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EPR Study of Radical Reactions of Secondary Amines in Liquid Phase
Šafaříková, Lenka ; Lehocký,, Marián (referee) ; Mazúr, Milan (referee) ; Omelka, Ladislav (advisor)
In the framework of Ph.D. thesis the evaluation of radical reactions of four groups of secondary amines R1–NH–R2 in the presence of some selected types of agents was performed using EPR spectroscopy. First group was represented by peroxoagents (3-chloroperbenzoic acid, tBuO2 radicals), the second group involved compounds of PbIV+ (PbO2, Pb(OAc)4) functioning as hydrogen-abstracting agents. In the presence of peroxyagents the formation of corresponding aminoxyl radicals R1–NO–R2 was demonstrated. In the case of surplus of tBuO2 radicals these radicals enter the consecutive reactions which products are new types of secondary aminoxyls. By the interpretation of reaction mechanism the intermediary formation of nitrones was assumed. These function in later steps of the reaction as spin traps for tBuO2 radicals. By the study of radical mechanism of amines R1–NH–R2 initiated by PbIV+ agents was proved, that these compounds hydrogen atom not only from –NH– group under formation of aminyl radicals, but also from C–H bonds in substituents R1, R2 (the formation of C-radicals). Because both groups of the radicals formed are characterized by high reactivity, their identification was possible only using spin-trapping method. In the course of the investigation of radical reactions of secondary amines the big amount of experimental EPR spectra was obtained. These exhibited in many cases very high hyperfine structure. Due to this fact it was necessary to perform the detailed evaluation on the basis of spectral simulation. Except of some special cases using this approach the interpretation of majority of registered EPR spectra was interpreted and EPR parameters were summarized in tables.
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Radical intermediates generated by the splitting of X-H bond in different types of H-donors
Šafaříková, Lenka ; Mazúr, Milan (referee) ; Omelka, Ladislav (advisor)
In the frame of submitted diploma thesis dealing with the radical products of the decomposition of different X-H bonds, primary attention was focused on the detection of radical intermediates from decomposed N-H bonds. This access was realized with secondary amines of N-alkylaniline group, as well as with other structures R1-NH-R2. The aim was to confirm the formation of unstable aminyl radicals R1-N•-R2, which is possible by using spin-trapping method. In the series of experiments, where the compounds of lead and cobalt, as well as stable radical DPPH were applied as initiators of the decomposition, the unambiguous evidence for aminyl radicals was found only in the case of N-alkylanilines. With other secondary amines the detection of aminyl radicals is an open problem, because their adducts with nitrosobenzene are in very low concentration. Besides the study of the decomposition of N-H bonds also the products of the decomposition of phenolic O-H bonds, as well as products of the decomposition of C-H bonds in alkylsubstituents in phenols was studied.
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Spin-trapping of radical products of H-transfer from oxygeneous donors
Šafaříková, Lenka ; Polovka, Martin (referee) ; Omelka, Ladislav (advisor)
Within the bachelor thesis the evaluation of experimental material focused on EPR study of spin-trapping of phenoxyl radicals on aromatic nitrosocompounds was performed. It was found that phenoxyl radicals from unhindered phenols add to nitrosogroup in the ortho-position. As a result, the nitroxyl radicals are formed. According to the structure of nitrosocompounds this nitroxyl radicals have the character either of phenoxazinoxyl radicals in the case of nitrosobenzene or derivatives of diphenylnitroxyl radical in the case of nitrosoduren. In the work is also documented the specific behavior of some phenols containing methyl group as the para substituent.
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Influence of technological factors on the hardness of wood
Šafaříková, Lenka ; Gašparík, Miroslav (advisor) ; Ruman, Daniel (referee)
Focus of the diploma thesis is to investigate the influence of the selected factors (type of wood, thickness, densification) on the wood hardness. For the experimental measurements the Brinell hardness test method was used. The hardness measurements were performed on the specimens made from two different types of wood. Obtained results were statistically analyzed into the graphs. The main goal of the thesis was to determine the change in the static hardness in dependence on the previously mentioned factors. From the experimental data it can be seen that the wood hardness increases with the higher degree of densification . This phehomenon applies to both investigated wood materials which are European beech (Fagus sylvatica) - hardwood specimen and European aspen (Populus tremula) - softwood specimen.
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EPR Study of Radical Reactions of Secondary Amines in Liquid Phase
Šafaříková, Lenka ; Lehocký,, Marián (referee) ; Mazúr, Milan (referee) ; Omelka, Ladislav (advisor)
In the framework of Ph.D. thesis the evaluation of radical reactions of four groups of secondary amines R1–NH–R2 in the presence of some selected types of agents was performed using EPR spectroscopy. First group was represented by peroxoagents (3-chloroperbenzoic acid, tBuO2 radicals), the second group involved compounds of PbIV+ (PbO2, Pb(OAc)4) functioning as hydrogen-abstracting agents. In the presence of peroxyagents the formation of corresponding aminoxyl radicals R1–NO–R2 was demonstrated. In the case of surplus of tBuO2 radicals these radicals enter the consecutive reactions which products are new types of secondary aminoxyls. By the interpretation of reaction mechanism the intermediary formation of nitrones was assumed. These function in later steps of the reaction as spin traps for tBuO2 radicals. By the study of radical mechanism of amines R1–NH–R2 initiated by PbIV+ agents was proved, that these compounds hydrogen atom not only from –NH– group under formation of aminyl radicals, but also from C–H bonds in substituents R1, R2 (the formation of C-radicals). Because both groups of the radicals formed are characterized by high reactivity, their identification was possible only using spin-trapping method. In the course of the investigation of radical reactions of secondary amines the big amount of experimental EPR spectra was obtained. These exhibited in many cases very high hyperfine structure. Due to this fact it was necessary to perform the detailed evaluation on the basis of spectral simulation. Except of some special cases using this approach the interpretation of majority of registered EPR spectra was interpreted and EPR parameters were summarized in tables.
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Radical intermediates generated by the splitting of X-H bond in different types of H-donors
Šafaříková, Lenka ; Mazúr, Milan (referee) ; Omelka, Ladislav (advisor)
In the frame of submitted diploma thesis dealing with the radical products of the decomposition of different X-H bonds, primary attention was focused on the detection of radical intermediates from decomposed N-H bonds. This access was realized with secondary amines of N-alkylaniline group, as well as with other structures R1-NH-R2. The aim was to confirm the formation of unstable aminyl radicals R1-N•-R2, which is possible by using spin-trapping method. In the series of experiments, where the compounds of lead and cobalt, as well as stable radical DPPH were applied as initiators of the decomposition, the unambiguous evidence for aminyl radicals was found only in the case of N-alkylanilines. With other secondary amines the detection of aminyl radicals is an open problem, because their adducts with nitrosobenzene are in very low concentration. Besides the study of the decomposition of N-H bonds also the products of the decomposition of phenolic O-H bonds, as well as products of the decomposition of C-H bonds in alkylsubstituents in phenols was studied.
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Spin-trapping of radical products of H-transfer from oxygeneous donors
Šafaříková, Lenka ; Polovka, Martin (referee) ; Omelka, Ladislav (advisor)
Within the bachelor thesis the evaluation of experimental material focused on EPR study of spin-trapping of phenoxyl radicals on aromatic nitrosocompounds was performed. It was found that phenoxyl radicals from unhindered phenols add to nitrosogroup in the ortho-position. As a result, the nitroxyl radicals are formed. According to the structure of nitrosocompounds this nitroxyl radicals have the character either of phenoxazinoxyl radicals in the case of nitrosobenzene or derivatives of diphenylnitroxyl radical in the case of nitrosoduren. In the work is also documented the specific behavior of some phenols containing methyl group as the para substituent.
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