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Preparation of asymmetrically substituted diphenylacetylenes usable in molecular electronics
Rejšek, Jan ; Jindřich, Jindřich (advisor) ; Veselý, Jan (referee)
Preparation of asymetrically substituted diphenylacetylenes usable in molecular electronics Abstract This bachelor's work deals with synthesis of assymetrically substituted diphenylacetylenes and their transformation into (η4 -cyclobutadiene)-(η5 - cyclopentadienyl)cobalt complexes, which should be used and researched as molecular rotors. Multistep synthesis concerning conversion of primary arylamines into tertiary by N-permethylation, nucleophilic acyl substitution and Sonogashira coupling was prepared asymmetrically substituted diphenylacetylene with, which consequently underwent cycloaddition [2 + 2] with cyclopentadienyldicarbonylcobalt. Creating (η4 -cyclobutadiene)-(η5 -cyclopentadienyl)cobalt complexe was identified by MS. Keywords: diphenylacetylene, Sonogashira coupling, (η4 -cyclobutadiene)- (η5 -cyclopentadienyl)cobalt complex, cycloaddition [2 + 2], molecular rotor
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Pyrazine Carbonyl Compounds - Building Blocks in Dynamic Combinatorial Systems
Coufal, Radek ; Drahoňovský, Dušan (advisor) ; Jindřich, Jindřich (referee)
This bachelor thesis deals with the synthesis of bifunctional carbonyl derivatives of pyrazine, which are further examined for their potential to form dynamic hemiacetals with monofunctional alcohols. Newly prepared, in the literature not yet described bifunctional trifluormethyl derivatives exhibit considerable ability to form hemiacetals in a dynamic system. The obtained results show that these substances may find application as building blocks of dynamic combinatorial systems.
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Synthesis of selectively disubstituted derivatives of alpha-cyclodextrin for chemosensoric applications
Diviš, Martin ; Jindřich, Jindřich (advisor) ; Kroutil, Jiří (referee)
Tato diplomová práce se zabývá problematikou vhodné selektivní derivatizace - cyklodextrinu pro jeho následné použití jako stacionárního chemosenzoru s fluorescenční skupinou. Byla vyvinuta a vypracována metodika pro přípravu selektivně disubstituovaného -CD. Dále byla vyvinuta metodika pro přípravu knihovny linkerů s fluoroforem a jejich navázání na CD. Také byly připraveny linkery pro připojení CD na pevnou fázi. Byla vyvinuta metodika pro připojení jednotlivých linkerů na CD za pomoci "click" reakcí, jmenovitě 1,3-dipolární cykloadice a reduktivní aminace. Nebyla připravena cílová série látek.
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Novel conjugated polymers of the metallo-supramolecular and polyelectrolyte class
Hladysh, Sviatoslav ; Vohlídal, Jiří (advisor) ; Strachota, Adam (referee) ; Jindřich, Jindřich (referee)
This thesis targets the development of conjugated polymers with improved process ability from solutions. Two types of ionic polymers are addressed: (i) conjugated metallo-supramolecular polymers (MSPs) composed of conjugated heteroaromatic unimers (building blocks) linked to chains by various metal ions giving charged main chains, and (ii) polythiophene polyelectrolytes containing ionic pendants. Processing advantages of conjugated polyelectrolytes consist in the possibility of their processing from solutions in green solvents such as alcohols or even water. The advantages of MSPs consist in the thermodynamic control of the degree of polymerization (length) of their chains in solutions by the choice of solvent and temperature. As a result, MSPs reversibly provide systems of low viscosity that can be processed from solutions more easily than high-molar-mass polymers giving highly viscous solutions. Synthesis of appropriately designed unimer(s) is the key step of preparation of an MSP. Within this thesis, a series of novel unimers composed of linear oligothiophene type (mono-, bi-, ter- a thieno-thiophene- diyl) central blocks capped with 2,6-bis(oxazoline-2-yl)pyridine (pybox) or 2,6-bis(imidazole-2-...
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Synthesis and properties of supramolecular polymers
Vitvarová, Tereza ; Vohlídal, Jiří (advisor) ; Jindřich, Jindřich (referee) ; Royal, Guy (referee)
New π-conjugated building blocks (unimers) for metallo-supramolecular polymers (MSPs), whose comprise: (i) substituted phosphole ring surrounded by two thiophene rings as the central block, (ii) 2,2':6',2''-terpyridine-4'-yl (tpy) end-groups as ion-selectors, and (iii) different linkers inserted between the central block and tpy end-groups, are described. Chemical and physical properties of those unimers were studied with attention on correlation between properties and structure of unimers. For example the unimer without linkers shows the UV/vis absorption maximum red shifted about 60 to 100 nm compared to bis(tpy)terthiophenes, which proves that replacing of the thiophene with phosphole unit significantly enhances the delocalization of electrons within the unimer molecule and significant area of absorption spectra can be covered. Introduction of linkers (ethynediyl, ethynediyl-thiophene-2,5-diyl, ethynediyl-1,4-phenylene) has a minor effect on the bandgap energy. All prepared unimers underwent self-assembling process with various metal ions (Co2+ , Cu2+ , Fe2+ , Ni2+ and Zn2+ ) resulting into metallo-supramolecular polymers. Three stages of the assembly of unimers into related MSPs were observed and characterized by absorption, fluorescence spectroscopy and size exclusion chromatography: 1)...
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Synthesis of sulphanylaminoderivatives of cyclodextrines and computational simulations of their complexes formation
Provazníková, Adéla ; Jindřich, Jindřich (advisor) ; Míšek, Jiří (referee)
This master thesis deals with synthesis of 6I -N-monosubstituted β-CD bearing a linear spacer of various lenghts containing disulfidic bond and terminated by amine. Whole series was succesfully prepared by nucleophilic substitution of toluenesulfonyl group on tosyl β-CD by a spacer's amine group. In case of the shortest spacer (cystamine) 35 % yield was achieved. Synthesis of β-CD derivatives using longer and more lipophilic spacer derived from di-, tri- and tetraethylenglycol yielded 66 to 85 %. The oligoethylene spacers were prepared by standard chemical modifications. A separation method using n-butanol elution mixtures was optimized for isolation of β-CD derivatives. To better understand the β-CD derivative behavior in solution, molecular dynamics (MD) computations were used. The synthetized species were intended to be used for fluorescent sensor construction. For the same reason the inclusion of small organic molecules in β-CD cavity was studied with molecular dynamic simulations. MD method for computation of relative binding energy was optimized and gave values of right sign and order of magnitude.
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Selectively substituted cyclodextrins for analytical and pharmaceutical applications
Benkovics, Gábor ; Jindřich, Jindřich (advisor) ; Lhoták, Pavel (referee) ; Šindelář, Vladimír (referee)
3 Selectively substituted cyclodextrins for analytical and pharmaceutical applications Abstract This thesis is focused on the selective modification of cyclodextrins, and its primary aim is the preparation and characterization of mono- and persubstituted derivatives of cyclodextrins in a regioselective and straightforward manner. The work is divided into two main parts describing synthetic strategies and applications of modified cyclodextrins with one or several substituents, respectively. The first section deals with the introduction of a single chromophoric moiety on the cyclodextrin scaffold such as cinnamyl, rhodaminyl, fluoresceinyl and eosinyl groups. The complete set of monocinnamyl-α-cyclodextrin regioisomers has been prepared by direct alkylation, and the self-assembling properties of the corresponding regioisomers were thoroughly investigated by dynamic light scattering and NMR experiments. These investigations revealed that the different isomers (mono-6-O-, mono-2-O- and mono-3-O- cinnamyl-α-cyclodextrin) form distinct supramolecular species through intermolecular association. A fast method for the unambiguous identification of the pure regioisomers has also been developed based on a series of 2D NMR measurements. Xanthene-modified β-cyclodextrins, other representatives of monosubstituted...
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Study of porphyrins substituted wich glycosylated steroids
Zelenka, Karel ; Trnka, Tomáš (advisor) ; Jindřich, Jindřich (referee) ; Kefurt, Karel (referee) ; Pouzar, Vladimir (referee)
I I 4. Conclusions This work is focused on syntheses of new zeso-substituted porphyrins containing glycosylated-steroid moieties and study oftheir physico-chemical and supramolecular propertres. In the first part oť this work, procedure for the synthesis of B glycosides 4 or 5 is described. No ťormation of ortohoesters was observed. Next part of this work consists oť searching for suitable protecting group for a saccharide part oť molecule and preparation of steroidaldehydes.Protectedglycosides10, ll,tó, 17,|9a+l9band20wereprepared.Suitable method for preparation ofaldehydes 14, 15, 23,24,29,30 an.34 is described (chapter 3.1). Following part of work describes preparation of porphyrins with protected sugar moiety. Symmetrical Al type porphyrins 35-41 were prepared. Also preparatio n of trans-A2ts1 ýpe porphyrins 43, 44 and A]B type 45, 4ó is described. Preparation oť porphyrins 47.50 with deprotected hydroxyl groups is described (Chapter 3.2). Solvent driven aggregation behavior oť the porphyrins was studied in aqueous solvent mixtures' Formation of aggregates of porphyrin 45 was proved using uv-vis spectroscopy (Chapter 3.3). Considering use oť prepared porphyrins in electrochemistry as a possible electrochemical sensors, polarographic and voltametric studies oť porphyrins 47-19 were per|ormed and showed...
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