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A comparative study of covalent glucose oxidase and laccase immobilization techniques at powdered supports for biosensors fabrication
Tvorynska, Sofiia ; Barek, J. ; Josypčuk, Bohdan ; Nesměrák, K.
In order to develop the optimal strategy and to deepen the knowledge in the field of enzyme immobilization, three different techniques of covalent binding for two enzymes (glucose oxidase and laccase) at powdered surfaces were compared. Immobilization protocol was optimized by changing supports (two mesoporous silica powders (SBA−15, MCM−41) and a cellulose powder), the functionalized\ngroups introduced at support surfaces (−NH and −COOH), and the methods of activation (glutaraldehyde and carbodiimide). Amino and carboxyl functionalized mesoporous silica and cellulose powders\nwere prepared by silanization using (3-aminopropyl)triethoxysilane and carboxyethylsilanetriol, respectively. It was found that coupling of both enzymes by their –NH groups through glutaraldehyde to -NH functionalized supports, in particular SBA15−NH and cellulose−NH for glucose oxidase, MCM41−NH for laccase, showed the highest activity and the best stability.
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(Spectro) Electrochemical Study of Cibalackrot Derivatives – Potential Chromophores for Singlet Fission\n
Šimková, Ludmila ; Lušpai, Karol ; Klíma, Jiří ; Ludvík, Jiří
Recently, substantial attention has been paid to the search for suitable chromophores for singlet fission. This photophysical effect promises to increase the maximum of theoretical efficiency of solar cells. One type of candidates are derivatives of cibalackrot. Redox properties are critical for their use. Our electrochemical work is focused on the study of oxidation and reduction of a series of substituted cibalackrot derivatives using classic voltammetric techniques and their combination with in situ UV-vis and EPR spectroscopy. The results show the reversible formation of the radical anion (cation) in the first reduction (oxidation) step enabling determination of ´´electrochemical´´ HOMO-LUMO gap.
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Spectroelectrochemistry of 1,10-phenantrolines Substituted by Pyrrolidine and Phenothiazine Redox-active Units
Sokolová, Romana ; Wantulok, J. ; Fiedler, Jan ; Nycz, J. ; Degano, I.
Compounds based on 1,10-phenanthroline (Phen) and their complexes are used in many fields, such as a stabilizing agent in the synthesis of nanoparticles, catalysts in homogeneous catalysis and as a semiconductor in organic light-emitting diodes (OLED) due to their coordination abilities. In this work, 1,10-phenanthrolines functionalized by pyrrolidine and phenothiazine units were studied by electrochemical methods. Cyclic voltammetry resulted in several oxidation and reduction voltammetric peaks. Structure-activity relationship was investigated using in situ spectroeletrochemistry, spectrophotometry, infrared spectroscopy and chromatography.
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Electrochemical Characterization of Self-Assembled Monolayers Containing Redox Switching Element
Nováková Lachmanová, Štěpánka ; Kocábová, Jana ; Vavrek, František ; Sebechlebská, Táňa ; Šebera, Jakub ; Kolivoška, Viliam ; Lukášek, J. ; Balzer, N. ; Valášek, M. ; Hromadová, Magdaléna
Adsorption properties of molecules containing [Ru(terpy)2]2+ and [Os(terpy)2]2+ redox switching element connected to the electrode surface by tripodal thiolate anchoring groups have been studied together with their charge transfer properties in the adsorbed form. STM-based current-voltage measurements confirmed that the conductance of self-assembled monolayer containing [Os(terpy)2]2+ redox switching element is lower than that containing [Ru(terpy)2]2+ element. This observation agrees with previously observed differences in the electron transfer rate constants of these molecules in their adsorbed state.
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Analysis of the Hydrated ions Clusters Impact on the Liquid/Liquid Interface
Mareček, Vladimír ; Samec, Zdeněk ; Trojánek, Antonín
Open circuit potential (OCP) measurements of the partition of tetrapentylammonium chloride (TPeACl) at the water/1,2-dichloroethane (DCE) interface reveal two remarkable processes. The first one is characterized by a decay of the OCP from its expected equilibrium value. This process has been ascribed to the extraction of the salt driven by its accumulation in the hydrated salt clusters in the DCE phase. The second process is characterized by the short-term potential spikes overlapping the long-term OCP records. These spikes are assumed to be associated with the collision and fusion of the hydrated salt clusters produced by the former process with the water/DCE interface.
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Redox Properties of Conjugated Phosphole Derivatives – Electrochemical Study
Koláčná, Lucie ; Polák, P. ; Tobrman, T. ; Ludvík, Jiří
The study describes pentasubstituted phospholes with a π-conjugated arms in positions 2 and 5 of the phosphole ring. According to the expectations, substituents with electron-donating groups led to lower oxidation potentials, the presence of electron-withdrawing groups shifts the reduction potential to less negative values. Because all studied phospholes have multiple substituents of both types, their resulting potentials represent the sum of their influences. Moreover, since many of the studied compounds have two redox centers (phosphole moiety itself and the pi-conjugated arm), their locations were determined and intramolecular interactions were followed, because substituents which can be conjugated with the π-system of phosphole are able to extend the delocalized π-system resulting in stabilization of primary redox intermediates. Chemical modification of phospholes using various combinations of substituents can set the desired electrochemical properties of studied molecules.
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Mercury Film Screen-Printed Electrodes
Josypčuk, Bohdan ; Šestáková, Ivana ; Tvorynska, Sofiia
Mercury film screen-printed electrodes (MF-SPEs) were designed, prepared and tested for the first time as perspective representatives among SPEs that allow measuring at high negative potentials. For this purpose, the precise electrochemical (coulometric) preparation procedure for mercury deposition at the working electrode surface of the commercial silver-SPE was developed and a universal method of preparing MF-electrodes from different metal-SPEs was described. An optimal electrolyzer construction for the mercury deposition, electrolyte composition, electrolysis potential, and an activation of electrode surfaces were proposed. Determination of the zinc content in food supplement tablets was used for the MF-SPEs practical testing.
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Electrochemical Techniques in Monitoring of Nervous System Drugs
Choińska-Mlynarczyk, Marta ; Hrdlička, Vojtěch ; Skopalová, J. ; Šelešovská, R. ; Kolivoška, Viliam ; Navrátil, Tomáš
Drugs of the nervous system (ATC group N) belong generally to the most commonly (mis)used substances worldwide. Their determination and monitoring of these drugs and their metabolites in various body fluids or environmental matrices represent a challenge for analytical chemists. Our research is focused on the application of electrochemical methods in the monitoring of the most frequently prescribed and the newly introduced nervous system drugs of precisely specified structures and/or of defined properties. For toxicological and pharmacokinetic reasons, emphasis has been placed on investigating the reaction mechanisms of their metabolite formation. New or alternative to commonly used electroanalytical methods applicable for monitoring and characterization of target compounds in their pure state, in body fluids, wastewaters, and other environmental matrices, has been developed. To improve the chemometric parameters and sensing characteristics, attention was paid to the construction of new electrochemical sensors, detectors (e.g. screen-printed, 3D printed), or cells, based on (modified/unmodified) traditional or nontraditional materials, preferably usable at the point-of-care.
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Voltammetric Determination of Psilocin and Psilocybin at Carbon-fiber PLA Electrode
Choińska-Mlynarczyk, Marta ; Navrátil, Tomáš
Psilocin and psilocybin are two neuroactive drugs. They can be used in experimental treatment in psychiatry, moreover, also as illicit drugs to achieve hallucinations and relaxation. Easy access to these two alkaloids indicates that their monitoring in the environment and the body fluids is necessary. Electrochemistry offers fast, simple, and easy methods of their determination using laboratory-manufactured electrodes from 3D printed carbon-fiber polylactic materials. This technique of electrode fabrication can be characterized by many benefits, e.g., desired shape or diameter of the electrode, well-developed voltammetric signals, and low background currents.
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