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The influence of humic acids methylation on the interaction of surface active agents
Bělušová, Anna ; Weidlich, Tomáš (referee) ; Smilek, Jiří (advisor)
The presented diploma thesis deals with the study of interactions between humic acids as the main component of soil organic matter with a model organic pollutant presented by cationic surfactant Septonex (which was expected to interact positively with humic acids due to its charge) through unconventional combination of dialysis and diffusion techniques realized in diffusion cells together with isothermal titration calorimetry capable of elucidating the nature of ongoing reactions from a thermodynamic point of view. The experiments were performed with a humic acid isolated by standard isolation procedure from Leonardite (1S104H) purchased from the International Society for Humic Substances, with humic acids isolated from lignite as well as modal chernozem. The aim of the submited diploma thesis is to assess the influence of carboxyl functional groups in the structure of humic acids to interactions with Septonex. For this reason, said samples of humic acids have been modified by selective methylation of their carboxyl functional groups, which can no longer participate in interactions with ionic substances. Results from diffusion cells and isothermal titration calorimetry confirmed the assumption that Septonex interacted with all types of unmodified humic acids more than with their methylated derivatives. Despite the available literature, it was surprising that the differences in the interaction of humic acids with Septonex were not diametrically different when comparing unmodified humic acids with their methylated derivatives. The extent of these interactions was assessed through the apparent equilibrium constant Kapp determined in the diffusion (dialysis) experiments and from the course of enthalpy curves from isothermal titration calorimetry. After the experiments and their evaluation, it can be concluded that humic acids and Septonex in their interactions, due to their structures, probably apply not only electrostatic interactions, especially through available carboxyl functional groups of humic acids and positively charged hydrophilic parts of Septonex molecules, but also a significant role have a hydrophobic effect, hydrogen bonds and Van der Waals forces.
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Viscosimetry of hyaluronan-amphiphile systems
Trojan, Martin ; Běťák, Jiří (referee) ; Chytil, Martin (advisor)
This bachelor thesis investigates the interaction between the polysaccharide sodium hyaluronate (HA) and some amphiphilic molecules. As amphiphilic molecules the aminoacids lysine and 6 – aminocaproic acids were chosen. The presence of the carboxylic group on HA and the aminogroup on the aminoacids suggests electrostatic interaction between these two compounds. This supposal offers the possibility to modificate HA and uses it as a new type of a carrier of bioactive compounds, for example medicals. The HA of two molecular weights (1.75MDa and 70kDa) were chosen for the study of the interactions with the aminoacids. Solutions of HA and stock solutions of the aminoacids were prepared for their mutual mixing in the various volume ratios. The solutions and the mixtures were measured in three types of environment: pure water, 0.15M solution of NaCl and in phosphate buffer (PBS) of pH 6. The interactions were investigated by means of reometry. Our results show, the presence of interactions between HA and the aminoacids mainly in the system consisting the 1.75 MDa HA and lysine in water. As a result of the interactions, a decrease in the viscosity of the mixtures comparing to the HA solutions was observed.
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SEC-MALLS study on hyaluronan-albumin interactions
Sereda, Alena ; Kalina, Michal (referee) ; Chytil, Martin (advisor)
This work is focused on interactions of hyaluronan (HA) and bovine serum albumin (BSA). These interactions were studied by SEC-MALLS method, where molar mass, root mean square (rms) radii, hydronamic radius and intrinsic viscosity of particles of the system were defined. Additionally, interactions were examined by measurement of DLS and zeta potential, where hydrodynamic radius and a value of the zeta potential were defined. The interactions were confirmed at any of the used media, but with different efficiency. Furthermore it was found out, that the high ionic strength minimizes the range of the interactions, magnifies the radii of the complexes, their intrinsic viscosity and zeta potential. It was proved that complexes become smaller in their radii and viscosity with growing BSA concentraton.
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Preparation and characterization of hydrogels based on cationic biopolymer
Tesařová, Barbora ; Mravec, Filip (referee) ; Smilek, Jiří (advisor)
Presented thesis deals with the preparation and characterization of hydrogels based on positively-charged biopolymer and negatively-charged tenside. As an appropriate representative of positively-charged polymer was chosen chitosan, because of his biocompatibility and biodegrability, and N,N,N-trimethylchitosan, which was synthetised from chitosan in this diploma thesis. The final product of synthesis was characterised by SEC-MALS, elemental analysis, infrared spectroscopy and nuclear magnetic rezonation. Interactions between these polymers and representatives of negatively-charged tensides, which are sodium dodecylsuphate and sodium tetradecylsulphate, were investigated. The main method used in this thesis was rheology, through it were investigated prepared hydrogels based on chitosan and tensides and also prepared microgels based on N,N,N-trimethylchitosan and tensides. The interactions between polymers and tensides have been proved.
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Hydrogels of Humic Acids
Cihlář, Zdeněk ; Lehocký,, Marián (referee) ; Pospíšilová,, Lubica (referee) ; Kučerík, Jiří (advisor)
Huminové kyseliny představují hlavní součást půdní organické hmoty. Jedná se o všudypřítomné sloučeniny s komplexní chemickou a fyzikálně-chemickou strukturou. Předkládaná práce shrnuje několik způsobů modifikací huminových kyselin provedených za účelem úpravy jejich vlastností. V první části byl studován vliv vzdušné oxidace lignitu na velikost výtěžku a fyzikálně-chemický charakter produkovaných regenerovaných huminových kyselin. Druhý krok představoval snahu stabilizovat strukturu lignitických huminových kyselin a zlepšit zádrž vody. Bylo provedeno síťování pomocí formaldehydu a karbodiimidů, které předpokládá vznik nových kovalentních vazeb v různých částech struktury huminových kyselin. Produkce zesíťované struktury byla motivována snahou vytvořit systémy podobné hydrogelům, založené na huminových látkách s možností úpravy jejich reaktivity a retence vody. Chemické složení a fyzikálně-chemické vlastnosti připravených vzorků byly studovány různými metodami, mezi nejdůležitější patří DSC a NMR relaxometrie. Chemické složení bylo studováno pomocí FTIR a elementární analýzy za účelem posoudit a porovnat změny s původním neupraveným vzorkem. Stability vzorků byly stanoveny pomocí termogravimetrie. Nejdůležitějším sledovaným parametrem této práce byla změna hydratačních charakteristik. K jejich studiu jsme vyvinuli a aplikovali několik nových termoanalytických a NMR relaxometrických přístupů. Ve snaze napodobit přírodní procesy byla studována sorpce vody huminovými kyselinami z prostředí s kontrolovanou vzdušnou vlhkostí. Byly pozorovány kvalitativní a kvantitativní hlediska sorpce vody. Zesíťování za použití formaldehydu způsobilo snížení sorpční kapacity vlhkosti. Tato změna je připisována separaci funkčních skupin a menší strukturní kompaktnosti. Zesíťované huminové kyseliny dále vykazovaly rychlejší příjem vody a přibližně třikrát větší kapacitu zádrže vody než původní huminové kyseliny. V případě použití karbodiimidu (ve vodě rozpustného N-Ethyl-N-(3-dimethylaminopropyl)karbodiimidu (EDC)) obsahovaly výsledné produkty 14–40 % původních karboxylových skupin. I přesto tyto látky překonaly schopnost sorpce vlhkosti původního nemodifikovaného vzorku o 10–14 % po kondiciaci v prostřední se 100% relativní vzdušnou vlhkostí. Navzdory rigidnější struktuře vykazovaly EDC deriváty rychlejší bobtnání a dosáhly téměř stejné kapacity zádrže vody po 18 dnech jako původní vzorek. Vzorky modifikované karbodiimidy vykazovaly známky degradace již po 3–9 dnech což částečně snižuje jejich využitelnost. Získané výsledky naznačují, že kapacita zádrže vody, kinetika bobtnání a schopnost sorpce vlhkosti huminových kyselin nejsou výhradně určeny koncentrací karboxylových skupin, nebo dalších polárních fragmentů, ale také jejich vzájemným rozmístěním a distribucí velikosti pórů na povrchu a také uvnitř struktury. Získané poznatky této studie mohou sloužit například k produkci půdních kondicionérů založených na huminových kyselinách, tj. remediačních preparátů s požadovanými, ale především nastavitelnými schopnostmi poutat a následně uvolňovat vodu do okolního prostředí. V neposlední řadě přispějí uvedené závěry ke zkvalitnění základního porozumění procesu hydratace v modifikovaných a původní vzorcích, což je přínosné ve vztahu k objasnění hydratace komplexních přírodních systémů a to zejména přírodní organické hmoty.
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Study on interactions of protonated aminoacids with low-molecular weight hyaluronan
Chlumská, Jana ; Kalina, Michal (referee) ; Chytil, Martin (advisor)
This bachelor thesis deals with interactions between hyaluronic acid (HA) of low molecular weight (110-130 kDa) and protonated aminoacids lysine and 6-aminocaproic acid. For investigation of these interactions, methods such as pH-metry, conductance measurement, viscometry and dynamic light scattering were used. The electrostacic interactions between carboxylic group of HA and the aminogroup of the aminoacids are presumed. Proving these interactions would allow us to physically modify HA and further more, using such a system as a carrier of pharmaceuticals. The interactions of protonated lysine with HA were studied in pure water or in the solution of NaCl (c = 15 mmol•dm-3). Interactions of 6-aminocaproic acid were studied only in pure water. Both aminoacids were in the concentration range 0.9-20 mmol•dm-3. The decrease in the viscosity of the solutions indicates the interactions for lysine; for 6-aminocaproic acid the interactions also occured, but not as signifciantly as for the system containing lysine.
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Water retention capacity of humic substances
Cihlář, Zdeněk ; Šmejkalová, Daniela (referee) ; Kučerík, Jiří (advisor)
Humic acids were extracted from South Moravian lignit. That humic sample was oxidized by either H2O2 or HNO3. In next step, oxidized humic acids were polymerized by formaldehyde in order to obtain cross-linked structures with improved water retention capacity. Affinity to water and water retention capacity of obtained products were studied by thermal analysis (DSC – differential scanning calorimetry and TGA – thermogravimetric analysis). In order to study above-mentioned parameters two different methods were used. First approach represented sorption of water to humic acids from three controlled humidities, for description of those processes TGA measurement was used. Second study was based on the DSC monitoring of water excess sorption. Results obtained from TGA measurements showed an increasing sorption ability with increasing relative humidity of the environment. DSC measurerents in hermetically sealed containers resulted in an increasing content of water bound by humic acids structures. All the modified samples of humic acids (oxidized as well as oxidized and modified by formaldehyde) gave higher retention capacity in comparion with the parental humic sample.
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New methods of protonated aminoacids preparation and their interactions with polyelectrolytes
Trojan, Martin ; Sedlařík,, Vladimír (referee) ; Chytil, Martin (advisor)
This Master thesis investigates the interaction between the polysaccharide sodium hyaluronate (HA) and some amphiphilic molecules. It is known that the presence of the carboxylic group on HA and the aminogroup on the amphiphiles leads to electrostatic interaction between these two compounds. This supposal offers the possibility to physically modify HA and use it as a new type of a carrier of bioactive compounds, for example medicals. However, successful carrier of bioactive compound has to resist a certain value of ionic strength. The high-molecular weights HA (1.75MDa) and amphiphile lysine were chosen for the study of the influence of ionic strength on the system HA – amphiphile. Our results show that system HA – amphiphile system is suppressed even by low concentrate solution of electrolyte. Therefore the system was reinforced by protonation of the aminoacid. The results show, that the interactions were reinforced, nevertheless negative influence of chlorine anions had to be eliminated by lyophilization. The solutions with strengthened system HA – amphiphile were used for the research of ionic strength influence. The amphiphiles lysine, 6 - aminocaproic acid and arginine were selected for this study. The interactions were investigated by means of reometry and conductometry.
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Interaction between surfactants and hyaluronan with different molecular weight.
Vašíčková, Kamila ; Lehocký,, Marián (referee) ; Pekař, Miloslav (advisor)
The behavior of the system consisted by mixture of two different molecular weight hyaluronates and surfactant was investigated. Mixtures were 17 kDa hyaluronate with 1,46 MDa, 73 kDa with 1,46 MDa, 300 kDa with 1,46 MDa, 806 kDa with 1,46 MDa and 1800 kDa with 1,46 MDa. These compounds were always mixed in the weight ratios 70:30, 50:50 and 30:70. As the surfactant cetrimonium bromide and TWEEN 20 were used. Interactions were studied in aqueous solution with different ionic strength. Sudan red was used as hydrophobic dye. In all experimental series with cetrimonium bromide was observed phenomenon of discontinuous separated phases, described as pearls. Samples containing pearls were tested on stability, were dried and rehydrated back, as were also heated in solution. Subsequently, the particle size was measured in the remaining sample after pearls were filtrated. Mixtures of hyaluronate were characterized by measuring the viscosity using rheology microrheology. It was found that these compounds are heterogeneous and each sample point is not the same viscosity.
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Study of hyaluronan-albumin systems using light scattering methods and calorimetry
Sereda, Alena ; Hermannová, Martina (referee) ; Chytil, Martin (advisor)
This thesis, which is a continuation of the previous Bachelor thesis, is dedicated to the study of polyelectrolyte complexes between hyaluronan (HA) and bovine serum albumin (BSA). Interactions between HA and BSA and a formation of complexes were studied by SEC-MALLS method, where a molar mass, a root mean square (rms) radius, a hydronamic radius and an intrinsic viscosity of particles of the system were defined. Furthermore the interactions were studied by calorimetric measurement ITC, where thermodynamic character of complex formation was determined. Additionally, dynamic and electrophoretic light scattering methods (DLS and ELS) were applied, where hydrodynamic radius and a value of the zeta potential were defined. Also the effect of higher temperature on the character and complex formation was examined by SEC-MALLS and ITC measurements. The interactions were confirmed at any of the used media, but with different efficiency. It was also proved that complexes become smaller in their radii and viscosity with growing BSA concentration. Furthermore it was proved, that the high ionic strength hinders surface charges of HA and BSA molecules and minimizes their mutual interactions. At the higher ionic strength the radii of the complexes, their intrinsic viscosity and zeta potential are increased. The higher temperature has only minimal effect on the formation of the complexes.
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