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Melting of a methylated CpG-containing DNA double helix
Bušková, Hana ; Římal, Václav (advisor) ; Hanyková, Lenka (referee)
The melting of a DNA double helix into two single strands is a crucial process for life on Earth. Previous experimental data on the self-complementary sequence CTTm5 CGAAG containing 5-methylcytosine suggests that the melting of an oligonucleotide might be a three-state, rather than two-state process. To assess this, 1 H NMR spectra were measured at varied concentrations of the oligonucleotide in temperatures between 274 and 366 K. Through analysis of the chemical shifts of aromatic hydrogens undergoing fast chemical exchange, we have determined that the most likely intermediate state between a double helix and a single stranded random coil is a structure consisting of two oligonucleotide molecules rather than a structured single strand.
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Microstructure, swelling and deformation behavior of methacrylate hydrogels with interpenetrating network structure
Sadakbayeva, Zhansaya ; Dušková - Smrčková, Miroslava (advisor) ; Hanyková, Lenka (referee) ; Kuta, Antonín (referee)
Title: Microstructure, swelling and deformation behavior of methacrylate hydrogels with interpenetrating network structure Author: Zhansaya Sadakbayeva Department: Department of Macromolecular Physics, Faculty of Mathematics and Physics, Charles University in Prague Supervisor: Ing. Miroslava Dušková-Smrčková, Dr., Institute of Macromolecular Chemistry, Czech Academy of Sciences Consultant: Prof. Ing. Karel Dušek, DrSc., Institute of Macromolecular Chemistry, Czech Academy of Sciences Abstract: This work is devoted to interpenetrating polymer network (IPN) hydrogels prepared by sequential processes of redox-initiated radical polymerization of the first network prepared from 2-hydroxyethyl methacrylate (HEMA), and UV- initiated radical polymerization of the second network prepared from 2-hydroxyethyl methacrylate (HEMA) or glycerol methacrylate (GMA). Microstructure, swelling and deformation responses of the IPN hydrogels and their constituent network hydrogels were tested by various techniques. The microstructure of the first poly(HEMA) network was found sensitive to polymerization conditions. A novel route for one-step synthesis of double-porous poly(HEMA) cryogel was proposed. The formation of the second poly(GMA) network in the environment of non-porous and macroporous poly(HEMA) parent networks was...
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Temperature-sensitive hydrogels
Šestáková, Eliška ; Hanyková, Lenka (advisor) ; Kouřilová, Hana (referee)
Hydrogely jsou měkké látky složené z polymerních sítí nabotnalých ve vodě. Některé z nich při změně teploty reagují skokovou změnou objemu. Tento fázový přechod je označován jako kolaps a odpovídá konformační změně, při které polymerní řetězce přechází z konformace klubka do konformace globule. Vlastnostmi se hydrogely podobají živým tkáním (chrupavkám, šlachám a sval·m), nejen proto jsou perspektivními materiály ohledně aplikací v biotechnologiích a farmacii. Tato práce se zabývá studiem kolapsu v hydrogelech tvořenými jednoduchými a dvojitými sítěmi (speciální případ dvou interpenetrujících polymerních sítí). Připravené vzorky (PNIPAAm, PNNDEAAm, PAMPS, PAAm a odpovídající dvojité sítě s PAAm jako druhou složkou) byly zkoumány pomocí botnacích, DSC a NMR experiment·. Botnací experimenty prokázaly, že dvojité sítě vykazují větší míru nabotnání a také vyšší kritickou teplotu než příslušné sítě jednoduché. Pomocí NMR a DSC experiment· byla určena entalpie kolapsu. Bylo zjištěno, že na signálech NMR se podílí jen část polymerních jednotek teplotně citlivého hydrogelu kv·li velké hustotě sesí'ování. 1
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Temperature-sensitive functional molecules
Spasovová, Monika ; Hanyková, Lenka (advisor) ; Starovoytova, Larisa (referee)
The object of our study is a phase separation of porphyrin derivative PNIPAm-TPP. This molecule combines the properties of temperature-responsive polymers with those of well- defined small organic molecules. It is one of the few small organic molecule which shows temperature responsive behavior. We studied its phase separation using high resolution NMR spectroscopy and optical microscope. We applied Flory-Huggins theory to experimental data gained from VT (variable temperature) experiments and we obtained a phase diagram with spinodal and binodal curve. We also obtained LCST (lower critical solution temperature) of the solution and its critical concentration.
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Stimuli Responsive Multicomponent Polymer Systems
Šťastná, Julie ; Hanyková, Lenka (advisor) ; Dušková - Smrčková, Miroslava (referee) ; Labuta, Jan (referee)
Title: Stimuli Responsive Multicomponent Polymer Systems Author: Julie Šťastná Department: Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics Supervisor: doc. RNDr. Lenka Hanyková, Dr., Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics Abstract: Combination of 1 H NMR spectroscopy, differential scanning calorime- try (DSC), dynamic mechanical measurement, and optical microscopy was used to investigate temperature-induced phase transition of three types of systems: i) in D2O solutions of poly(N-isopropylmethacrylamide-co-acrylamide) (P(NIPMAm/- AAm)) random copolymers and in interpenetrating networks ii) poly(N-isopropyl- methacrylamide/poly(N-isopropylacrylamide) (PNIPMAm/PNIPAm), and iii) po- ly(vinylcaprolactam)/poly(N-isopropylacrylamide) (PVCL/PNIPAm). In all sys- tems influence of composition of the system on the phase transition was studied. For i) both the NMR and DSC data showed dependence on the acrylamide (AAm) content in the copolymer. NMR data was used to construct van't Hoff plots and changes of the enthalpy ∆H and entropy ∆S were studied. As it follows from comparison of ∆H values for NMR and DSC the size of the domains undergoing the transition as a whole decreases with increasing AAm...
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Spektroskopické a teoretické studium supramolekulárních komplexů symetrických porfyrinů s chirálními guesty
Březina, Václav ; Hanyková, Lenka (advisor) ; Šoltésová, Mária (referee)
Certain types of porphyrins can be used as achiral agent for determination of enantiomeric excess (ee) of chiral molecules. Particular organic chiral molecule (guest) and porphyrin (host) form host-guest complex while inducing nonequiv- alency of particular proton resonances in symmetrical host. It causes splitting of NMR signals linearly dependent on ee of guest. In this work we investigated com- plexation of di-brombenzylated oxoporphyrin with chiral camphorsulfonic acid. NMR titration revealed that they form complex with 1:1 stoichiometry with as- sociation constant K ≈ 5 × 104 l/mol. We confirmed linear dependence of split- ting of host β-protons on ee of guest. Low temperature measurements revealed two conformations of host-guest complex with population around 0.7:0.3 (at −60 ◦ C). DFT quantum mechanical computations at BLYP/3-21G* level revealed also two conformations with population 0.79:0.21. NMR shifts were computed on this geometries with method GIAO/PBE1PBE/6-31G(2df,2pd) and compared to experimental values. 1
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Self-Assembly in Mixture of Surfactants and Stimuli-Responsive Polymers with Complex Architecture
Bogomolova, Anna ; Filippov, Sergej (advisor) ; Štěpánek, Miroslav (referee) ; Hanyková, Lenka (referee)
Title: Self-assembly in mixture of surfactants and stimuli-responsive polymers with complex architecture Author: Anna Bogomolova Department: Physical and Macromolecular Chemistry Supervisor: PhD. Sergey K. Filippov, IMC AS CR, v.v.i. Supervisor's e-mail address: filippov@imc.cas.cz Abstract: The issue of construction of complex multi-block copolymers is currently one of the most researched areas. It became a logic consequence of the continuous development in polymer chemistry. Nowadays, a great interest is attracted to multi- responsive block copolymers. As a rule, they consist of hydrophilic, hydrophobic and responsive blocks. That responsive block can be either thermo-sensitive or pH-sensitive as well as sensitive to some other external stimuli. In the present work, we will try to cover topic of stimuli-responsive block copolymers and their interactions with different types of surfactants. Understanding of polymer/surfactant interactions can be a crucial step for future modeling of drug/polymer or protein(DNA)/surfactant interactions. There is a great interest in the investigation of polymer-surfactant interactions. However, while the homopolymer-surfactant interactions are characterized well enough, the same interactions for block copolymers are poorly described. The main development in the latter topic...
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Study of dynamical behaviour of H2O/D2O mixtures by NMR relaxation
Dvořák, Petr ; Lang, Jan (advisor) ; Hanyková, Lenka (referee)
Title: Study of dynamical behavior of H2O/D2O mixtures by NMR relaxation Author: Petr Dvořák Department: Department of Low Temperature Physics Supervisor: doc. RNDr. Jan Lang, Ph.D., Department of Low Temperature Physics Abstract: The subject of this diploma thesis is the chemical exchange in the mixture of light and heavy water, which was studied by methods of high resolution NMR. The first part of this thesis concerns methodology of sample preparation and methodology of measurement of relaxation times of mixture of light and heavy wa- ter. Experimental complications with elution of ions from tube glass, degassing of samples, radiation damping and sample heating by radio-frequency pulses were solved there. In the second part of this thesis the relaxation parameters of chemical exchange of selected sample at various temperatures were measured. Interpretations of experimental data (ionization, molecular clusters and isotopic equilibrium) was suggested. Keywords: NMR, relaxation, water, dynamics, chemical exchange
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Study of temperature-induced phase separation in copolymer solutions
Šťastná, Julie ; Hanyková, Lenka (advisor)
Title: Study of temperature-induced phase separation in copolymer solutions Author: Julie Brüllová Department: Department of Macromolecular Physics Supervisor: RNDr.Lenka Hanyková, Dr. Supervisor's e-mail address: hanykova@kmf.troja.mff.cuni.cz Abstract: The temperature-induced phase transition of poly(acrylamide/N-isopropylmethacryl- amide) random copolymers in D2O solutions and in mixtures of D2O/ethanol and D2O/aceton is studied in this work. This phenomenon is on the molecular level analogous with a phase transition (collapse) in hydrogels. Nuclear magnetic resonance (NMR) spectroscopy was used for the study. Results showed that with increasing content of acrylamide in the copolymer the transition tempe- rature is shifted to higher values, the transition is more gradual and smaller fraction of copolymer is phase separated. The same behaviour was found for higher content of ethanol or acetone in the solvent. If this content and the content of acrylamide is very high, the phase transition in dependence on the composition of solvent appears. The relaxation experiments showed that after the phase separation a part of solvent molecules remains bound to globular structures and its mobility is rescticted. Keywords: temperature induced phase separation, poly(acrylamide/N-isopropylmethacrylamide) random...
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The Study of Dynamic Behaviour and Interactions During the Temperature-Induced Phase Separation in Polymer Solutions
Kouřilová, Hana ; Hanyková, Lenka (advisor) ; Štěpánková, Helena (referee) ; Dušková - Smrčková, Miroslava (referee)
Title: The Study of Dynamic Behaviour and Interactions During the Tempera- ture-Induced Phase Separation in Polymer Solutions Author: Hana Kouřilová Department / Institute: Charles University in Prague, Faculty of Mathemat- ics and Physics, Department of Macromolecular Physics Supervisor of the doctoral thesis: doc. RNDr. Lenka Hanyková, Dr. Abstract: 1 H and 13 C high-resolution NMR spectroscopies were used for the phase separation investigation in three types of polymer solutions: i) poly(N -isopropylmethacrylamide)/D2O/ethanol with or without negatively charged comonomer sodium methacrylate, ii) random copolymers poly(N -isopro- pylmethacrylamide-co-acrylamide) in D2O, D2O/ethanol and D2O/acetone and iii) D2O solutions of polymer mixtures poly(N -isopropylmethacrylamide)/poly(N - vinylcaprolactam). For i) cononsolvency effect and influence of temperature on the phase separation was studied. Differences between mesoglobules formed as a consequence of cononsolvency effect and of temperature were found. While inside the cononsolvency-induced mesoglobules no bound ethanol molecules were detect- ed, in the mesoglobules formed by the effect of temperature ethanol molecules were present. The charge introduced into the polymer chains strenghtens polymer- solvent interactions. For ii) mesoglobules were found to be...
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