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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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Application of micro-Raman spectroscopy to analysis of artworks
Váňová, Hana ; Němec, Ivan (advisor) ; Šloufová, Ivana (referee)
This thesis deals with the application of micro-Raman spectroscopy to analysis of artworks. The main topic of the thesis was to qualify, select and eventually optimize methods acceptable to identification of indigo dye in the paint layers of artworks. Selected dye was studied in various states using set of excitation lasers emitting in the visible region. There was also studied the real usage of resonance and surface-enhanced methods. The result of the thesis are the conclusions related with the suitability of particular techniques of Raman spectroscopy to identify the target pigment in the art.
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Vibrational modes of nucleic acids components characterized by means of variable proton-deuterium exchange
Zoul, David ; Štěpánek, Josef (advisor) ; Šloufová, Ivana (referee)
Although the nucleon acid oscillatory spectra have been studied for a long period of time, many of oscillating modes have not been properly explained regarding their geometric sensitivity and weak binding. One of the possibilities how to acquire experimental data for interpretation of theese modes is to confront oscillating spectra of isotopes. The simplest is proton - deutron exchange. When molecules dissolve in heavy water they rapidly exchange the heteroatoms, but this is simultaneous for more stages, which leads to dynamic equilibrium state among various isotope forms. Statistic analysis of temporal progression of Raman spectra give us the possibility to analyze the spectra and to obtain unique experimental data. This technique is very promising for more complex nucleon acid segments to gain more structural information. This diploma thesis represents pilot study of introduced methodics. The objective is to implement adaptation of Raman spectrometr for given types of expiments and undertake first series of measurements. The results should clarify application bounds of proposed method refering to sensitivity, time constant of incident isotope exchange, severity of read-out in comparasion of achieved accuracy of the measurement.
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Surface-enhanced Raman microspectroscopy of biomolecules and biological systems
Šimáková, Petra ; Procházka, Marek (advisor) ; Michl, Martin (referee) ; Šloufová, Ivana (referee)
The aim of this thesis was using surface-enhanced Raman scattering (SERS) microspectroscopy for the study of biomolecules and biological systems. The main probe molecule was cationic porphyrin H2TMPyP, however, other porphyrins, tryptophan and two lipids were also used. The sensitivity and reproducibility of several solid SERS substrates: (i) Au and Ag nanoparticles (NPs) immobilized via a bifunctional linker, (ii) AgNPs immobilized by drying, (iii) highly ordered Au and Ag film-over-nanosphere (FON) and (iv) Ag-coated insect wings were compared. On most of the solid substrates, the lowest detected H2TMPyP concentration was ~10-8 M. The highest sensitivity was provided by the dried drops of AgNPs/analyte mixture, where concentrations 1×10-10 M TMPyP, 1×10-5 M tryptophan, 2×10-7 M DSPC and 3×10-7 M DMTAP were detected. Nevertheless, the spectral reproducibility was decreased due to porphyrin metallation and perturbation of the lipid spectra in comparison to their Raman spectra from solution. The highest reproducibility was achieved by AuFON and Ag-coated insect wings. Finally, the AgNPs modified by PEG polymers were tested for intracellular application using HeLa cancer cells. Metallation of H2TMPyP served to probe the accessibility of PEG- AgNPs surface. The results proved that the accessibility...
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Raman Microspectroscopy in Microfluidic Devices
Peksa, Vlastimil ; Mojzeš, Peter (advisor) ; Šloufová, Ivana (referee)
Miniaturization of devices to study chemical interactions and processes in liquid samples has led to the emergence of microfluidics and construction of lab-on-a-chip systems. Present work was devoted to implementation, development and testing of microfluidic systems with detection by confocal Raman microscopy and surface enhanced Raman scattering under the conditions of training department. Several options of performing standard macroscopic measurements in microscopic scales were explored. A method for measuring thermal stability of biopolymers in microsystems with contactless detection of temperature has been designed and tested. Furthermore, possibilites for studying the SERS effect within microfluidic channels were explored. It was demonstrated that the microfluidic chips provide promising opportunity to study hydrodynamics of liquids at microscopic level and chemical reactions and kinetics.
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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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Monitoring of surface reactions on plasmon nanoparticles by surface-enhanced Raman spectroscopy
Kožíšek, Jan ; Šloufová, Ivana (advisor) ; Procházka, Marek (referee)
The presented diploma thesis is focused on finding conditions suitable for the study of surface reactions, especially Suzuki-Miyaura cross-coupling reaction (SMCR), by the surface- enhanced Raman scattering (SERS) method. The first part of the work deals with the optimization of the conditions of individual reactions using the classical synthetic Schlenk technique. Traditional, published, conditions for SMCR were gradually modified during the work so that the reactions could be performed in aqueous media and at room temperature, i.e., under conditions suitable for SERS spectroscopy. The following catalysts were tested: (i) PEPPSI - the traditional SMCR catalyst; (ii) palladium ions; (iii) Pd colloids; (iv) bimetallic colloids of Pd and plasmonic metal (Ag, Au) in the form of core-shell and alloy; (v) Ag and Au colloids with additions of palladium salt or N- heterocyclic carbenes (NHC-catalysts). Two groups of substrates were used: substrates with functional groups with high affinity for the surfaces of metal nanoparticles (NPs) and substrates without these anchoring functional groups. Substrates without the anchoring functional groups can be expected to enter the SMCR reaction from solution. In the second part of this diploma thesis selected reaction mixtures for SMCR were performed in septum...
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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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Microcrystalline inclusions in microalgae studied via Raman microscopy
Suja, Matyáš ; Mojzeš, Peter (advisor) ; Šloufová, Ivana (referee)
Many freshwater, terrestrial or marine microalgae contain various microcrystalline inclusions that they use in their life cycle. However, the identification of the molecular composition of these inclusions via many physical or chemical methods is often very difficult and susceptible to many measurement errors. Therefore, the chemical composition of these microcrystals in many microalgae has not been determined at all or may be incorrect. One of the high precision methods capable of determining the composition of microcrystalline bodies within microalgae is Raman confocal microscopy. This very promising method of optical vibrational spectroscopy allows rapid and non-destructive molecular analysis of objects. Raman microscopy does not require chemical extraction, modification or other color marking or staining of the sample. Therefore, it can directly measure living cells at various stages of their natural development. The chemical composition of the sample is then characterized by its corresponding Raman vibrational spectrum. The aim of this diploma thesis is to determine the presence of microcrystals in different species of microalgae, study the conditions of their occurrence and identify their chemical composition via Raman microscopy.
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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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