|
|
Molecular recognition in the gas phase: Chiral recognition
Vinklová, Nicole ; Roithová, Jana (advisor) ; Bednář, Petr (referee)
This thesis deals with molecular recognition of chiral compounds in the gas phase. Tandem mass spectrometry was used as a detection method in this case. Compounds, which have been studied, were MacMillan organocatalysts and proline with different chirality. Three experiments were carried out. Determination of activation energy for fragmentation of proline complexes with amines, where we have studied complexes with 2-aminobutane and 2-aminohexane of different chirality. Fragmentation studies of diastereoisomeric complexes of Cu2+ and three chiral ligands were carried out at two different collision energies. There the largest chiral effect was observed. The last topic was a measurement of the rate constants. It was aimed at dissociation and exchange reactions of complexes. Keywords: mass spectrometry, kinetic method, chiral compounds, chiral recognition, proline, organocatalysis
|
|
|
Analytical and bioanalytical assessment of novel anticancer drugs
Šesták, Vít ; Štěrbová, Petra (advisor) ; Bednář, Petr (referee) ; Šatínský, Dalibor (referee)
Charles University Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical Chemistry and Pharmaceutical Analysis Candidate: Mgr. Vít Šesták Supervisor - specialist: PharmDr. Ján Stariat, Ph.D. Supervisor: doc. PharmDr. Petra Kovaříková, Ph.D. Title: Analytical and bioanalytical assessment of novel anticancer drugs Pharmaceutical analysis plays an indispensable role in the development of novel safer, cheaper and more effective drugs and chaperones them from their first synthesis throughout their existence. To date, the method most commonly used in pharmaceutical analysis is liquid chromatography (LC) with various detection modalities. Separation via LC enables analysis of very complex mixtures such as biological samples or samples from stability studies. The soaring interest in LC hyphenated with mass spectrometry (MS) in pharmaceutical analysis is partly due to its increasing affordability and mainly due to its ability to separate the molecules of the analyte according to their mass-to-charge ratio (m/z). The additional dimension of separation grants it a superior selectivity. In addition, MS provides priceless information on the structure of the analyte - be it the m/z or fragmentation spectra. In its theoretical part, this dissertation deals with basic description of liquid...
|
|
|
Development and optimization of sample preparation step for fast chromatographic analysis
Pilařová, Veronika ; Nováková, Lucie (advisor) ; Bednář, Petr (referee) ; Šatínský, Dalibor (referee)
Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department of analytical chemistry Candidate Mgr. Veronika Pilařová Supervisor Assoc. Prof. Lucie Nováková, Ph.D. Title of Doctoral Thesis Development and optimization of sample preparation step for fast chromatographic analysis. The aim of the dissertation thesis is the development of modern extraction methods for the sample purification and for the analytes isolation and preconcentration from various biological materials, including biological fluids (plasma, serum, vaginal lavages) and plant material. Modern approaches have a lots of advantages such as a lower consumption of sample and organic solvents, extraction speed-up, better sample purification, matrix removal and lower influence of matrix effects. Extracts from modern microextraction methods can be analyzed by separation methods including ultra-high performance liquid chromatography and supercritical flluid chromatography coupled with mass spectrometry. The separation methods enable fast high-throughput analysis with sensitive and selective detection. Individual projects show the possibilty of use of the modern approaches in the sample preparation field, where the microextraction by packed sorbent (MEPS), microextraction by solid phase extraction in pipette tips...
|
|
|
Analytical and bioanalytical assessment of novel anticancer drugs
Šesták, Vít ; Štěrbová, Petra (advisor) ; Bednář, Petr (referee) ; Šatínský, Dalibor (referee)
Charles University Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical Chemistry and Pharmaceutical Analysis Candidate: Mgr. Vít Šesták Supervisor - specialist: PharmDr. Ján Stariat, Ph.D. Supervisor: doc. PharmDr. Petra Kovaříková, Ph.D. Title: Analytical and bioanalytical assessment of novel anticancer drugs Pharmaceutical analysis plays an indispensable role in the development of novel safer, cheaper and more effective drugs and chaperones them from their first synthesis throughout their existence. To date, the method most commonly used in pharmaceutical analysis is liquid chromatography (LC) with various detection modalities. Separation via LC enables analysis of very complex mixtures such as biological samples or samples from stability studies. The soaring interest in LC hyphenated with mass spectrometry (MS) in pharmaceutical analysis is partly due to its increasing affordability and mainly due to its ability to separate the molecules of the analyte according to their mass-to-charge ratio (m/z). The additional dimension of separation grants it a superior selectivity. In addition, MS provides priceless information on the structure of the analyte - be it the m/z or fragmentation spectra. In its theoretical part, this dissertation deals with basic description of liquid...
|
|
|
HPLC determination of silybin diastereoisomers in plasma of laboratory animals
Kolářová, Petra ; Tesařová, Eva (advisor) ; Bednář, Petr (referee)
Silybin is the main component of silymarin, a standardized extract obtained from the seeds of milk thistle (Silybum marianum). Flavonolignan silybin has antioxidant, hepatoprotective, chemoprotective and antitumor activities. Natural silybin occurs as an approximately equimolar mixture of two diastereoisomers - silybin A and silybin B. Analytical separation of these diastereoisomers is possible but preparative separation is complicated. The biological activity of the silybin A is different from the silybin B. Silybin diastereoisomers are mainly conjugated to glucuronides and sulfates in organism. A mixture of both silybin diasteroisomers is used in the majority of reported biological, chemical and pharmacokinetic studies. For the first time, optically pure silybin A and silybin B were used for pharmacokinetic study in this thesis. The object of this work was determination of the concentration of free and total silybin in rats plasma in relation to time. Theoretical introduction describes the current state of the problem of chemistry, pharmacology and pharmacokinetics of silybin diastereoisomers. Second part is focused on the selection of appropriate analytical column, chromatographic method and suitable procedure for preparation of biological samples for the determination of the silybin...
|
|
|
Chiral recognition by mass spectrometry
Kosíková, Lenka ; Roithová, Jana (advisor) ; Bednář, Petr (referee)
Title: Chiral recognition by mass spectrometry Author: Bc. Lenka Kosíková Department: Department of Organic Chemistry Supervisor: doc. Mgr. Jana Roithová, Ph.D. This work is focused on the use of mass spectrometry as the analytical method for chiral recognition in the gas phase. We have examined formation of complexes (S and R) isomers [dimethyl-2,2'-dihydroxy-1,1'binaphthalene-3,3'-dicarboxylate] with sodium. Chiral effect for the fomation of sodium dimers is 1,34±0,06 and that for formation of trimers 2,38±0,22 in favor of the formation of homochiral complexes. Part of the work is devoted to the preparation of isotopically labeled ester [(R)-(−)- di(D3-methyl)-2,2'-dihydroxy-1,1'binaphthalene-3,3'-dicarboxylate]. Mixing of equimolar amounts of D3-(R) and unlabeled (S) isomers leads to the artificial racemate, while we can still distinguish the enantiomers using mass spectrometry. Another part represents the study of the complex formation between (S and R) isomers of [dimethyl-2,2'-dihydroxy-1,1'binaphthalene-3,3'-dicarboxylate] with the metal complex [(S,S)-1,5-diaza-cis-decalin]Cu(OH)I depending on the molar ratios in the solution. I have showed that the molar concetration of the catalyst in the solution plays an important role in the complex formation and that the ESI source spectra of...
|
|
|
Application of Ultra-high Pressure Liquid Chromatography with Mass Spectrometry Detection in Analysis of Polyphenols
Spáčil, Zdeněk ; Solich, Petr (advisor) ; Bednář, Petr (referee) ; Šatínský, Dalibor (referee)
DOCTORAL THESIS ABSTRACT 7 ABSTRACT Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department of Analytical Chemistry Candidate: Zdeněk Spáčil, M.Sc. Supervisor: prof. RNDr. Petr Solich, CSc. Title of Doctoral Thesis: Application of Ultra-High Pressure Liquid Chromatography with Mass Spectrometry Detection in Analysis of Polyphenols The major focus of presented doctoral thesis is development of advanced separation methods utilizing liquid chromatography (LC) and mass spectrometry (MS) for the analysis of polyphenols. The general aspects of techniques are discussed in theoretical part and the actual practical impact is documented by the results published in four original articles appended in the supplement I-IV. LC was used in each published study, while combined with MS in the last two works (supplement III-IV). Thus, the semi-quantitative data acquired by emerging laser desorption/ionization (LDI) MS technique were confirmed by UHPLC-MS. The broad availability, versatile configuration, convenient handling and well understood principles make LC the "method of choice" for variety of scientific applications to analyze diverse analytes. LC-MS coupling is convenient and robust offering two-staged separation: i) chromatographic separation and pre-concentration into narrow bands using LC and...
|
|
|
Molecular recognition in the gas phase: Chiral recognition
Vinklová, Nicole ; Roithová, Jana (advisor) ; Bednář, Petr (referee)
This thesis deals with molecular recognition of chiral compounds in the gas phase. Tandem mass spectrometry was used as a detection method in this case. Compounds, which have been studied, were MacMillan organocatalysts and proline with different chirality. Three experiments were carried out. Determination of activation energy for fragmentation of proline complexes with amines, where we have studied complexes with 2-aminobutane and 2-aminohexane of different chirality. Fragmentation studies of diastereoisomeric complexes of Cu2+ and three chiral ligands were carried out at two different collision energies. There the largest chiral effect was observed. The last topic was a measurement of the rate constants. It was aimed at dissociation and exchange reactions of complexes. Keywords: mass spectrometry, kinetic method, chiral compounds, chiral recognition, proline, organocatalysis
|
|
|
Development and optimization of sample preparation step for fast chromatographic analysis
Pilařová, Veronika ; Nováková, Lucie (advisor) ; Bednář, Petr (referee) ; Šatínský, Dalibor (referee)
Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department of analytical chemistry Candidate Mgr. Veronika Pilařová Supervisor Assoc. Prof. Lucie Nováková, Ph.D. Title of Doctoral Thesis Development and optimization of sample preparation step for fast chromatographic analysis. The aim of the dissertation thesis is the development of modern extraction methods for the sample purification and for the analytes isolation and preconcentration from various biological materials, including biological fluids (plasma, serum, vaginal lavages) and plant material. Modern approaches have a lots of advantages such as a lower consumption of sample and organic solvents, extraction speed-up, better sample purification, matrix removal and lower influence of matrix effects. Extracts from modern microextraction methods can be analyzed by separation methods including ultra-high performance liquid chromatography and supercritical flluid chromatography coupled with mass spectrometry. The separation methods enable fast high-throughput analysis with sensitive and selective detection. Individual projects show the possibilty of use of the modern approaches in the sample preparation field, where the microextraction by packed sorbent (MEPS), microextraction by solid phase extraction in pipette tips...
|
|
| |
guest ::
RSS feed.