT levels\nwere 6 or 3 times higher than MT in tapeworms of the control group. Obtained results support\npossibility of using MT concentration in Himenolepis diminuta for biomonitoring.
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Determination of Selected Drugs using 3D Printed Electrodes
Choińska-Mlynarczyk, Marta ; Hrdlička, Vojtěch ; Navrátil, Tomáš
The main aim of this research was to develop a new method for voltammetric determination of\npopular antidepressants, analgesics, and illicit drugs using a laboratory-made 3D printed\nelectrode and to compare the achieved results with those registered using a commercially\navailable glassy carbon electrode. These experiments represent the first step in the development\nof a method applicable in clinical and forensic praxis for the rapid and inexpensive\ndetermination of commonly misused groups of biologically active compounds.
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The use of Boron Doped Diamond Electrode for Determination of 5-hydroxyindoleacetic Acid
Hrdlička, Vojtěch ; Navrátil, Tomáš
A new method for voltammetric determination of clinical biomarker 5-hydroxyindoleacetic\nacid (HIAA) at the boron-doped diamond electrode (BDDE) was developed. Anodically and\ncathodically pretreated BDDEs were tested in the pH ranges from 1 to 12, pre-treatment at\n+2.0V/60 s, and pH 3 was found to be the optimum.\nThe optimum square wave voltammetry (SWV) parameters were: f = 12 Hz, amplitude 60\nmV, and potential step 4 mV. SWV concentration dependency was constructed in the range\nfrom 0.1 to 100 μmol L−1, limits of determination and detection were 0.3 and 0.1 μmol L−1,\nrespectively. HIAA oxidation electrode process at BDDE was diffusion-controlled, as\nuncovered by cyclic voltammetry. Interestingly, HIAA peak potential was constant in various\nranges of pH, indicating a non-Nernstian behavior at the BDDE, in contrast to a previously\npublished electrooxidation mechanism consisting of a coupled H+/e− transfer.
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Ion Transfer Voltammetry across the Polarized Ionic Liquid/Water Interface: Base for Electrochemical Sensors
Langmaier, Jan ; Samec, Zdeněk
Some electrochemical techniques such as voltammetry at the polarized interfaces between two\nimmiscible electrolyte solutions (ITIES) represent interesting alternatives to classical\nelectrochemistry. The benefit of the ion transfer voltammetry lies in the possibility of detection\nof ionic species which are not otherwise redox active. The methodology enables apart of direct\ndetermination of ionic samples (including pharmaceutical and clinical ones) also to monitor\nreaction processes (acido-basic, enzymatic, etc.), determination of reaction substrates and\nproducts in one experimental step, evaluation of reaction and transport kinetics, and estimation\nof lipophilicity of involved species.
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Preparation, Testing and Application of Amalgam Screen-Printed Electrodes
Josypčuk, Bohdan ; Langmaier, Jan ; Tvorynska, Sofiia
Silver amalgam screen-printed electrodes (AgA-SPEs) were designed, prepared, and tested for\nthe first time as perspective representatives among SPEs for measuring at high negative\npotentials. The precise coulometric preparation procedure for mercury deposition at the\nworking electrode surface of the commercial silver-SPE was developed. An optimal\nelectrolyzer construction for the mercury deposition, electrolyte composition, and electrolysis\nconditions were proposed. The maximum value of hydrogen overvoltage (-1979 ± 4 mV) was\nfound on AgA-SPE with 50% (w/w) of Hg content in 0.1 mol L-1 NaOH, which is more negative\nthan with the original silver-SPE for 387 mV (-1592 ± 12 mV).
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Comparison of the Covalent Laccase Immobilization at Amino- and Carboxylfunctionalized Mesoporous Silica, Glassy Carbon, and Graphite Powders using Different Coupling Agents for Optimal Biosensor Preparation
Tvorynska, Sofiia ; Barek, J. ; Josypčuk, Bohdan
In order to find the most suitable immobilization protocol, a comparison of three strategies\nbased on the application of –NH2 and –COOH functionalized supports with the different\nactivation agents (glutaraldehyde and carbodiimide) have been conducted for the covalent\nenzyme (laccase) attachment. Two kinds of the supports, namely mesoporous silica (SBA−15,\nMCM−41) and carbonaceous (glassy carbon, graphite) powders, have been used. It was found\nthat a biosensor consisted of tubular detector of silver solid amalgam as a working electrode\nand the enzymatic mini-reactor with laccase covalently attached to glutaraldehyde activated\n–NH2 functionalized MCM−41 shows the best results regarding sensitivity and stability for\ndopamine detection.
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Construction and application of the amperometric uric acid biosensors based on the covalent immobilization of uricase by different strategies
Tvorynska, Sofiia ; Barek, J. ; Josypčuk, Bohdan
In this work, a promising combination of a biosensor based on the\nenzymatic mini-reactor with the detection principle of four-electron\nreduction of the consumed oxygen at highly negative potential has\nbeen developed for uric acid determination using flow injection\nanalysis. The construction of the biosensor provides a spatial\nsegregation of the biorecognition (uricase-based mini-reactor) and\ndetection (tubular detector of silver solid amalgam (TD-p-AgSA))\nparts. To find out the most appropriate enzyme immobilization\nprotocol, three different strategies of the covalent attachment for\nuricase from Bacillus fastidiosus have been compared. It was found\nthat the biosensor with the mini-reactor based on the covalent\nattachment of uricase via glutaraldehyde to -NH2 functionalized\nmesoporous silica powder MCM-41 showed extremely high stability\n(>1 year) and reusability (at least 600 measurements) The biosensor's\npractical applicability was confirmed by successful determination\nof uric acid in human urine.
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