This Ph.D. thesis deals with synthesis of monosubstituted cyclodextrin derivatives and investigating their properties. Alkylation of -cyclodextrin with allyl or cinnamyl bromide followed by peracetylation of remaining hydroxyl groups and separation of isomers resulted in the set of peracetylated 2I - O-, 3I -O- and 6I -O-alkylated cyclodextrins in up to 27% yields. Oxidative cleaveage of peracetylated allyl or cinnamyl derivatives resulted in a complete set of peracetylated 2I -O-, 3I -O- and 6I -O- formylmethyl or carboxymethyl derivatives which are useful precursors for preparation of regioselectively monosubstituted derivatives of -cyclodextrin. Moreover, a quick method to recognize single 2I -O-, 3I -O- and 6I -O- monosubstituted peracetylated cyclodextrins from each other using only 1 H NMR spectrum has been proposed. Ru-carbene complex catalyzed cross-metathesis of monoallyl -, -, and -cyclodextrins with perfluoroalkylpropenes resulted in the formation of the corresponding perfluoroalkylated cyclodextrins. The reactions proceeded under standard reaction conditions and the desired compounds were obtained in reasonable yields. Dynamic light scattering measurements proved the ability of the prepared compounds to aggregate in water solution forming nanoparticles in the range of tens and...

This work deals with the use of methoxymethyl protecting group in chemistry of cyclodextrins, where this group has not been used very often so far. The work deals with development of optimal methods for introduction and for subsequent removal of the group and shows its usefulness in the preparation of new 6I -O-monosubstituted cyclodextrin derivatives, which are hard to get by standard methods. Key words: cyclodextrin derivatives, methoxymethyl group, protecting group

This master thesis deals with the preparation of the cyclodextrin (CD) derivatives that are suitable for complexation of the electron-rich aromatic compounds such as helicenes. The basic skeleton of native CD was perbenzoylated in all positions 2, 3 and 6 in the first place. Then the nucleophilic attack of carboxylates of benzoic acids with electron- withdrawing groups (NO2) or electron-donating group (NH2) to per(6-deoxy-6-iodo)-CD derivatives were used to prepare the perbenzoylated CD derivatives in the postition 6. Binding constant was determined for the prepared benzoylated derivatives of CD and the racemate of the hexahelicene using the NMR titration. Perbenzoylated derivatives of β-CD in all position 2,3 and 6 with one azido group in position 6 were prepared as well. These derivatives could be covalently bonded as chiral selectors in the stationary phase for the HPLC separation of aromatic enantiomers. Keywords: cylodextrins, persubstitution, benzoyl, 4-nitrobenzoyl, 3,5-dinitrobenzoyl, helicenes, NMR titration, binding constants

Ce travail vise à obtenir un matériau possédant des propriétés de complexation grâce aux cyclodextrines (CyD) et à démontrer la faisabilité de la synthèse en milieu CO2 supercritique (scCO2). L'adaptation en scCO2 de la polyaddition directe entre une α-CyD et un diisocyanate n’a montré qu’une faible conversion après 7 heures de réaction (presque totale en 4 heure en milieu liquide), en raison de la complexation possible du diisocyanate par la CyD, de l’insolubilité de la CyD dans le scCO2 ou d’une diminution de la vitesse de réaction nécessitant un temps supérieure pour atteindre une conversion plus élevée. Des études supplémentaires sont nécessaires pour confirmer ses hypothèses. La conception d’un monomère original pouvant être scCO2-soluble, par acétylation des hydroxyles de la CyD, fonctionnalisé par 3 isocyanates a montré, par polyaddition avec une alkyldiamine, en milieu solvant, une forte dépendance de la masse molaire avec la concentration (jusqu’à 16,89 kg/mol à 50 %pds en monomères). En milieu scCO2, la conversion du monomère original a été totale, avec des masses molaires atteintes supérieures à celles en milieu liquide à concentration identique, démontrant l’intérêt d’un tel milieu en remplacement de solvants organiques dans le cas d’une conception bien adaptée. L’extension de la gamme de concentrations et des conditions opératoires (température, pression) reste à réaliser pour conclure à l’intérêt du scCO2 par rapport à ce monomère original à base de CyD / This work aims at obtaining a polymeric material possessing complexation abilities thanks to cyclodextrins (CyD) within its framework and demonstrating the feasibility of the synthesis in supercritical CO2 medium (scCO2). Contrary to liquid medium, the polymerization of α-CyD and a diisocyanate in scCO2 shows only low conversion after 7 hours due to the possible complexation of the diisocyanate by the CyD, the insolubility of the CyD in scCO2 medium or insufficient time to achieve high conversion due to diminution of the reaction rate. New studies have to be done in order to confirm these hypothesis. The design of an original monomer which could be soluble in scCO2 thanks to acetyl groups fixed on the CyD and functionalized by 3 isocyanates, leads to a strong dependency of the molar mass with the concentration of monomers (up to 16.89 kg/mol at 50 %w of monomers) when reacted with a diaminoalkyle chain extender in solvent medium. In scCO2 medium, full conversion of this monomer is achieved, with higher molar masses obtained than in liquid medium at the same concentration. This demonstrates the potential of such a synthesis medium instead of organic solvents when design is well adapted. However, more experiments are needed to study the influence of concentration, temperature and pressure on larger scales to conclude in the interest of scCO2

This diploma work is devoted to the preparation and analytical testing of modified gold electrodes in QCM. The sensitivity and selectivity response towards selected aromatic analytes in aqueous phase was monitored. Studied analytes were 1-methylnaphthalene, 2-methylnaphthalene, naphthalene, o-xylene and toluene. These compounds are frequently used in chemistry industry and other industrial branches and, are known to be harmful to human organism and environment. Using QCM method it is possible to detect them rapidly and relatively easily.

This diploma thesis deals with the application of two permanently positively charged monosubstituted β-cyclodextrin derivatives (PEMEDA-β-CD, PEMPDA-β-CD) as chiral selectors in capillary electrophoresis. Use of PEMPDA-β-cyclodextrin in capillary electrophoresis has not been reported in literature. Properties of PEMEDA-β- cyclodextrin are already known, but its application for separation of amino acid enantiomers has not been published yet. Cyclodextrin derivatives were tested as additives in different buffers of different pH and with eventual addition of organic modifier. As suitable background electrolyte 15 mmol·l-1 borate buffer, pH = 9.5 without organic modifier was chosen. Furthermore the influence of chiral selector on separation and eventual enantioseparation of chosen analytes was evaluated. Addition of cyclodextrin derivatives in concentration range 0.0 - 5.0 was tested. Fourteen anionogenic analytes, including native amino acids, N- blocked amino acids and profens, were detected with UV-VIS detector at optimal wavelength 214, 254 or 280 nm. Both chiral selectors were suitable for enantioseparation of N-boc-D,L-tryptophan, which was baseline separated at concentration of selector as low as 0.5 mmol·l-1 . Tested amino acids blocked with terc-butoxycarbonyl and D,L-ketoprofen were partially...

In the first part of the doctoral thesis, the capillary electrophoresis was used to test the potential chiral separation properties of monosubstituted cyclodextrin derivatives, namely PEMEDA- and PEMPDA-β-cyclodextrins for the group of selected analytes. Both selectors exhibited excellent enantioseparation properties for N-boc-D,L-tryptophan, where the enantiomers were completely separated even at 0.5 mmol·l-1 concentration of the cyclodextrin derivative in the background electrolyte. However, the differences between the enantiodiscrimination properties of individual derivatives were minimal. The second test group consisted of two cyclodextrin derivatives, namely 2-O- and 3-O- cinnamyl-α-cyclodextrins. These derivatives are able to form supramolecular polymers in aqueous solutions that disintegrate at elevated temperature. The formation of these polymers was tested by NMR and DLS experiments. None of the tested cyclodextrin derivatives showed enantiodiscrimination properties towards a group of selected analytes. In the frame of antipredatory study, HPLC-MS/MS method working in HILIC mode was used for separation of ten pterin derivatives and riboflavin, which can be present as pigments in insects, reptiles or amphibians as a part of their warning coloration. The developed methodology was applied for...