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Vývoj katalyzátoru pro epoxidaci methylesterů
Pham, Tien Thanh ; Krajčovič, Jozef (oponent) ; Kučerík, Jiří (vedoucí práce)
Diplomová práce je zaměřená na studium heterogenních katalyzátorů v epoxidaci methylesteru řepkového oleje. Epoxidy těchto komponent mají uplatnění v řezných olejích, kde by mohly nahradit dosud využívající oleje z fosilních zdrojů. Epoxidace je katalyzovanou reakcí pomocí homogenních katalyzátorů na bázi minerálních kyselin. Ty však mají korozivní vlastnosti a špatně se separují po reakci. Tato práce je však zaměřená na studium heterogenních katalyzátorů. Produkty reakce byly analyzovány pomocí GC, SIMDIS a ATR-FTIR. Pro určení složení, strukturních, texturních a redukčních vlastností katalyzátorů byly využity pokročilé analytické metody jako ICP-OES, XRF, XRD, SEM, rtuťová porozimetrie a TPR H2.
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Charakterizace kovů v atmosférickém aerosolu
Cigánková, Hana ; Ličbinský, Roman (oponent) ; Vojtíšek,, Michal (oponent) ; Krajčovič, Jozef (vedoucí práce)
Předložená disertační práce se zabývá charakterizací prvků ve dvou velikostních frakcích městského aerosolu, který byl vzorkován ve všech ročních obdobích na venkovní terase Ústavu analytické chemie AV ČR v Brně v roce 2018. V teoretické části práce jsou shrnuty základní informace o analýze a zdravotních rizicích atmosférického aerosolu a na něm vázaných kovech. Dále jsou v práci popsány metody stanovení inhalační biodostupnosti částic aerosolu a metody používané pro stanovení oxidativního potenciálu. V první části práce je podrobně popsáno vzorkování a analýza částic městského aerosolu. Byla stanovena hmotnostní koncentrace obou velikostních frakcí částic aerosolu a celková koncentrace 21 prvků vázaných na částice. Pomocí obohacovacího faktoru a pozitivní maticové faktorizace byly vypočítány pravděpodobné zdroje analyzovaných prvků. Druhá část práce se zabývá stanovením oxidativního potenciálu aerosolu a biodostupné koncentrace analyzovaných prvků ve třech simulovaných plicních tekutinách (deionizovaná voda, simulovaná kapalina plicních sklípků a Gamblův roztok). Kromě stanovení oxidativního potenciálu reálných vzorků byly stanoveny i oxidativní potenciály jednotlivých prvků. Ze získaných výsledků byl vypočítán pravděpodobný příspěvek prvků ke změřenému oxidativnímu potenciálu.
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Synthesis of soluble nature-inspired N, N-alkylated riboflavin derivatives, study of the effect of alkyl groups
Ivanová, Lucia ; Maier,, Lukáš (oponent) ; Krajčovič, Jozef (vedoucí práce)
By flavin's unique structure, nature predestined riboflavin and its derivatives to the participation in redox processes within the bodies of all the living organisms. These biomolecules draw attention with intriguing optical properties and photosensitising abilities. Nature-inspired flavin derivatives share these qualities, and there is also a possibility of fine-tuning for the particular application from the chemical point of view. The thesis deals with two main aims. The first aim handles the synthesis of the trimer heteroaromatic precursor and 1,2-diketone. These key intermediates are essential for the future synthesis of the central aromatic core of the novel NH-free non-fused flavin derivative. The thesis introduces and verifies three approaches, including oxidation of diarylalkynes, nucleophilic addition of a corresponding organolithium compound to a Weinreb amide and benzoin condensation. The second aim covers the properties customization of NH-free fused systems by implementation of linear and bulky alkyl side-chains on the nitrogen atoms N1 and N3 of the alloxazine dilactam. N,N-alkylation introduced an increase in solubility in common organic solvents dichloromethane and chloroform. For the derivatives with 2-(adamantan-1-yl)ethyl substituents, high thermal stability was observed via TGA.
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Synthesis of advanced adamantane containing intermediates based on para-bis (2-thienyl) phenylene. Influence of intramolecular hydrogen bonds on photoisomerization
Veselý, Dominik ; Pospíšilík, Karel (oponent) ; Krajčovič, Jozef (vedoucí práce)
This diploma thesis describes study and onward synthesis of advanced organic structures with potential application in the field of organic electronics and, in particular, molecular photoswitches. In the theoretical part of the thesis are closely described most commonly used conventional molecular photoswitches with special attention to the influence of the structural modifications on properties and applications of the given derivatives. Next passage is dedicated to study of donor-acceptor systems, as fundamental building blocks for synthesis of advanced derivatives. The possibilities of derivatization with a goal of improving the physicochemical properties of these compounds are also discussed. In the final chapter are proposed modern synthetic methods for preparation of novel materials for organic electronics. This section is connected with an experimental part, where are designed and consequently synthesised 4 novel imine derivatives with dodecyl and adamantyl-ethyl side chain.
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Evoluce jaderných a plastidových genomů u euglenidů
Hrdá, Štěpánka ; Hampl, Vladimír (vedoucí práce) ; Krajčovič, Juraj (oponent) ; Škaloud, Pavel (oponent)
Řasy tvoří rozmanitou skupinu jednoduchých fotosyntetizujících eukaryotických organismů s polyfyletickým původem. Dělí se na řasy s primárním plastidem (Archaeplastida), který tato eukaryota získala pozřením sinice, tedy prokaryota, a řasy s komplexním plastidem, které získaly plastid pozřením jiného eukaryota s primárním nebo již komplexním plastidem. Řasy s komplexním plastidem jsou chiméry obsahující geny pocházející z hostitelské buňky, a dále geny pocházející nejen z plastidu, ale také z jádra a někdy i mitochondrie endosymbionta, případně i genetický materiál pocházející od jejich předchozích stálých nebo přechodných endosymbiontů. Jednou ze skupin, která získala plastid od zelených řas, jsou krásnoočka (Euglenophyta). Tato práce se zabývá genomy tří organismů, které zastupují jednotlivé aktéry endosymbiotického procesu u euglenofyt. Jsou to původně heterotrofní hostitel ze třídy Euglenida, fototrofní endosymbiont ze třídy zelených řas Prasinophyceae a výsledný fototrofní euglenid ze skupiny Euglenophyceae. Znalost jejich genomů by měla pomoci osvětlit průběh endosymbiotického přenosu genů (EGT) při formování řas s komplexním plastidem. U zástupce fototrofních euglenidů Eutreptiella gymnastica jsme anotovali plastidový genom, který jsme publikovali jako tehdy teprve třetí ve skupině...
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Modification of Organic High Performance Pigments for Applications in Organic Electronics
Cigánek, Martin ; Imramovský, Aleš (oponent) ; Vyňuchal, Jan (oponent) ; Krajčovič, Jozef (vedoucí práce)
The doctoral thesis deals with the study, synthesis and chemical derivatization of molecules belonging to the group of organic high-performance pigments and their potential application in the fields of organic electronics. The theoretical part of the work is focused on the latest trends in the area mentioned above, both from the application potential of specific derivatives and in terms of synthetic possibilities and their structural derivatization. The experimental part describes in detail the preparation of a wide range of intermediates and final products, including derivatives of diketopyrrolopyrroles (DPP), benzodifuranone (BDF), epindolidione (EP), naphthyridinedione (NTD) and thiophene-based polymer (PT). A total of 103 molecules were synthesized, of which 49 were final products, and 27 of them were completely novel, as yet unpublished. Herein, the main motive for the derivatization of pigment molecules is the incorporation of bulky adamantyl substituents into the resulting derivative structures. In the next part of the work, individual chemical modifications leading to the final products are discussed in more detail. In the series of N,N'-; N,O'- and O,O'-substituted DPP derivatives, the influence of both the alkyl chains’ character and binding position in the DPP molecule on the selectivity of the reaction, the thermal and optical properties of the resulting derivatives is comprehensively described.
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Synthesis and Study of Nano-Structured Perovskites for Applications in Organic Electronics
Jančík Procházková, Anna ; Kuřitka, Ivo (oponent) ; Částková, Klára (oponent) ; Krajčovič, Jozef (vedoucí práce)
Diversity and unique properties, such as exceptionally high photoluminescence quantum yields (PLQYs), predetermine metal halide perovskite nanoparticles (PNP) to be applied in optoelectronic and photonic devices. In this work, nature-inspired capping agents were employed not only for the PNP stabilization but also for modifying their surface to broaden the functionality of the resulting material. In the very beginning, a ligand-assisted precipitation technique was optimized for the preparation of the PNP. Here, adamantane-1-amine (AdNH2) alongside hexanoic acid (HeA) were chosen as capping agents for nanoparticles stabilization and passivation. It was demonstrated that the choice of the solvent system and the precipitation temperature have a crucial effect on the resulting optical properties of the colloidal solutions. Simultaneously, the influence of concentration of precursor chemicals on the resulting morphology and optical properties was investigated. Also, different carboxylic acids were tested as capping agents among AdNH2 and the colloidal stability of the resulting colloidal solutions was evaluated. To demonstrate the diversity of the ligand-assisted precipitation technique of PNP preparation, L-lysine and L-arginine were employed initially for the surface passivation. As a result, colloidal solutions with emission within a narrow bandwidth of the visible spectrum and remarkable photoluminescence quantum yield (PLQY) close to 100% were obtained. Blocking -amino group of L-lysine by tert-butoxycarbonyl group suggested preferential binding of the side chain of L-lysine to the perovskite core. Furthermore, defined amounts of water were added into the precursor solutions which caused shifts of emission spectra due to quantum confinement effects. Water molecules were assumed to form highly mobile species leading to the enhancement of controlling the perovskite lattice growth. Merging perovskite nanomaterials with peptides are expected to pave a way to the new class of materials possessing exceptional optoelectronic properties alongside self-assembly and sensing abilities. As a proof-of-concept, a cyclic(RGDFK) pentapeptide was used for PNP stabilization. However, peptides are known for their sensitivity to their environment. Therefore, peptide nucleic acid (PNA) was used for PNP stabilization as a robust artificial analogue for deoxyribonucleic acid (DNA). Here, optical properties of thymine-based PNA monomer and trimer stabilized PNP were studied. Additionally, the sensing ability of the PNA ligand for adenine moiety was demonstrated by photoluminescence quenching via charge transfer. We envision that combining the unique tailored structure of PNA and the prospective optical features of PNP could expand the applications especially in the field of optical sensing devices.
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Synthesis and Characterization of New Organic Materials for Organic Electronics
Richtár, Jan ; Vícha,, Robert (oponent) ; Weidlich,, Tomáš (oponent) ; Krajčovič, Jozef (vedoucí práce)
In the modern era, organic electronics and bioelectronics go through tremendous development efforts to obtain novel organic materials with features usually unattainable by conventional silicon-based electronics. This thesis concerns the synthesis and characterization of novel organic materials for organic electronics. It deals with the synthesis of novel pentafluorosulfanylated heterocyclic building blocks, alkylated high-performance organic pigments, and bioinspired organic -conjugated materials with tunable physico-chemical properties and rational synthetic approaches towards their preparation. Pentafluorosulfanyl group (SF5) is appreciated for the high electronegativity, lipophilicity, thermal and chemical stability. It influences positively optical and electronic properties, solubility, and stability to a degree often superior to more established CF3-analogues. Two types of derivatives of 3-SF5-substituted pyrrolidines were synthesized by six and four-step synthetic approaches serving as potential versatile building blocks for the incorporation into advanced aromatic and heteroaromatic -conjugated systems via nitrogen atoms as the fluorinated terminal groups. A model derivative was introduced as a terminal group in an electron-deficient heteroaromatic system by nucleophilic substitution. Hydrogen-bonded high-performance organic pigments attract a lot of attention due to their impressive semiconducting properties, strong 2D molecular association, high thermal, chemical and photochemical stability, and non-toxicity. Nevertheless, they suffer from limited solubility and processability which is commonly solved by the introduction of solubilizing groups. Moreover, particularly bulky rigid adamantyl-bearing groups are known to improve molecular packing, thermal stability, and resulting properties due to the self-organizing ability of adamantane. The adamantylmethyl and adamantylethyl groups were incorporated into selected hydrogen-bonded dyes and pigments from groups of carbonyl azaacenes, rylene-diimides and indigoids by means of nucleophilic substitution aiming towards increasing solubility and processability while preserving the thermal stability and favorable solid-state molecular packing. Physico-chemical studies of quinacridone and epindolidione series showed thermal stability comparable or higher than for H-bonded derivatives, good solubility in organic solvents, strong fluorescence in solid state and solution in VIS region and distinct molecular packing in single crystals as was observed from X-ray analysis. Flavins are ubiquitous bio-inspired organic material with indispensable biological functions, promising physico-chemical properties, chemical and application versatility. Consequently, the focus was put on the tuning of the optical, electronic, electrochemical, thermal and other properties by the extension of the -conjugated system of said materials. Initially, two complementary synthetic approaches were envisaged in order to provide NH-free flavin series which was to undergo comprehensive physico-chemical studies. Afterwards, two different approaches were proposed to synthesize N,N’-dialkylated flavins incorporating butyl, adamantylethyl and triethyleneglycol-derived substituents. The alkylation enhanced solubility in organic solvents and aqueous media, increased fluorescence in solid state and solutions, and tuned the thermal properties depending on the alkyl substitution.
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Nature-inspired macro cyclic systems for bioorganic applications
Prekopová, Terézia ; Cigánek, Martin (oponent) ; Krajčovič, Jozef (vedoucí práce)
The bachelor thesis deals with nature-inspired macrocyclic compounds and their possible use in organic bioelectronics. The theoretical part of this bachelor thesis introduces semiconductor materials in organic bioelectronics and provides a general overview of selected classes of macrocyclic compounds currently occurring. It includes their history, properties, reactivity and use in various industries. An important point of this part are cyclodextrins, which are characterized by their high biocompatibility and affinity for a wide range of guests depending on the structure of the cyclodextrin. They are capable of molecular recognition to form inclusion complexes with guest particles. The work also deals with chemical modifications of cyclodextrins in order to improve selected physicochemical properties and practical applications of cyclodextrins. The experimental part consists of the synthesis, purification and characterization of key macrocyclic -cyclodextrin derivatives selectively modified at position 6 of one glucopyranose unit for the synthesis and study of advanced supramolecular structures for potential applications in organic bioelectronics.
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