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Electrochemical Valorization of Lignocellulosic Biomass Amination of Furfural and 5-Hydroxymethylfurfural
Donkeng Dazie, Joel ; Koláčná, Lucie ; Urban, Jiří ; Lamač, Martin ; Ludvík, Jiří
Furfural (FF) and 5-hydroxymethylfurfural (HMF) isolated from waste lignocellulosic biomass represent renewable sources. The present contribution deals with the transformation of FF and HMF into furfuryl amines which are important precursors namely for pharmaceutical synthesis. First, FF and HMF underwent condensation reactions with various amines which were electrochemically monitored to optimize the process. The resulting Schiff bases were identified by NMR and subsequently electrochemically reduced in basic media. The vicinal diamine (aminopinacol) was the main product besides the expected furfuryl amines. This reaction is a contribution to green synthesis because it was performed electrochemically, in water, and without any metallic catalysts.
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Redox Properties of Pyrene-Cyclohexene Conjugates – Electrochemical Study
Koláčná, Lucie ; Čubiňák, M. ; Tobrman, T. ; Ludvík, Jiří
The series of 16 compounds for "organic electronics" comprising the double-bond cyclohexene core extended by pyrene and/or other aromatics were electrochemically characterized by rotating disk voltammetry in N,N-dimethylformamide. Due to multiple substitutions, the resulting potential gap represents the sum of all substituent effects. Different combinations of substituents can be used to achieve the desired properties of cyclohexene-pyrene derivatives. The electrochemical data presented in this contribution facilitate further tuning of properties of these molecules and systems to achieve features required in material chemistry just by means of chemical modification.
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Electrochemistry of Acetaminophen
Mikysek, T. ; Ludvík, Jiří
The contribution is focused on electrochemical oxidation of acetaminophen mainly in non-aqueous media. The influence of various organic solvents as well as the pH effect is described herein. The redox properties of acetaminophen were studied by means of cyclic voltammetry, and rotating-disk voltammetry. We found that the protonation/deprotonation of acetaminophen acts as a ratedetermining step, where the stability of phenoxy radical intermediate plays an important role.
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Electrochemically Investigated pH-dependent Redox Properties of Copper Complexes of Azamacrocyclic Ligands
Koláčná, Lucie ; Maďar, M. ; Kubíček, V. ; Ludvík, Jiří
Investigated Cu(II) complexes are based on plain or cross-bridged cyclam. The\nelectrochemically inactive cyclam was modified by carboxylate, phosphonate, or phenolate\npendant arms. Cu(II) represents the main redox center of the complexes. Modification of the\nligand causes a changed pattern of complex redox response in buffered aqueous solution.\nIrreversible Cu(II) reduction results in complex decomposition to amalgamated copper and\nligand in excess. After Cu(0) electrochemical in situ re-oxidation, copper and ligand are recomplexed.\nComplexes undergo isomerization, accelerated by increasing the temperature. The\ninfluence of pH on complex isomerization and the reversibility of its reduction was described.
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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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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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Oxidation Processes of N-methylguanines
Trnková, L. ; Třísková, I. ; Liška, Alan ; Ludvík, Jiří
The oxidation processes of N-methylguanines were investigated in both experimental and\ntheoretical way. Voltammetric oxidation potentials of guanine and its methyl analogues,\nacquired on polymer pencil graphite electrode (pPeGE), were compared with the HOMO\n(SOMO) energies calculated by density functional (DFT) methods. Our study contributes to\nunderstanding not only the oxidation processes of methylated guanines but also their role in\nepigenetics.
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Differences in Electrochemical Reduction of Mono- and Polynuclear Acylgermanes
Šimková, Ludmila ; Dunlop, David ; Liška, Alan ; Ludvík, Jiří
Recently, titanocene derivatives have been investigated in term of their potential use as\ncytostatics in the treatment of oncological diseases. The potentials for reduction or oxidation of\nindividual substances are one of the key properties which fundamentally affect the cytostatic\nefficiency. Our previous results led us to investigate the redox properties of series of titanocene\ndifluoride and dichloride derivatives. This study is mainly focused on the effect of the\nsubstitution of cyclopentadienyl ring and the halide anion on the redox properties of the\nderivative.
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Differences in Electrochemical Reduction of Mono- and Polynuclear Acylgermanes
Liška, Alan ; Frühwirt, P. ; Haas, M. ; Ludvík, Jiří ; Gescheidt-Demmer, G.
Ail the studied compounds accept first electron under formation a stable anion radical. The\ncorresponding reduction potentials in aprotic media depend on electronic (inductive,\nmesomeric) properties of the substituents, their number, and position. Here, aromatic acyl group\n(benzoyl group with various substitution on aromatic ring) is the principal substituent. The\nredox properties of presented organoelement compounds with central heteroatom Ge (Si, Sn)\nare controlled by peripheral carbonyl groups (in role of redox centers), their number, and\naromatic ring substitution. The measured first reduction potentials E1 values are found in wide\nrange (> 900 mV) due to the fact that the redox centers are carbony 1 groups connected through\nheteroatom in case of acylgermanes, while for di- and trinuclear derivatives (which are\nmolecules with multiple redox centers) the easiest reducible center is the bridging aromatic unit\ninfluenced by the closest carbonyl groups. Thus, it is possible to distinguish both groups ofnonequivalent\ncarbonyl substituents.
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