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Chemical and Physical Transformations of Humic Acids
Vlčková, Zoja ; Pospíšilová, Ľubica (oponent) ; Janoš,, Pavel (oponent) ; Pekař, Miloslav (vedoucí práce)
This work is a pilot study testing the relationships between biological properties and structure of humic acids extracted from original and modified South-Moravian lignite, mine Mír, Mikulčice. In first part of the work, methods suitable for increase of the humic acid yield were explored. Lignite oxidation in gas phase turned out to be relatively instrumentally demanding and insufficiently effective. Therefore, only oxidation in liquid phase was explored further along with modification with short-chained organic acids. Modification with short-chained organic acids was inspired by processes enhancing biological functions in rhizosphere, i.e. the root system produces exudates causing changes in the supramolecular structure of the surrounding organic matter, improving its mobility and cell-walls penetration. Primary structure of humic acids produced in this work was investigated by elemental analysis, solid state NMR, EPR and UV-VIS spectroscopy. Despite the fact that only minor differences were found, conducted assessment of biological activity and genotoxic potential showed that humic acids and their respective humates isolated from lignite with different pre-treatment show different bioactivity. Therefore, supramolecular structure of samples in diluted solutions was investigated by means of HPSEC, HRUS and densitometry measurements. Two counterions – potassium and ammonium – were tested. Obtained results confirm the assumption that observed quality of humates depends on counterion, concen-tration of humate and also on the method of lignite pre-treatment. Both selected pre-treatment methods showed potential to produce humic acids with variable biological properties, applicable in agriculture, environmental chemistry and potencially also in pharmacology.
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Hydrogels of Humic Acids
Cihlář, Zdeněk ; Lehocký,, Marián (oponent) ; Pospíšilová,, Lubica (oponent) ; Kučerík, Jiří (vedoucí práce)
Humic acids (HAs) are the main components of the soil organic matter. They are ubiquitous substances with complex chemical and physicochemical structure. In this study, several modifications of HAs were carried out in order to modify their properties. In the first part, the influence of lignite air oxidation on the yield and physicochemical character of regenerated humic acids were studied. In the second step, to stabilize the structure of lignite humic acids and improve the water holding capacity, we applied formaldehyde and carbodiimides crosslinking procedures leading to covalent coupling of humic acids moieties. The production of crosslinked structures was motivated by the attempt to design HAs-based systems resembling hydrogels, with the possibility to modify their reactivity and water retention. Samples were analyzed for their chemical composition and physicochemical properties using various techniques, among the most important were DSC and NMR relaxometry. The chemical composition was studied using FTIR and elemental analysis in order to assess the changes in comparison to pristine humic acids. The stabilities of derivatives were determined by using thermogravimetry. The most important parameter studied in this work was the change in hydration characteristics. For this reason, we developed and applied several new thermoanalytical and NMR relaxometry approaches. In particular, to mimic the situations occurring in nature, we studied sorption of water on humic acids from controlled humidities and monitored qualitative and quantitative aspects of water sorption. Crosslinking by formaldehyde induced a reduction in moisture sorption capacity, which was attributed to the separation of functional groups and a decrease in structural compactness. In addition, the crosslinked humic acids exhibited faster water uptake and approximately three-fold higher water holding capacity than pristine humic acids. In case of carbodiimide coupling (by using water-soluble N-Ethyl-N-(3-dimethylaminopropyl)carbodiimide (EDC)), the derivatives of humic acids contained only between 14–40 % of original free carboxylic groups. Despite that, they exceeded the moisture harvesting ability of parental humic acids around 10–14 % after their equilibration at 100% relative humidity. Although, they showed also more rigid structure, the EDC derivatives showed also faster swelling kinetics and reached almost the same water holding capacity as original sample after 18 days. However, carbodiimides derivatives began to degrade already after 3–9 days during swelling tests, which subsequently decreased their performance. The results suggest that water holding capacity, swelling kinetics and moisture harvesting ability of humic acids are not influenced exceptionally by the amount of free carboxylic groups or other polar functionalities, but also by their spatial arrangement and the distribution of pore sizes on the surface and inside the humic structure. The knowledge gained in this study is beneficial, among others, for the production of soil humic acids-based conditioners, i.e. remediation agents having required and simultaneously adjustable ability to bind and release water into the surrounding environment. Last, but not least, the presented findings improve the fundamental understanding the hydration processes in pristine and modified humic acids, which is beneficial to elucidate the hydration of complex natural systems, and of in particular of natural organic matter.
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Retence vody v huminových kyselinách
Cihlář, Zdeněk ; Šmejkalová, Daniela (oponent) ; Kučerík, Jiří (vedoucí práce)
Huminové kyseliny byly vyextrahovány z jihomoravského lignitu. Takto získaný neupravený vzorek huminových kyselin byl oxidován buď H2O2 nebo HNO3. Oxidované huminové kyseliny byly dále modifikovány pomocí formaldehydu za účelem vytvořit zesíťovanou strukturu, která by zvýšila retenci vody v těchto materiálech. Afinita a retence vody v připravených vzorcích byla studována pomocí termické analýzy (DSC – diferenční kompenzační kalorimetrie a TGA – termogravimetrické analýzy). Ke studiu zmíněných parametrů bylo využito dvou odlišných způsobů hydratace vzorků huminových kyselin. První přístup představoval sorpci vody na huminových kyselinách při třech kontrolovaných vzdušných vlhkostech, k jehož popisu bylo využito TGA. Druhý pohled byl založen na sorpci jednorázově přidaného nadbytečného množství vody, který byl charakterizován pomocí DSC. Výsledky získané z TGA vzorků huminových kyselin umístěných v prostředí s definovanou relativní vzdušnou vlhkostí naznačují zvyšující se sorpční schopnost s rostoucí relativní vzdušnou vlhkostí okolní atmosféry. Na základě hodnot získaných z DSC měření v hermeticky uzavřených vzorkovnicích lze poukázat na zvyšující se množství vody vázané strukturou huminových kyselin po dobu jednoho měsíce. Všechny upravené vzorky huminových kyselin (oxidované i oxidované a modifikované pomocí formaldehydu) vykazovaly vyšší retenci vody v porovnání s nemodifikovaným vzorkem.
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Hydrogels of Humic Acids
Cihlář, Zdeněk ; Lehocký,, Marián (oponent) ; Pospíšilová,, Lubica (oponent) ; Kučerík, Jiří (vedoucí práce)
Humic acids (HAs) are the main components of the soil organic matter. They are ubiquitous substances with complex chemical and physicochemical structure. In this study, several modifications of HAs were carried out in order to modify their properties. In the first part, the influence of lignite air oxidation on the yield and physicochemical character of regenerated humic acids were studied. In the second step, to stabilize the structure of lignite humic acids and improve the water holding capacity, we applied formaldehyde and carbodiimides crosslinking procedures leading to covalent coupling of humic acids moieties. The production of crosslinked structures was motivated by the attempt to design HAs-based systems resembling hydrogels, with the possibility to modify their reactivity and water retention. Samples were analyzed for their chemical composition and physicochemical properties using various techniques, among the most important were DSC and NMR relaxometry. The chemical composition was studied using FTIR and elemental analysis in order to assess the changes in comparison to pristine humic acids. The stabilities of derivatives were determined by using thermogravimetry. The most important parameter studied in this work was the change in hydration characteristics. For this reason, we developed and applied several new thermoanalytical and NMR relaxometry approaches. In particular, to mimic the situations occurring in nature, we studied sorption of water on humic acids from controlled humidities and monitored qualitative and quantitative aspects of water sorption. Crosslinking by formaldehyde induced a reduction in moisture sorption capacity, which was attributed to the separation of functional groups and a decrease in structural compactness. In addition, the crosslinked humic acids exhibited faster water uptake and approximately three-fold higher water holding capacity than pristine humic acids. In case of carbodiimide coupling (by using water-soluble N-Ethyl-N-(3-dimethylaminopropyl)carbodiimide (EDC)), the derivatives of humic acids contained only between 14–40 % of original free carboxylic groups. Despite that, they exceeded the moisture harvesting ability of parental humic acids around 10–14 % after their equilibration at 100% relative humidity. Although, they showed also more rigid structure, the EDC derivatives showed also faster swelling kinetics and reached almost the same water holding capacity as original sample after 18 days. However, carbodiimides derivatives began to degrade already after 3–9 days during swelling tests, which subsequently decreased their performance. The results suggest that water holding capacity, swelling kinetics and moisture harvesting ability of humic acids are not influenced exceptionally by the amount of free carboxylic groups or other polar functionalities, but also by their spatial arrangement and the distribution of pore sizes on the surface and inside the humic structure. The knowledge gained in this study is beneficial, among others, for the production of soil humic acids-based conditioners, i.e. remediation agents having required and simultaneously adjustable ability to bind and release water into the surrounding environment. Last, but not least, the presented findings improve the fundamental understanding the hydration processes in pristine and modified humic acids, which is beneficial to elucidate the hydration of complex natural systems, and of in particular of natural organic matter.
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Chemical and Physical Transformations of Humic Acids
Vlčková, Zoja ; Pospíšilová, Ľubica (oponent) ; Janoš,, Pavel (oponent) ; Pekař, Miloslav (vedoucí práce)
This work is a pilot study testing the relationships between biological properties and structure of humic acids extracted from original and modified South-Moravian lignite, mine Mír, Mikulčice. In first part of the work, methods suitable for increase of the humic acid yield were explored. Lignite oxidation in gas phase turned out to be relatively instrumentally demanding and insufficiently effective. Therefore, only oxidation in liquid phase was explored further along with modification with short-chained organic acids. Modification with short-chained organic acids was inspired by processes enhancing biological functions in rhizosphere, i.e. the root system produces exudates causing changes in the supramolecular structure of the surrounding organic matter, improving its mobility and cell-walls penetration. Primary structure of humic acids produced in this work was investigated by elemental analysis, solid state NMR, EPR and UV-VIS spectroscopy. Despite the fact that only minor differences were found, conducted assessment of biological activity and genotoxic potential showed that humic acids and their respective humates isolated from lignite with different pre-treatment show different bioactivity. Therefore, supramolecular structure of samples in diluted solutions was investigated by means of HPSEC, HRUS and densitometry measurements. Two counterions – potassium and ammonium – were tested. Obtained results confirm the assumption that observed quality of humates depends on counterion, concen-tration of humate and also on the method of lignite pre-treatment. Both selected pre-treatment methods showed potential to produce humic acids with variable biological properties, applicable in agriculture, environmental chemistry and potencially also in pharmacology.
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Study of Hydrophobic Domains in Humic Acids
Čechlovská, Hana ; Šimon, Peter (oponent) ; Franců, Juraj (oponent) ; Pekař, Miloslav (vedoucí práce)
The nature of hydrophobic domains in humic acids was studied from different points of view. To shed light on the meaning of fluorescent spectra, the measured samples underwent the sequential extraction which partially revealed the role of water-soluble components, free and bond lipids in optical properties of humic acids. The results indicated that the fluorescence peaks traditionally attributed to the superposition of individual chemical structures are rather a result of aggregation properties of humic molecules and hydrophobic effect driving aromatic molecules together forming aggregates apparently large molecular weight. Further, it seems that there is a significant influence of non-fluorophores and non-chromophores on the optical properties of humic acids. Results are consistent with the theory on supramolecular structure of humic acids. Next, the aggregation, conformational behaviour and thermodynamic stability of humic acids were studied by high resolution ultrasonic spectroscopy. It was demonstrated that humic molecules are able to interact and form aggregates at very low concentration (
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Retence vody v huminových kyselinách
Cihlář, Zdeněk ; Šmejkalová, Daniela (oponent) ; Kučerík, Jiří (vedoucí práce)
Huminové kyseliny byly vyextrahovány z jihomoravského lignitu. Takto získaný neupravený vzorek huminových kyselin byl oxidován buď H2O2 nebo HNO3. Oxidované huminové kyseliny byly dále modifikovány pomocí formaldehydu za účelem vytvořit zesíťovanou strukturu, která by zvýšila retenci vody v těchto materiálech. Afinita a retence vody v připravených vzorcích byla studována pomocí termické analýzy (DSC – diferenční kompenzační kalorimetrie a TGA – termogravimetrické analýzy). Ke studiu zmíněných parametrů bylo využito dvou odlišných způsobů hydratace vzorků huminových kyselin. První přístup představoval sorpci vody na huminových kyselinách při třech kontrolovaných vzdušných vlhkostech, k jehož popisu bylo využito TGA. Druhý pohled byl založen na sorpci jednorázově přidaného nadbytečného množství vody, který byl charakterizován pomocí DSC. Výsledky získané z TGA vzorků huminových kyselin umístěných v prostředí s definovanou relativní vzdušnou vlhkostí naznačují zvyšující se sorpční schopnost s rostoucí relativní vzdušnou vlhkostí okolní atmosféry. Na základě hodnot získaných z DSC měření v hermeticky uzavřených vzorkovnicích lze poukázat na zvyšující se množství vody vázané strukturou huminových kyselin po dobu jednoho měsíce. Všechny upravené vzorky huminových kyselin (oxidované i oxidované a modifikované pomocí formaldehydu) vykazovaly vyšší retenci vody v porovnání s nemodifikovaným vzorkem.
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