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Cellulose dissolution: Comparison of two non-derivatizing solvent systems and the effect of additives
Kotov, Nikolay ; Dybal, Jiří (advisor) ; Pop-Georgievski, Ognen (referee) ; Šloufová, Ivana (referee)
Title: Cellulose dissolution: Comparison of two non-derivatizing solvent systems and the effect of additives Author: Nikolay Kotov Institute: Institute of Macromolecular Chemistry, Czech Academy of Sciences Supervisor of the doctoral thesis: RNDr. Jiří Dybal, CSc. Consultant: Mgr. Adriana Šturcová, Ph.D. Institute of Macromolecular Chemistry, Czech Academy of Sciences, Department of Vibrational Spectroscopy Abstract: Cellulose is an abundant renewable material, which processing and applicability is limited owing to cellulose inability to dissolve in commonly used solvents. Only specific solvents or their combinations are able to dissolve cellulose and its dissolution processes remain unclear till nowadays. Aim of this thesis was to acquire new experimental information on the changes which cellulose exhibits upon dissolution in two exemplary solvents: an ionic liquid 1-butyl-3-methylimidazolium chloride (bmimCl) and in an organic solvent N,N-dimethylacetamide (DMAc) with lithium chloride (LiCl). The main tool for that investigation is vibrational spectroscopy which provides valuable information about the polymer structure. Similarities and differences found in the spectra of cellulose in those two solvents and influence of cellulose on the solvents are analyzed. Furthermore, influence of additives on the...
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Preparation and study of novel crystalline materials for nonlinear optics based on nitrogen-containing heterocycles
Kloda, Matouš ; Němec, Ivan (advisor) ; Schwendt, Peter (referee) ; Holubová, Jana (referee)
The presented Ph.D. thesis is aimed at the preparation and characterisation of novel crystalline materials with application potential in nonlinear optics (NLO). The main goal was preparation of crystalline salts and adducts (cocrystals) of selected nitrogen-containing heterocycles with a range of organic and inorganic acids. Based on previous study and quantum- chemical calculations, the following starting heterocycles were selected: 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 3-amino-1,2,4-triazine and 3-amino-5,6-dimethyl- 1,2,4-triazine. The prepared materials were characterised mainly by X-ray diffraction and vibrational spectroscopy and the interpretation of the vibrational spectra was based on quantum-chemical calculations. The systems based on aminopyrimidines were the first field of study in presented thesis. The thesis represents a finalisation of our previous study focused on inorganic salts and cocrystal in the case of 2-aminopyrimidine. The characterisation of a pair of cocrystals with boric acid was accomplished. The 12 new salts and adducts were prepared and characterised in the case of 4-aminopyrimidine and only one crystalline product - adduct with succinic acid - was obtained in the case of 5-aminopyrimidine. The systems based on 3-amino-1,2,4-triazine and its...
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Preparation and study of novel crystalline materials for nonlinear optics based on nitrogen-containing heterocycles
Kloda, Matouš ; Němec, Ivan (advisor) ; Schwendt, Peter (referee) ; Holubová, Jana (referee)
The presented Ph.D. thesis is aimed at the preparation and characterisation of novel crystalline materials with application potential in nonlinear optics (NLO). The main goal was preparation of crystalline salts and adducts (cocrystals) of selected nitrogen-containing heterocycles with a range of organic and inorganic acids. Based on previous study and quantum- chemical calculations, the following starting heterocycles were selected: 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 3-amino-1,2,4-triazine and 3-amino-5,6-dimethyl- 1,2,4-triazine. The prepared materials were characterised mainly by X-ray diffraction and vibrational spectroscopy and the interpretation of the vibrational spectra was based on quantum-chemical calculations. The systems based on aminopyrimidines were the first field of study in presented thesis. The thesis represents a finalisation of our previous study focused on inorganic salts and cocrystal in the case of 2-aminopyrimidine. The characterisation of a pair of cocrystals with boric acid was accomplished. The 12 new salts and adducts were prepared and characterised in the case of 4-aminopyrimidine and only one crystalline product - adduct with succinic acid - was obtained in the case of 5-aminopyrimidine. The systems based on 3-amino-1,2,4-triazine and its...
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Spectroscopy study of metal complexes with terpyridyl ligands
Kožíšek, Jan ; Šloufová, Ivana (advisor) ; Procházka, Marek (referee)
The work is focused on preparation and characterization of octahedral Fe(II) complexes of 2,2′:6′,2′′-terpyridine (tpy) substituted in 4' position by various groups: Cl (tpyCl), chlorophenyl (tpyPhCl) and 2-thienyl (Ttpy)). Formation and stability of prepared complexes were studied by UV/vis spectroscopy on the basis of titration of tpy ligands by Fe(II) ions. The molar absorption coefficient of the metal-to-ligand charge transfer (MLCT) band was found to increase in the order: tpy < tpyCl < tpyPhCl < Ttpy. The MLCT band position increases in the same order, starting from 551 nm for [Fe(tpy)2]2+ to 576 nm for [Fe(Ttpy)2]2+ . Raman scattering (RS) spectra of tpy ligands were obtained upon non-resonance 780 nm excitation. Four excitation wavelengths (445, 532, 633 a 780 nm) were used for measurement Fe(II) complexes. The excitation profiles of both Raman scattering and surface-enhanced Raman scattering (SERS) spectra were constructed for [Fe(tpyCl)2]2+ complex. On the basis of DFT calculations performed for this complex, the Raman active modes have been assigned to the symmetry species of the D2d point group. Similarly as for the previously studied [Fe(tpy)2]2+ complex, activation of E modes in the region of MLCT band suggests contribution of Herzberg-Teller mechanism to the overall molecular...
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Elementary Processes at Low Temperatures - Reactions of H3+ and N2H+ in Afterglow Plasmas
Kálosi, Ábel ; Plašil, Radek (advisor) ; Rubovič, Peter (referee) ; Španěl, Patrik (referee)
Electron-ion recombination and ion-neutral interactions play a piv- otal role in the chemical evolution of molecules in the Interstellar Medium (ISM). Physical conditions under which these processes un- dergo in the ISM include a wide range of temperatures and particle number densities. This work contributes to the experimental study of named low temperature phenomena in the range of 30 K to 300 K focusing on the reactions of hydrogen-containing light molecules. The employed experimental techniques are based on a combination of a Stationary Afterglow (SA) instrument with a Continuous Wave Cavity Ring-down Spectrometer (cw-CRDS). The main contributions of this work can be split into three topics. (1) The proton and deuteron con- taining isotopic system of H3 + ions. The isotopic fractionation process in collisions with hydrogen and deuterium gas was investigated in low temperature discharges, nominal ion temperatures of 80 K to 140 K, to deduce relative ion densities in the experiments. These are necessary for afterglow studies of isotopic effects in electron-ion recombination of the studied ions. (2) Vibrational spectroscopy of N2H+ ions focusing on first overtone (2ν1 band) transitions and ion thermometry, the first step towards studies of electron-ion recombination. (3) The role of para/ortho spin...
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Cellulose dissolution: Comparison of two non-derivatizing solvent systems and the effect of additives
Kotov, Nikolay ; Dybal, Jiří (advisor) ; Pop-Georgievski, Ognen (referee) ; Šloufová, Ivana (referee)
Title: Cellulose dissolution: Comparison of two non-derivatizing solvent systems and the effect of additives Author: Nikolay Kotov Institute: Institute of Macromolecular Chemistry, Czech Academy of Sciences Supervisor of the doctoral thesis: RNDr. Jiří Dybal, CSc. Consultant: Mgr. Adriana Šturcová, Ph.D. Institute of Macromolecular Chemistry, Czech Academy of Sciences, Department of Vibrational Spectroscopy Abstract: Cellulose is an abundant renewable material, which processing and applicability is limited owing to cellulose inability to dissolve in commonly used solvents. Only specific solvents or their combinations are able to dissolve cellulose and its dissolution processes remain unclear till nowadays. Aim of this thesis was to acquire new experimental information on the changes which cellulose exhibits upon dissolution in two exemplary solvents: an ionic liquid 1-butyl-3-methylimidazolium chloride (bmimCl) and in an organic solvent N,N-dimethylacetamide (DMAc) with lithium chloride (LiCl). The main tool for that investigation is vibrational spectroscopy which provides valuable information about the polymer structure. Similarities and differences found in the spectra of cellulose in those two solvents and influence of cellulose on the solvents are analyzed. Furthermore, influence of additives on the...
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Crystal and molecular structure study of garnets from selected localities of the České středohoří Mts.
Píšová, Barbora ; Skála, Roman (advisor) ; Laufek, František (referee)
Major and minor element contents of garnets from mantle peridotites and eclogites brought to the surface by volcanic rocks of the České středohoří Mts. were determined by an electron probe microanalyzer. Garnets are homogenous and their chemical composition corresponds to solid solution containing 65-71 % pyrope, other end members significantly present are almandine, uvarovite and grosulare. This method also help to discover polyphase inclusions chemically corresponding to amphiboles (pargasite, cummingtonite, magnesio-hornblende and katophorite). Next to amphiboles following minerals were found in inclusions: omphacite, carbonates, phlogopite, clinochlore, olivine, apatite, spinel group minerals, and sulfidic phases potentially close to pentlandite. Samples were also analyzed by powder X-ray diffraction. Qualitative phase analysis confirmed pyrope homogeneity. The refinement of crystal structure parameters was performed by the Rietveld method. Raman microspectroscopy showed shifts of individual bands in the Raman spectra compared to those of pure pyrope. Position of bands in spectra differs due to the substitution of Ca for Mg at the dodecahedral sites of the structure. Mutual positive correlations among elements Cr, Ca, Mg, Al, Si, Mn, Ti and Na were observed. Correlations were found also between...
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Synthesis and study of crystalline materials for NLO
Janatková, Tereza ; Němec, Ivan (advisor) ; Vojtíšek, Pavel (referee)
This thesis is focused on preparation and study of new compounds of chosen organic bases with potential use in nonlinear optics. 2-amino-5-nitropyrimidine, 2-amino-4-methylpyrimidine and their salts with inorganic and organic acids are compounds of the main interest. Diffraction and vibrational-spectroscopic methods of characterization were used in combination with quantum chemical calculation methods. Another aim of this thesis was preparation of new salts of chosen pyrimidine derivates with the use of methylsulphonic acid. Part of this section is devoted to completion of pyridinium methylsulphonate phase transition and nonlinear optical property studies.
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Molecular crystals for NLO applications - compounds of 1H-pyrazole-carboxamidine
Kohúteková, Soňa ; Němec, Ivan (advisor) ; Šloufová, Ivana (referee)
Title: Molecular crystals for NLO applications - compounds of 1H-pyrazole-carboxamidine Author: Bc. Soňa Kohúteková Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Ivan Němec, Ph.D. Abstract: The aim of this diploma thesis is preparation and characterisation of novel compounds of 1H-pyrazole-carboxamidine in consideration of their potential application in the field of nonlinear optics. This thesis is focused on preparation of crystalline salts or adducts combining 1H-pyrazole-carboxamidine with selected inorganic and organic acids. Prepared materials were characterised mainly by the means of vibrational spectroscopy and X-ray diffraction analysis. Quantum-chemical calculations were used for a prediction of nonlinear optical properties as well as for interpretation of measured vibrational spectra. Four different approaches of calculations were used for an optimisation of computing time together with accuracy of the fit of calculated and measured spectra. Finally, measurements of second harmonic generation efficiency of two powder samples with non-centrosymmetric crystal structures were performed. Key words: NLO, vibrational spectroscopy, crystal structure, quantum-chemical calculations
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Characterization of proteins of 2'-5' oligoadenylate pathway by means of vibrational spectroscopy
Víšová, Ivana ; Kopecký, Vladimír (advisor) ; Bednárová, Lucie (referee)
The work concerns to structural characterization of two important proteins of 2'-5' oligoadenylate pathway participating in an immune response of organism to a viral infection. Studied proteins were ankyrin domain of mouse RNase L, the C-terminal part of human phosphodiesterase 12 and the complete human phosphodiesterase 12. The proteins were characterized by Raman spectroscopy, infrared spectroscopy, electronic circular dichroism, dynamic light scattering and in addition by two non-spectroscopic methods- differential calorimetry and electrophoresis. For each protein the secondary structures, thermal stability, weight of oligomers and generally a basic characterization by above mentioned methods were provided.
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