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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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Oxidation and Reduction of Selected 1,10-Phenantrolines
Wantulok, J. ; Sokolová, Romana ; Nycz, J. E. ; Degano, I.
Derivatives of 1,10-phenanthroline (Phen) are well-known bident ligands which had a lot of interesting applications thanks to their coordination abilities. Selected 1,10-phenanthroline compounds were studied by electrochemical methods. Depending on their different substituents were observed several oxidation and reduction voltammetric peaks. The study involves also in situ spectroeletrochemistry, infrared spectroscopy and identification of products by HPLC-DAD and HPLC-ESI MS/MS.
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Studium elektronových vlastností a reakčních mechanismů komplexů Pt(IV) metodami kvantové chemie.
Šebesta, Filip ; Burda, Jaroslav (vedoucí práce) ; Straka, Michal (oponent)
U platinových komplexů byly stejně jako u mnoha sloučenin dalších tranzitních kovů prokázány protirakovinné účinky. Cílem dnešní medicíny je nahradit používané cisplatinové komplexy látkami, které vykazují méně vedlejších účinků. Tato práce se zabývá reakcí 5'˗dGMP (2'˗deoxyguanosin˗5'˗monofosfát) a cGMP (cyklický 2'˗deoxyguanosinmonofosfát) s platičitým komplexem PtIV (dach)Cl4 (dach=diaminocyklohexan). V oxidačním procesu GMP pomocí tetraplatiny dochází nejprve k jeho navázání na guanin do pozice N7. Následuje nukleofilní atak 5'-fosfátu nebo 5'-hydroxylu na uhlík C8 guaninu, kdy dojde k přenosu dvou elektronů a výsledkem reakce je 8˗oxo-guanin a PtII (dach)Cl2. Vzniklý Pt(II) komplex narozdíl od kineticky inertního reaktantu vykazuje protirakovinnou aktivitu. U cGMP končí mechanismus substituční reakcí za vzniku PtIV (dach)Cl3(N7-cGMP). Optimalizace struktur jsou provedeny na úrovni DFT s funkcionálem B3LYP v bázi 6-31G(d) s použitím implicitního solvatačního modelu IEFPCM/UA0. Na úrovni B3LYP/6˗311++G(2df,2pd) v solvatačním modelu IEFPCM/sUAKS byly dále stanoveny energetické parametry reakce. Nakonec byly ze znalosti tranzitních stavů určeny rychlostní konstanty a porovnány s experimentálními hodnotami.
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Searching for Electrochemical Reduction Mechanism of Azidophenyl DNA Labels
Daňhel, Aleš ; Trošanová, Zuzana ; Balintová, Jana ; Hocek, Michal ; Fojta, Miroslav
This contribution brings new information to sporadic scientific results concerned to electrochemical reduction of aromatic azides. Selected compounds used as perspective DNA labels or their structural constituents such as, 4-azidophenyltrifluoroboronic acid, 4-azidophenyl modified deoxycytidine and next probable analogous compounds and/or products of their reduction, were voltammetrically studied and compared to each other in order to reveal a mechanism of their electrochemical reduction at mercury electrodes in aqueous media. Preliminary results obtained by cyclic voltammetry at mercury and carbon based electrodes and by mass spectrometry of the products isolated from batch electrolysis on mercury pool by preparative chromatography are discussed.
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