A presente tese descreve o estudo cinético e mecanístico da desativação do estado singlete- e triplete-excitado de flavinas por esteróis (colesterol e ergosterol), vitamina D, coenzima Q10, vitamina K, ácidos graxos e metabólitos da cafeína. Através da análise de Stern-Volmer da supressão de fluorescência da riboflavina pelo colesterol, ergosterol, vitamina D, vitamina K, e pela coenzima Q10 observa-se que o estado singlete excitado da riboflavina é desativado com constante de velocidade superior ao limite da difusão. No entanto, a presença de colesterol, ergosterol, vitamina D, vitamina K e coenzima Q10 não afeta o tempo de vida do estado singlete excitado da riboflavina como demonstrado por experimentos de contagem de fótons resolvido no tempo sugerindo a formação de um complexo precursor [riboflavina...substrato]. O complexo 1:1 formado entre a riboflavina e a vitamina D apresenta Ka = 4 x 104 ± 3 mol⋅L-1 a 25 0C com ΔH0 = -36 ± 7 kJ⋅mol-1 e ΔS0 = -5 ± 3 J⋅mol-1 ⋅K-1. O complexo 1:1 entre a riboflavina e a vitamina K (vit K) e a riboflavina com a coenzima Q10 (CoQ10) apresentam Ka = 1 x 103 ± 1 mol⋅L-1 com ΔH0 = -110 ± 22 kJ⋅mol-1 e ΔS0 = 51 ± 9 J ⋅mol-1⋅K-1 para a vit K e Ka = 4 x 102 ± 1 mol⋅L-1, ΔH0 = -120 ± 27 kJ ⋅mol-1 e ΔS0 = 41 ± 7 J ⋅mol-1⋅K-1 para a CoQ10 a 25 0C. Para a desativação do estado triplete da riboflavina, foram obtidas constantes bimoleculares de velocidade variando de 1,4 x 108 L ⋅mol-1⋅s-1 (vit D) a 1,4 x 109 L ⋅mol-1⋅s-1 (CoQ10). Observa-se supressão da emissão de fluorescência da riboflavina na presença de metabolitos da cafeína, no entanto, sem alterar o tempo de vida do estado singlete excitado da riboflavina sugerindo a formação de um complexo precursor [riboflavina...substrato]. O complexo formado entre a riboflavina e os metabólitos da cafeína apresentam Ka = 295 ± 1 mol⋅L-1 com ΔH0 = -45 ± 8 kJ⋅mol-1 e ΔS0 = 12 ± 1 J⋅mol-1⋅K-1 para o ácido 1,7-dimetil úrico, Ka = 289 ± 1 mol⋅L-1 com ΔH0 = -38 ± 5 kJ ⋅mol-1 e ΔS0 = 9 ± 2 J ⋅mol-1⋅K-1 para o ácido 1-metil úrico e Ka = 275 ± 1 mol⋅L-1 com ΔH0 = 16 ± 3 kJ ⋅mol-1 e ΔS0 = 6 ± 1J ⋅mol-1⋅K-1 para a 1,7-dimetilxantina a 25 0C. Para a desativação do estado triplete da riboflavina, foram obtidas constantes de velocidade de 3kq = 4,2 x 108 L.mol-1.s-1 para a 1,7-dimetilxantina, 3kq = 1,0 x 108 L.mol-1.s-1 para o ácido 1,7-dimetil úrico e 3kq = 1,4 x 108 L.mol-1.s-1 para o ácido 1-metil úrico. Os ésteres metílicos (oleato de metila, ácido linoléico conjugado (CLA), linoleato de metila, linolenato de metila, araquidonato de metila, eicosapentanoato de metila, e docosahexanoato de metila) não desativam o estado singlete-excitado da riboflavina. Entretanto, os ésteres metílicos se mostraram reativos frente ao estado triplete da riboflavina com constantes de velocidades 3kq variando de 8,4 x 105 a 3,3 x 107 L⋅smol-1 ⋅s-1 com uma dependência linear do número de hidrogênios bis-alílicos com excessão do CLA. / The present thesis describes the kinetic and mechanistic studies of flavin singlet- and triplet-excited states deactivation by sterols (ergosterol and cholesterol), vitamin D, coenzyme Q10, vitamin K, fatty acids, and caffeine metabolites. From the Stern-Volmer analysis of the riboflavin fluorescence quenching by cholesterol, ergosterol, vitamin D, vitamin K and coenzyme Q10, it is noted that the singlet-excited state of riboflavin is deactivated with a rate constant exceeding the diffusion limit. However, the presence of cholesterol, ergosterol, vitamin D, vitamin K, coenzyme Q10 did not affect the lifetime of singlet-excited riboflavin as probed by single photon counting experiments suggesting the formation of a ground-state precursor complex [riboflavin ...substrate]. The 1:1 complex formed between riboflavin and vitamin D showed Ka = 4 x 104 ± 3 mol⋅L-1 a 25 0C with ΔH0 = -36 ± 7 kJ⋅mol-1 and ΔS0 = -5 ± 3 J⋅mol-1 ⋅K-1. The 1:1 complex formed between riboflavin and vitamin K (vit K) and riboflavin with coenzyme Q10 (CoQ10) showed Ka = 1 x 103 ± 1 mol⋅L-1 with ΔH0 = -110 ± 22 kJ⋅mol-1 and ΔS0 = 51 ± 9 J ⋅mol-1⋅K-1 for vit K e Ka =4 x 102 ± 1 mol⋅L-1, ΔH0 = -120 ± 27 kJ ⋅mol-1 and ΔS0 = 41 ± 7 J ⋅mol-1⋅K-1 for CoQ10 a 25 0C. For the deactivation of triplet riboflavin, bimolecular rate constants were found to vary from 1,4 x 108 L ⋅mol-1⋅s-1 (vit D) a 1,4 x 109 L ⋅mol-1⋅s-1 (CoQ10). The caffeine metabolites quench fluorescence emission of riboflavin however, without affecting the lifetime of the singlet-excited state, suggesting the formation of a ground state precursor complex [riboflavin ... substrate]. The complex formed between riboflavin and caffeine metabolites showed Ka = 295 ± 1 mol⋅L-1 with ΔH0 = -45 ± 8 kJ⋅mol-1 and ΔS0 = 12 ± 1 J⋅mol-1⋅K-1for 1,7-dimetyl uric acid, Ka = 289 ± 1 mol⋅L-1 with ΔH0 = -38 ± 5 kJ ⋅mol-1 and ΔS0 = 9 ± 2 J ⋅mol-1⋅K-1 for 1-methyl uric acid and Ka = 275 ± 1 mol⋅L-1 with ΔH0 = 16 ± 3 kJ ⋅mol-1 and ΔS0 = 6 ± 1J ⋅mol-1⋅K-1 for 1,7-dimethylxanthine at 25 0C. For the deactivation of triplet riboflavin, rate constant were obtained with 3kq = 4,2 x 108 L.mol-1.s-1 para a 1,7-dimethylxanthine, 3kq = 1,0 x 108 L.mol-1.s-1 for 1,7-dimethyl uric acid, and 3kq = 1,4 x 108 L.mol-1.s-1 for 1-methyl uric acid. The methyl esters (methyl oleate, conjugated linoleic acid (CLA), methyl linoleate, methyl linoleate, methyl arachidonate, methyl eicosapentanoate, and methyl docosahexanoate) did not quench the singlet-excited riboflavin. However, the methyl esters were shown to be reactive towards triplet riboflavin with rate constants ranging from 8,4 x 105 a 3,3 x 107 L⋅mol-1 ⋅s-1and depending linearly with the number of bis-allylic hydrogens with exception to CLA.

In the development of noninvasive optical biopsy, normal tissues can be statistically differentiated from precancerous and cancerous tissues by analyzing their autofluorescence spectra. The observed cancer hallmarks in the spectra are manifestations of biochemical and morphological changes in tissue during cancerous transformation. For detection of colorectal cancers, it has been hypothesized that the major contributors to tissue fluorescence are three endogenous fluorophores – reduced nicotinamide adenine dinucleotide (NADH), flavin adenine dinucleotide (FAD) and collagen. Separating and identifying endogenous fluorophores in cells/tissues using capillary electrophoresis (CE) with laser–induced fluorescence (LIF) detection holds promise as a simple and fast method to analyze fluorophore compositions in tissues during the cancerous transformation. To this end, we have established the extraction and separation protocols for quantifying endogenous fluorophores in Chinese Hamster Ovary (CHO) cells, human colorectal adenocarcinoma cells (HT–29) and human normal colon cells (FHC). Flavin mononucleotide (FMN), FAD, NADH and nicotinamide adenine dinucleotide phosphate (NADPH) have been identified in the cell extracts by spiking them with standards and quantified by standard addition methods. The influence of cell densities and cell growth stages on fluorophore composition has been closely examined. Two–dimensional (2D) correlation coefficient mapping of electropherograms of HT–29 and FHC cell extracts reveals that the HT–29 cell extracts with higher cell density can be differentiated from FHC and HT–29 cell extracts with lower cell density, which is also demonstrated by the comparison of peak area ratios of NADH and NADPH. The electropherograms for 2D correlation analysis are pretreated by aligning their prominent peaks to account for peak shifting. A challenge in biological spectroscopy of cells and tissue is the identification of endogenous components that contribute to the overall complex spectra and the diagnostic signature. We propose 2D generalized correlation of CE–LIF electropherograms and fluorescence spectra in order to resolve the overlapped fluorescence spectra into their individual components. Separation of the endogenous fluorophores in normal and cancer cells by CE–LIF has provided us insight into fluorophore compositions and tools for classifications of cells. It has also prepared us for extraction and separation of tissues under different physiological conditions to assist cancer diagnosis.

A presente tese descreve o estudo cinético e mecanístico da desativação do estado singlete- e triplete-excitado de flavinas por esteróis (colesterol e ergosterol), vitamina D, coenzima Q10, vitamina K, ácidos graxos e metabólitos da cafeína. Através da análise de Stern-Volmer da supressão de fluorescência da riboflavina pelo colesterol, ergosterol, vitamina D, vitamina K, e pela coenzima Q10 observa-se que o estado singlete excitado da riboflavina é desativado com constante de velocidade superior ao limite da difusão. No entanto, a presença de colesterol, ergosterol, vitamina D, vitamina K e coenzima Q10 não afeta o tempo de vida do estado singlete excitado da riboflavina como demonstrado por experimentos de contagem de fótons resolvido no tempo sugerindo a formação de um complexo precursor [riboflavina...substrato]. O complexo 1:1 formado entre a riboflavina e a vitamina D apresenta Ka = 4 x 104 ± 3 mol⋅L-1 a 25 0C com ΔH0 = -36 ± 7 kJ⋅mol-1 e ΔS0 = -5 ± 3 J⋅mol-1 ⋅K-1. O complexo 1:1 entre a riboflavina e a vitamina K (vit K) e a riboflavina com a coenzima Q10 (CoQ10) apresentam Ka = 1 x 103 ± 1 mol⋅L-1 com ΔH0 = -110 ± 22 kJ⋅mol-1 e ΔS0 = 51 ± 9 J ⋅mol-1⋅K-1 para a vit K e Ka = 4 x 102 ± 1 mol⋅L-1, ΔH0 = -120 ± 27 kJ ⋅mol-1 e ΔS0 = 41 ± 7 J ⋅mol-1⋅K-1 para a CoQ10 a 25 0C. Para a desativação do estado triplete da riboflavina, foram obtidas constantes bimoleculares de velocidade variando de 1,4 x 108 L ⋅mol-1⋅s-1 (vit D) a 1,4 x 109 L ⋅mol-1⋅s-1 (CoQ10). Observa-se supressão da emissão de fluorescência da riboflavina na presença de metabolitos da cafeína, no entanto, sem alterar o tempo de vida do estado singlete excitado da riboflavina sugerindo a formação de um complexo precursor [riboflavina...substrato]. O complexo formado entre a riboflavina e os metabólitos da cafeína apresentam Ka = 295 ± 1 mol⋅L-1 com ΔH0 = -45 ± 8 kJ⋅mol-1 e ΔS0 = 12 ± 1 J⋅mol-1⋅K-1 para o ácido 1,7-dimetil úrico, Ka = 289 ± 1 mol⋅L-1 com ΔH0 = -38 ± 5 kJ ⋅mol-1 e ΔS0 = 9 ± 2 J ⋅mol-1⋅K-1 para o ácido 1-metil úrico e Ka = 275 ± 1 mol⋅L-1 com ΔH0 = 16 ± 3 kJ ⋅mol-1 e ΔS0 = 6 ± 1J ⋅mol-1⋅K-1 para a 1,7-dimetilxantina a 25 0C. Para a desativação do estado triplete da riboflavina, foram obtidas constantes de velocidade de 3kq = 4,2 x 108 L.mol-1.s-1 para a 1,7-dimetilxantina, 3kq = 1,0 x 108 L.mol-1.s-1 para o ácido 1,7-dimetil úrico e 3kq = 1,4 x 108 L.mol-1.s-1 para o ácido 1-metil úrico. Os ésteres metílicos (oleato de metila, ácido linoléico conjugado (CLA), linoleato de metila, linolenato de metila, araquidonato de metila, eicosapentanoato de metila, e docosahexanoato de metila) não desativam o estado singlete-excitado da riboflavina. Entretanto, os ésteres metílicos se mostraram reativos frente ao estado triplete da riboflavina com constantes de velocidades 3kq variando de 8,4 x 105 a 3,3 x 107 L⋅smol-1 ⋅s-1 com uma dependência linear do número de hidrogênios bis-alílicos com excessão do CLA. / The present thesis describes the kinetic and mechanistic studies of flavin singlet- and triplet-excited states deactivation by sterols (ergosterol and cholesterol), vitamin D, coenzyme Q10, vitamin K, fatty acids, and caffeine metabolites. From the Stern-Volmer analysis of the riboflavin fluorescence quenching by cholesterol, ergosterol, vitamin D, vitamin K and coenzyme Q10, it is noted that the singlet-excited state of riboflavin is deactivated with a rate constant exceeding the diffusion limit. However, the presence of cholesterol, ergosterol, vitamin D, vitamin K, coenzyme Q10 did not affect the lifetime of singlet-excited riboflavin as probed by single photon counting experiments suggesting the formation of a ground-state precursor complex [riboflavin ...substrate]. The 1:1 complex formed between riboflavin and vitamin D showed Ka = 4 x 104 ± 3 mol⋅L-1 a 25 0C with ΔH0 = -36 ± 7 kJ⋅mol-1 and ΔS0 = -5 ± 3 J⋅mol-1 ⋅K-1. The 1:1 complex formed between riboflavin and vitamin K (vit K) and riboflavin with coenzyme Q10 (CoQ10) showed Ka = 1 x 103 ± 1 mol⋅L-1 with ΔH0 = -110 ± 22 kJ⋅mol-1 and ΔS0 = 51 ± 9 J ⋅mol-1⋅K-1 for vit K e Ka =4 x 102 ± 1 mol⋅L-1, ΔH0 = -120 ± 27 kJ ⋅mol-1 and ΔS0 = 41 ± 7 J ⋅mol-1⋅K-1 for CoQ10 a 25 0C. For the deactivation of triplet riboflavin, bimolecular rate constants were found to vary from 1,4 x 108 L ⋅mol-1⋅s-1 (vit D) a 1,4 x 109 L ⋅mol-1⋅s-1 (CoQ10). The caffeine metabolites quench fluorescence emission of riboflavin however, without affecting the lifetime of the singlet-excited state, suggesting the formation of a ground state precursor complex [riboflavin ... substrate]. The complex formed between riboflavin and caffeine metabolites showed Ka = 295 ± 1 mol⋅L-1 with ΔH0 = -45 ± 8 kJ⋅mol-1 and ΔS0 = 12 ± 1 J⋅mol-1⋅K-1for 1,7-dimetyl uric acid, Ka = 289 ± 1 mol⋅L-1 with ΔH0 = -38 ± 5 kJ ⋅mol-1 and ΔS0 = 9 ± 2 J ⋅mol-1⋅K-1 for 1-methyl uric acid and Ka = 275 ± 1 mol⋅L-1 with ΔH0 = 16 ± 3 kJ ⋅mol-1 and ΔS0 = 6 ± 1J ⋅mol-1⋅K-1 for 1,7-dimethylxanthine at 25 0C. For the deactivation of triplet riboflavin, rate constant were obtained with 3kq = 4,2 x 108 L.mol-1.s-1 para a 1,7-dimethylxanthine, 3kq = 1,0 x 108 L.mol-1.s-1 for 1,7-dimethyl uric acid, and 3kq = 1,4 x 108 L.mol-1.s-1 for 1-methyl uric acid. The methyl esters (methyl oleate, conjugated linoleic acid (CLA), methyl linoleate, methyl linoleate, methyl arachidonate, methyl eicosapentanoate, and methyl docosahexanoate) did not quench the singlet-excited riboflavin. However, the methyl esters were shown to be reactive towards triplet riboflavin with rate constants ranging from 8,4 x 105 a 3,3 x 107 L⋅mol-1 ⋅s-1and depending linearly with the number of bis-allylic hydrogens with exception to CLA.

This thesis focuses on autofluorescence of flavins in gram-negative bacteria Cupriavidus necator H16 and its mutant strain PHB-4. The main methods used were fluorescence microscopy and flow cytometry. To confirm the presence of flavins, excitation and emission spectra of the bacterial suspension were measured, which were compared with flavin standards. In the part of testing cells without stress response, the autofluorescence of bacteria in PBS buffer and cell suspensions stained with fluorescence probe BODIPY 493/503 was measured. The ratio of short fluorescence lifetime to long autofluorescence lifetime, and its dependence on fluorescence probe was compared with previous conditions. Autofluorescence of the supernatant was measured; it was found that the relative amplitude of long lifetime was multiple times higher than in the cell. In the part devoted to the stress response, this thesis was focused on the amount of dissolved oxygen in the production medium and the effect on bacterial autofluorescence. Then differently concentrated hydrogen peroxide was used, the best results were obtained from the concentration of 100 mM in media. For comparison a combination of hydrogen peroxide with ferro-ammonium sulphate was used, but there was no big difference. Sodium azide and antimycin A were selected as substances that directly influence on bacterial respiratory chain. Both compounds affected change in the ratio of the relative amplitudes, but the distribution of these lifetimes and the autofluorescence change over time was affected only by sodium azide.

An overexposure to ultraviolet radiation can cause sunburn and some forms of skin cancer. UV light causes many different photoproducts. The cys-syn cyclobutylpyrimidine dimer (CPD) is the major photoproduct upon UV irradiation. DNA photolyase (PL) is a light-driven flavoprotein that repairs CPD in UV-damaged DNA. This repair process occurs in the presence of blue light through ultrafast photo-induced electron transfer from reduced anionic flavin adenine dinucleotide (FADH¯) to the CPD by an unknown mechanism. Since the excited state flavin transfers an electron to repair the damaged DNA, it is of utmost importance that we understand better the excited state properties of the flavins. In this work the excited state electronic properties of all three-oxidation states of flavin: oxidized form (FAD), semiquinone radical form (FADH•) and reduced anionic form (FADH¯) were studied using Stark spectroscopy and complimented by time dependent density functional theory (TD-DFT) calculations. These results are presented and discussed in Chapter 3 and 4. The difference dipole moments (Δμ) and the difference polarizabilities (Tr(Δα01)) were experimentally determined for first two lowest optically accessible states. The results are discussed in the context of photoreduction of flavins in wider class of flavoprotein blue light photoreceptors and catalytic electron transfer process in DNA repair. In the later part of this thesis (Chapters 5 and 6) the excited state electronic properties of monomeric 2-Aminopurine (2AP), 8-Vinyladenine 8VA were presented. These 8VA, 2AP are examples of fluorescent nucleotide analogues of adenine that can be incorporated into DNA with little perturbation of the normal double-helical structure. The fluorescence of these analogues is quenched when incorporated in double-stranded DNA (dsDNA). The basic mechanism underlying the fluorescence quenching by base stacking of 2AP and 8VA are is not well understood, and thus exploring the excited state electronic structures of these bases is an important first step. We have explored the excited state properties of 2AP and 8VA in frozen LiCl and ethanol solutions using Stark spectroscopy. High-level ab initio and TD-DFT calculations were performed to compliment the experimental results. / Chemistry

The excited state electronic structures of several biologically important chromophores were studied by Stark spectroscopy. The extent of charge redistribution upon excitation to the lowest excited states of the oxidized and semiquinone forms of flavin adenine dinucleotide (FAD) bound to the light activated DNA repair enzyme DNA photolyase have been studied previously by this technique. This work focuses on the catalytically active form, the two-electron reduced anion. To facilitate analysis of this experiment, the Stark spectra of a simple flavin derivative that is soluble in organic solvents was measured. The results of the analysis of these data are in agreement with previously a published linear dichroism experiment that found the absorption spectrum of flavins in this redox state arises from two distinct electonic transitions in the visible/near-ultraviolet spectral range, a fact that has not been incorporated into the analysis of many ultrafast spectroscopic experiments of reduced anionic flavins/flavoproteins. The difference dipole moment of the second, more intense, transition was found to be about twice as large as that of the lowest energy transition. With the aid of ab initio calculations, the directions of these dipole moments in the molecular frame were assigned. For both transitions, it was found that negative charge density is shifted toward the xylene ring of the flavin upon excitation. Another important consideration for the correct analysis of the photolyase spectra is the possibility of contamination by small amounts of the antenna chromophore, which also has absorption intensity in the near-ultraviolet region. We chose to study the cofactor for E. coli photolyase, 5,10-methenyltetrahydrofolate, and its photodecomposition product, 5,10-methylenetetrahydrofolate. The difference dipole moments for the lowest energy transitions of both of these chromophores were found to be quite large, ranging from 9-12 D fc and lying primarily along the transition dipole moment. Additionally, the difference polarizability of both chromophores was large, on the order of 200-300 Å3 fc2 . The Stark spectra of reduced anionic FAD in photolyase agrees well with the findings of the experiments on flavin in organic solvent; the magnitude of the difference dipole moments in both cases match within experimental error. While the direction of the difference dipole moment for the lowest transition is also the same in both cases, that of the second transition is changed in the protein matrix. The assignment of these vectors in the molecular frame shows that the two dipole moments are coincident for the cofactor bound to photolyase. This finding, where electron density is shifted toward the point of the flavin ring closes to the DNA lesion bound to the enzyme, is strong evidence that direct electron transfer takes place from the isoalloxazine ring of FAD to the DNA substrate in the catalytic cycle. The usefulness of Stark spectroscopy in investigating photoinduced charge redistribution was also shown for the donor-π-acceptor flavin dyad, azobenzylflavin (ABFL). The difference dipole moment was found to be 22 D, an approximately three-fold increase from the largest difference dipole moment found in naturally occurring flavins. This extensive charge redistribution corresponds to a large hyperpolarizability of the chromophore that suggests that ABFL may be useful in nonlinear optical applications. Transient absorption was used to supplement these experiments by monitoring the decay kinetics of ABFL after excitation. It was found that ABFL undergoes ultrafast charge recombination within 6 ps after excitation, leading to depopulation of the charge separated state before useful work can be performed for applications requiring electron transfer. These studies provide the ground work for rational design of other ABFL-like derivatives for use in a variety of applications. / Chemistry

Organická elektronika a bioelektronika zažívá v moderním věku obrovskou snahu o vývoj nových organických materiálů s vlastnostmi, které běžná elektronika na bázi křemíku obvykle nedosahuje. Tato práce se zabývá syntézou a charakterizací nových organických materiálů pro organickou elektroniku. Zaobírá se přípravou nových pentafluorsulfanylových heterocyklických stavebních bloků, alkylovaných vysokoúčinných organických pigmentů a bioinspirovaných organických -konjugovaných materiálů s modifikovatelnými fyzikálně-chemickými vlastnostmi a racionálními syntetickými přístupy k jejich přípravě. Pentafluorsulfanylová skupina (SF5) je ceněna pro svou vysokou elektronegativitu, lipofilitu, tepelnou a chemickou stabilitu. Pozitivně ovlivňuje optické a elektronické vlastnosti, rozpustnost a stabilitu v často lepší míře než u zavedených CF3-analogů. Šesti a čtyřkrokovou syntézou byly připraveny dva typy derivátů 3-SF5-substituovaných pyrrolidinů, které mohou sloužit jako všestranné stavební jednotky pro začlenění do pokročilých aromatických a heteroaromatických -konjugovaných systémů prostřednictvím atomů dusíku jako fluorované terminální skupiny. Modelový derivát byl zaveden jako terminální skupina do elektronově chudého heteroaromatického systému nukleofilní substitucí. Vodíkovými můstky vázané vysokovýkonné organické pigmenty přitahují velkou pozornost díky svým působivým polovodivým vlastnostem, silné 2D molekulární asociaci, vysoké tepelné, chemické a fotochemické stabilitě a nízké toxicitě. Přesto jsou pouze omezeně rozpustné a zpracovatelné, což lze vyřešit zavedením solubilizačních skupin. Je známo, že obzvláště objemné rigidní skupiny nesoucí adamantyl zlepšují uspořádání molekulární struktury, tepelnou stabilitu a výsledné vlastnosti díky samoorganizační schopnosti adamantanu. Adamantylmethylová a adamantylethylová skupina byla zavedena do vybraných barviv a pigmentů ze skupiny karbonylových azaacenů, rylen-diimidů a indigoidů pomocí nukleofilní substituce se zaměřením na zvýšení rozpustnosti a zpracovatelnosti při zachování tepelné stability a efektivní molekulární organizaci v pevné fázi. Fyzikálně-chemické studie série derivátů quinacridonu a epindolidionu ukázaly srovnatelnou, nebo vyšší tepelnou stabilitu než u nesubstituovaných derivátů, dobrou rozpustnost v organických rozpouštědlech, silnou fluorescenci v pevné fázi a roztoku v oblasti VIS a unikátní krystalovou strukturu pozorovanou z RTG analýzy. Flaviny jsou všudypřítomné bioinspirované organické materiály s nepostradatelnými biologickými funkcemi, výhodnými fyzikálně-chemickými vlastnostmi, chemickou a aplikační všestranností. Cílem práce byla modifikace optických, elektronických, elektrochemických, tepelných a dalších vlastností rozšířením -konjugovaného systému syntetizovaných materiálů. V první fázi byly navrženy dva syntetické přístupy pro přípravu série NH-nesubstituovaných flavinů, u kterých byly provedeny komplexní fyzikálně-chemické studie. Poté byly navrženy dva přístupy k syntéze N,N'-dialkylovaných flavinů s inkorporovaným butylovým, adamantylethylovým a triethylenglykolovým substituentem. Alkylací byla zvýšena rozpustnost v organických rozpouštědlech a vodném prostředí, zesílena fluorescence v pevné fázi a v roztocích a modifikovány tepelné vlastnosti v závislosti na zavedeném alkylovém substituentu.