Institute of Organic Chemistry and Biochemistry

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2020-01-13
08:29
Lokalizace poloh dvojných a trojných vazeb u methylesterů mastných kyselin pomocí HPLC/APCI-MS2
Horká, Petra ; Vrkoslav, Vladimír ; Cvačka, Josef
Poloha a počet dvojných vazeb v alifatickém řetězci ovlivňuje fyzikální, chemické a biologické vlastnosti lipidů, avšak jednoznačné určení poloh těchto násobných vazeb je problematické. V roce 2012 byla publikována metoda kapalinové chromatografie s chemickou ionizací za atmosférického tlaku s hmotnostní detekcí (HPLC/APCI-MS) [1] vhodná pro analýzu polohy dvojných vazeb využívající tvorby molekulových aduktů [M + C3H5N]+. při APCI za přítomnosti acetonitrilu. Methylestery mastných kyselin (FAMEs) byly analyzovány HPLC/APCI-MS2 se 100% acetonitrilem jako mobilní fází. Při APCI docházelo v plynné fázi k tvorbě reaktivních částic, vznikajících ze složek mobilní fáze, které se vázaly na násobné vazby v alifatickém řetězci FAMEs za vzniku aduktu [M + C3H5N]+.. Kolizně indukovanou disociací (CID) aduktu [M + C3H5N]+., se získaly diagnostické fragmenty určující polohu (polohy) násobných vazeb. Zmíněná metoda byla evaluována pro běžně analyzované polynenasycené FAMEs s tradiční polohu dvojných vazeb (methylene-interrupted).

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2019-12-09
08:15

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2019-12-09
08:15

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2019-12-09
08:15
Structural characterization of fatty acids with triple bond and unusual double bond positions by HPLC/APCI-MS2
Horká, Petra ; Vrkoslav, Vladimír ; Cvačka, Josef
Fatty acid methyl esters (FAMEs) were analyzed by reversed-phase HPLC coupled to atmospheric pressure chemical ionization (APCI) mass spectrometry. Acetonitrile was used as mobile phase. The gas-phase reactions of acetonitrile and unsaturated FAMEs in the APCI source provided [M + C3H5N]+• adducts. Subsequent MS/MS analysis of these ions gave diagnostic fragments. The formation and fragmentation of the acetonitrile-related adducts were utilized for the structural characterization of FAME with isolated double bonds in (Z)-9,19-hexacosadienoic acid methyl ester, FAME with conjugated double bonds in (Z)-9,11-octadecadienoic acid methyl ester and FAME with a triple bond in 9-octadecynoic acid methyl ester.

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2019-12-09
08:15
Method optimization for simultaneous separation of six triazole fungicides in HPLC
Kovač, Ishak ; Martín Miján, P. ; Del Sol Vega Alegre, M. ; Dejmková, H. ; Jaklová Dytrtová, Jana ; Schwarzová, K.
Triazole pesticides are widely used in agriculture against fungi pathogens. Their application is not restricted on just one member of the group, more importantly, the application is usually carried out in the mixture of two or more triazoles. Hence, this work focuses on simultaneous separation and detection of six triazole fungicides: penconazole, tebuconazole, propiconazole, cyproconazole, fenbuconazole, and difenoconazole. Two different columns were tested with different parameters for isocratic and gradient elution in HPLC with UV detector. On Purospher Reverse Phase-18 column with gradient elution isomers of triazoles cyproconazole and propiconazole were successfully separated. However, on this column, there was an overlap of some triazoles. In contrast, the isocratic elution on Kromasil Eternity-5-PhenylHexyl column showed sufficient separation capabilities. In further research, chiral separation of triazoles will be considered using capillary electrophoresis.

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2019-12-09
08:15
Aldrithiol-2 as a new derivatization agent for double bond localization in unsaturated compounds by mass spectrometry
Strmeň, Timotej ; Cvačka, Josef
A new method for localizing double bonds in lipids using derivatization with 2,2'-clipyridyl disulfide (Aldrithio-2) and electrospray ionization mass spectrometry (EST-MS) is presented. The derivatization introduces a permanent charge to the molecules. When collisionally activated, the derivatives provide diagnostic peaks useful for establishing the position of the original double bond. Since permanent charge of the derivative significantly increases the detectability of analytes, the method works well also for of very low polarity like hydrocarbons.

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2019-11-25
10:16

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2019-01-07
14:42
Penconazole and its behaviour in the presence of copper
Jakl, M. ; Jaklová Dytrtová, Jana
Penconazole is a fungicide frequently used in agriculture. Its possible impact to (non-)target species is influenced by its interactions e.g. with copper, typically present in soil as an ion (or in week complexes) or in bodies, as a part of enzymes. This study brings the information potentially useful in the evaluation of penconazole fate in the environment. The studies based on the electrospray gas phase experiments provide an estimate of the penconazole reactivity in copper presence including its possible degradation pathways.

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2019-01-07
14:42
Temperature-programed micro-HPLC analysis of fatty acid methyl esters with APCI-MS detection
Vrkoslav, Vladimír ; Rumlová, Barbora ; Cvačka, Josef
HPLC/APCI-MS analysis at microliters-per-minute flow rates was optimized for separation of fatty acid methyl esters (FAMEs). HPLC C18 column with an internal diameter of 0.3 mm and isocratic elution using 99.9 % acetonitrile and 0.1% formic acid were employed. Standard APCI ion source was suitable for detection of FAMEs at 10 μl/min flow rate with the detection limit of micrograms-per-milliliter. APCI-MS spectra with predominant [M + H]+ molecular adducts were observed. The main advantage of micro-flow measurements is the possibility of using a temperature gradient, which significantly reduces retention times of FAMEs with longer aliphatic chain. The significant reduction of solvent consumption is also an important economic and environmental advantage. The positions of double bonds in FAME chains were established using acetonitrile-related adducts and tandem mass spectrometry. The optimized method was applied for analysis of FAMEs in triacylglycerol fraction of black currant seeds oil.

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2019-01-07
14:42
Determination of binding constants of human insulin complexes with serotonin, dopamine, arginine, and phenol by pressure assisted partial filling affinity capillary electrophoresis
Šolínová, Veronika ; Žáková, Lenka ; Jiráček, Jiří ; Kašička, Václav
A new method, pressure assisted partial filling affinity capillary electrophoresis (PF-ACE), has been developed to study noncovalent interactions of the hexamer of human insulin (HI) with cationic ligands, such as phenolic neurotransmitters serotonin and dopamine, and amino acid arginine, or with anionic ligand phenol, in alkaline aqueous solutions. The apparent binding constants, Kb, of the HI-ligand complexes were determined from the dependence of the effective migration time changes of the above ligands on the variable zone lengths of HI dissolved in the background electrolyte and hydrodynamically introduced into the bare fused silica capillary close to the UV detector. The HI interactions with the above ligands were found to be moderately strong, with Kb values in the range 385-1314 L/mol.

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