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Numerical optimization of solid-state NMR experiments
Šmelko, Andrej ; Tošner, Zdeněk (advisor) ; Chlan, Vojtěch (referee)
Numerical optimizations of solid-state nuclear magnetic resonance experiments are one of the possible solutions to its low sensitivity. Using the Average Hamiltonian Theory, the negative effects of the radiofrequency field inhomogeneity on magnetization transfer were investigated. To overcome these effects, the Average Hamiltonian Theory was employed in the optimization of commonly used techniques such as Ramp-CP and Adiabatic-CP, optimization of pulses with arbitrarily modulated amplitude and new periodic pulses with arbitrarily modulated amplitudes and phases. Both types of shaped pulses achieved significantly higher efficiencies than Ramp- CP and Adiabatic-CP. The highest efficiency enhancement was calculated at high spinning frequencies and low dipolar coupling constants where the effect of the inhomogeneity is the strongest.
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Supramolecular complexes of oxoporphyrinogens with organic molecules
Březina, Václav ; Hanyková, Lenka (advisor) ; Mojzeš, Peter (referee) ; Tošner, Zdeněk (referee)
Title: Supramolecular complexes of oxoporphyrinogens with organic molecules Author: Václav Březina Department: Department of Macromolecular Physics Supervisor: doc. RNDr. Lenka Hanyková, Dr., Department of Macromolecular Physics Abstract: Oxoporphyrinogens are flat macrocyclic molecules possessing binding and protonation sites, and capable of light absorption in the visible region. These properties are prerequisites for a colori- metric molecular sensor, i.e. a specific detector of other molecules in the sample. In this work, we studied chromic properties of three oxoporphyrinogens, OxP and its partially (Bz2OxP) and fully (Bz4OxP) N-benzylated derivatives. Their colorimetric response to organic acids is caused by protonation and subsequent formation of supramolecular host-guest complex. We have shown that colorimetric sensitivity is highest for OxP and gradually weakens for Bz2OxP and Bz4OxP since the N-benzylation blocks the central binding sites, decreasing binding affinity of the ox- oporphyrinogens. Furthermore, solvatochromic response of the oxoporphyrinogens to varying solvent polarity showed similar sensitivity decrease in Bz2OxP and Bz4OxP. The chromic and binding properties were studied by UV/vis and NMR spectroscopy, host-guest binding models were applied to describe the formation of...
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Measurement of transverse relaxation using spin echo methods
Škoch, Antonín ; Tošner, Zdeněk (advisor) ; Hanyková, Lenka (referee)
Title: Measurement of transverse relaxation using spin echo methods Author: MUDr. Antonin Skoch, Ph.D. Department: Department of Low Temperature Physics Supervisor: RNDr. Zdenek ToSner, Ph.D. NMR laboratory, of Faculty of science, Charles University in Prague Supervisor's e-mail address: tosner(o)karlov.mff.cuni.cz Abstract: The study of TI relaxation in systems with homonuclear J-coupling is complicated by modulation in the relaxation curve. This J-modulation can be removed when CPMG sequence is used and the period of repetition of refocusing pulse Tfulfils a condition r « * ( 1 ) Ai' where Av is the frequency difference of coupled nuclei. However, the condition (I) cannot be in practice always fulfilled. The aim of this work was to investigate J-modulation and relaxation behaviour of homonuclear J-coupled system in various parameters of CPMG sequence. Simulations based on numerical solution of Liouville-von Neumann equation and Redfield theory were performed. Relaxation curves of Chh group of citrate were measured on high-resolution NMR spectrometer. It was found that the suppression of J-modulation can be achieved also for T longer than required by the condition (1) providing that the refocusing angle in CPMG for both J-coupling partners 9^180ř. The simulations yielded conditions for T when J-modulation...
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NMR studies of metabolicaly active peptides
Hexnerová, Rozálie ; Tošner, Zdeněk (advisor) ; Obšil, Tomáš (referee)
The regulation of metabolic and mitogenic cellular processes is a complex system, depending on the precise function of several signalling cascades. One example is the insulin pathway, which is mediated by a group of three sequentially and structurally highly similar hormones (insulin, insulin-like growth factor (IGF) -I and -II) and their homologous tyrosine kinase receptors (IR-A, IR-B, IGF-1R). Such a high degree of homology leads to crosstalk in receptor communication, with each of the ligands triggering different biological responses. The design of insulin analogues activating primarily metabolic effects or IGF antagonists suppressing an unfavourable mitogenic response is one of the main goals in this research field, which can be facilitated by identification of the regions responsible for receptor binding. The work included in this thesis is focused on the effects on receptor interactions following the introduction of selected elements from the IGF-I primary sequence into the IGF-II molecule. In particular, these include a point mutation of Ser29 to Asn, an insertion of Gly-Ser after Arg34 , an insertion of Pro-Gln after Ser39 , or combination of both insertions. Although the IGF-II modifications described here negatively affected binding affinity towards IR-A, they did not enhance the IGF-1R...
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Support material for teaching NMR spectroscopy at secondary schools
Tomanová, Marie ; Tošner, Zdeněk (advisor) ; Hrubý, Martin (referee)
Nuclear magnetic resonance is an important, irreplaceable and very common method used in chemistry and medicine. From this perspective, it is highly desirable to implement NMR spectroscopy into high school education. But unfortunately there is not enough material in the Czech language, which would correspond to a high school student's level of knowledge. This thesis looks at creating support materials for teaching NMR spectroscopy and the possibilities of its implementation into high school education. For this purpose, following materials were prepared: an educational text, tests and a database of measured spectra (appendix on CD). Materials were tested in the form of a directed interview and then modified according to the results. This testing confirmed that the text is clear, motivating, and that this topic would be appreciated by both students and teachers. The materials will be available for teachers and high school students at the educational portal studiumchemie.cz. Powered by TCPDF (www.tcpdf.org)
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Measurement of transverse relaxation using spin echo methods
Škoch, Antonín ; Tošner, Zdeněk (advisor) ; Hanyková, Lenka (referee)
Title: Measurement of transverse relaxation using spin echo methods Author: MUDr. Antonin Skoch, Ph.D. Department: Department of Low Temperature Physics Supervisor: RNDr. Zdenek ToSner, Ph.D. NMR laboratory, of Faculty of science, Charles University in Prague Supervisor's e-mail address: tosner(o)karlov.mff.cuni.cz Abstract: The study of TI relaxation in systems with homonuclear J-coupling is complicated by modulation in the relaxation curve. This J-modulation can be removed when CPMG sequence is used and the period of repetition of refocusing pulse Tfulfils a condition r « * ( 1 ) Ai' where Av is the frequency difference of coupled nuclei. However, the condition (I) cannot be in practice always fulfilled. The aim of this work was to investigate J-modulation and relaxation behaviour of homonuclear J-coupled system in various parameters of CPMG sequence. Simulations based on numerical solution of Liouville-von Neumann equation and Redfield theory were performed. Relaxation curves of Chh group of citrate were measured on high-resolution NMR spectrometer. It was found that the suppression of J-modulation can be achieved also for T longer than required by the condition (1) providing that the refocusing angle in CPMG for both J-coupling partners 9^180ř. The simulations yielded conditions for T when J-modulation...
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