Bonding is an emotional and biological process that creates a bond between a mother and her child and is among others important for easier breastfeeding, faster recovery of the mother etc. It is important to support it by an early contact between the mother and her newborn child. The diploma thesis aims to compare the discourse regarding mother-infant bonding and its support in our country around the year of 1980, when the rooming-in system appears, up to the present, with the milestone between 1998 and 2000, when the Centre of Active Birth was established as a result of changes in birth care that occurred then and which started to offer a different kind of care from the model that was known and used in the Czech Republic at that time. Emphasis will be put on the development of the discourse, changes in birth and after-birth care it has brought and changes of its participants and the role which women have as receivers of care. The theoretic part introduces the relatively little-known term 'bonding' and its support from the biological and social points of view, then discourse analysis will be applied in the methodological and experimental parts of the thesis. Analysed materials included media communication both in printed and electronic forms available at each analysed period. Keywords:...

Transient Liquid phase bonding (TLP) has evolved as a viable method of joining difficult-to-weld superalloys with potential of producing joints with comparable mechanical properties to the base material. Although the high temperature properties of aerospace superalloys have been studied extensively, there is little information on the corrosion behaviour of these special class of materials that had been subjected to TLP bonding. In this work, electrochemical assessment of the corrosion behaviour of TLP bonded nickel-based superalloy was performed. Microstructural evaluation of the TLP bonded joint revealed the presence of a centreline eutectic when isothermal solidification was not completed and the corrosion resistance increased with a decrease in this eutectic width. The use of a composite interlayer produces TLP joints with smaller eutectic size and results in complete isothermal solidification in shorter processing time. Complete isothermal solidification, achieved with the composite interlayer, results in a uniform chromium distribution in the joint centre and produced a corrosion performance similar to the as-received cast base metal. It was found that aside from the mere presence of chromium, which is widely recognised as necessary for corrosion resistance, its uniform distribution within the joint region is imperative for achieving adequate corrosion resistance in TLP joints. / May 2016

The aim of this thesis was to increase understanding of how rumination, defined as the behaviours and thoughts that focus an individual’s attention on their depressive symptoms and on the implications of these symptoms (Nolen-Hoeksema, 1991), affects the relationship between postnatal depressive symptoms and maternal sensitivity. Study 1 examined the impact of self-reported maternal rumination on perceived maternal attunement and mood, and the role of perceived social support and infant temperament in this relationship in a community sample of mothers (N = 203). Rumination mediated the relationship between maternal depressive symptoms and maternal responsiveness when infant negative affect was low but not high. Contrary to predictions, rumination did not mediate the relationship between social support and maternal attunement. Study 2 incorporated a second assessment point approximately six months later with the same sample. Prospective analyses were undertaken to examine the directional relationship between rumination and maternal attunement in the context of depressive symptoms. Unexpectedly, analyses revealed that maternal bonding prospectively predicted rumination at six months, after controlling for rumination at baseline. The converse relationship was not significant. This was contrary to the thesis hypothesis that increased rumination would predict impaired attunement at six months. Partially consistent with the thesis hypotheses, the relationship between rumination and maternal attunement was moderated by depressive symptoms at baseline; such that mothers who were low in depressive symptoms and had lower bonding at baseline reported higher levels of rumination at 6 months. Study 3 also explored the directional relationships between maternal mood, rumination and maternal attunement at a state level in a daily diary study with a community sample of mothers (N = 94) with infants aged between 3 and 14 months. Consistent with the findings of study 2, state maternal bonding at Time 1 predicted both state maternal rumination and state maternal mood at Time 2, and state rumination at Time 2 mediated the relationship between state bonding at Time 1 and state mood at Time 2. In the final study, the causal relationships between an experimentally induced state of ruminative thinking and observed maternal behaviours in a mother-infant interaction task were examined in a sample of dysphoric and non-dysphoric mothers (N = 79) and their infants. The analyses examined change in mother-infant interaction quality from baseline to post rumination induction, and subsequent change following an infant stressor task. Findings revealed a significant reduction in maternal sensitivity and mother-infant dyadic synchrony in the rumination group, but not the control group. For maternal sensitivity, the effect of rumination was exacerbated following the stressor task. Contrary to predictions, this relationship was not moderated by dysphoric symptoms. The findings of this thesis indicate that ruminative thinking directly impairs observed maternal behaviours, but that perceived poorer maternal attunement also increases self-reported ruminative thinking. The significance of these findings for theoretical explanations of rumination in a postnatal context are considered, and the clinical implications for parenting programmes and interventions for both mothers in the community as well as those considered at risk are discussed.

published_or_final_version / Endodontics / Master / Master of Dental Surgery

Crystal structures of anhydrous pinacol, the hexagonal pinacol, pinacol monohydrate, and pinacol hexahydrate were studied. In all the structures crystal packing is unusual and complicated. The origin of the complexity may be the difficulty in filling space densely and while also satisfying the H-bonding requirements when the molecule has few internal degrees of freedom. Five 15-crown-5 complexes of M(NO3)2 (M = Cu, Zn, Mg, Co, Mn) were synthesized and characterized using X-ray diffraction and differential scanning calorimetry. The system is rich in polymorphs. Nine definite solid-state phases were identified. More phases probably exist in the solid state at temperatures slightly above the room temperature. Most phase transformations in this system take place in single crystals without the loss of crystallinity. The nine phases crystallize in five crystal structures. The crown ether ligands have very similar conformation in all the structures. The asymmetric units in all the structures are complicated and pseudosymmetric, which is the consequence of the presence of the packing problem. The origin of the packing problem that leads to the complicated phase behavior is the odd number of -CH2-O-CH2- units in the crown ether ligand.

Paddlewheel complexes are molecules in which two interacting metal atoms are bridged by four chelating ligands. This class of complexes has a large range of electronic variability while keeping a rigid geometric structure. This variability has led to their use as catalysts, strong reductants, anti-tumor agents, and electron transfer agents. This dissertation examines the effects of changing both the dimetal core and the surrounding ligands on the electronic structure properties of the paddlewheel complexes. Examination of Bi₂(O₂CCF₃)₄, a p-orbital dimetal paddlewheel complex, provided a way to probe the orbitals that are important in metal-ligand σ bonding. The b(1g) and b(2u) ligand orbitals of Bi₂(O₂CCF₃)₄ have no dimetal orbital counterpart, unlike the case of the more familiar d-orbital dimetal paddlewheel complexes such as Mo₂(O₂CCF₃)₄. This had the effect of destabilizing these ligand orbitals compared to d-orbital paddlewheel complexes. The ligand a1g orbital in Bi₂(O₂CCF₃)₄ was also destabilized due to nodal differences in the dimetal σ orbital. The unusual coincidence of Mo-Mo σ and π ionization bands is due to a greater amount of ligand character in the Mo-Mo σ orbital compared to its ditungsten analogue, which has separate ionization bands for the σ and π bonds. A series of p-substituted dimolybdenum tetrabenzoate complexes was synthesized and studied by photoelectron spectroscopy in order to further examine the delocalization of electron density from the metals to the ligands in these complexes. A 0.89 eV shift in the δ ionization band was observed from Mo₂(O₂CPh-p-OMe) ₄ and Mo₂(O₂CPh-p-CF₃)₄. Overlap effects are the major factor causing the shift in the δ bond ionization, as the calculated charges on the molybdenum and oxygen atoms did not vary significantly on change of substituent. Molybdenum and tungsten guanidinate paddlewheel complexes have promise as good reducing agents due to their extremely low ionization energies. The solubility of the complexes poses a problem for their widespread adoption for use as reducing agents. Alkyl substituents were added to the complexes to increase their solubility. W₂(TEhpp)₄ was observed to have the lowest ionization energy at 3.71 eV (vertical ionization) and 3.40 eV (onset ionization) of any molecule yet prepared.

The gaseous free radicals, alkaline-earth metal monoalkylamides, monoacetylides, monoformamidates and monopyrrolidates, consisting of a metal atom (Ca or Sr) bonded to a single ligand, were synthesized in a Broida oven. The electronic and vibrational structures of these molecules were studied by low-resolution laser spectroscopy techniques. These inorganic molecules are ionic, well represented by the structure M⁺L⁻ (M = Ca, Sr: L = ligand). Three electronic transitions were identified for the metal monoalkylamides and the metal monoformamidates. The formamidate anion bonds to the metal in a bidentate fashion through the oxygen and nitrogen atoms. Two electronic transitions were observed for the metal monopyrrolidates. The pyrrolide anion ring bonds to the metal to provide these "open-faced sandwich" type molecules with pseudo-C₅ᵥ symmetry. For the metal monoacetylide molecules, only one electronic transition (Ā²Π-Ẋ²Σ⁺) was observed. Several vibrational frequencies were determined for these inorganic molecules from the low-resolution spectra. The Ā²Π-Ẋ²Σ⁺ transition of the calcium monoacetylide molecule was rotationally analyzed at high-resolution using the filtered laser excitation spectoscopy technique. The rotational line positions were fitted to a ²Π-²Σ⁺ Hamiltonian to obtain several rotational constants. The calcium-carbon bond length in CaCCH was calculated for the ground (2.248 Å) and excited (2.200 Å) electronic states. The vibration-rotation spectra of the gaseous bismuth hydride and bismuth deuteride molecules were recorded, using a diode laser system. The 1-0 fundamental band and several hot bands with Δv-1 were rotationally analyzed. The rotational line positions were fitted first, to a Dunham energy expression and then to a ³Σ⁻ Hamiltonian, to obtain ground state rotational constants. The bismuth-hydrogen (deuterium) bond distance was calculated to be 1.809 Å (1.807 Å).

The bonding in a series of ligand-bridged metal dimer complexes has been characterized by He(I) and He(II) photoelectron spectroscopy and approximate molecular orbital calculations. Bridging ligands such as carbonyl, nitrosyl, methylene and pyrazolyl in the complexes [CpFe(NO)]₂, [Cp*Fe(NO)]₂, [CpRu(NO)]₂, [Cp*Co(CO)]₂, [CpFe(CO)₂]₂, [Cp*Fe(CO)₂]₂, [CpFe(CO)]₂-μCO-μCH₂, [Cp*Fe(CO)]₂-μCO-μCH₂, [CpFe(NO)]₂- μCh₂, [CpRu(NO)]₂-μCH₂, [CpCo(CO)]₂-μCH₂, [CpRh(CO)]₂-μCH₂, [Ir(pyrazolyl)(CO)₂]₂, [Ir(3-methylpyrazolyl)(CO)₂]₂ and [Ir(3,5-dimethylpyrazolyl)(CO)₂]₂ are investigated and their effects upon metal-metal interactions are surveyed. Due to the presence of two d⁷ or d⁸ late metal atoms per molecule, these complexes display many overlapping ionization bands in a narrow valence ionization region. Attention has been given to modelling the photoelectron single ionization with asymmetric and symmetric Gaussians. The overlapping ionizations are successfully represented in terms of the model bandshapes. Thermodynamic relationships between bond dissociation and photoelectron ionization energies are also investigated. With relationships of this type, trends in bond energies may be correlated with ionization energies. Ligand inductive and bonding effects as well as small changes in molecular geometry cause shifts in the metal-based ionizations, which aid chemical understanding and interpretation of the molecular orbital picture. By comparing a series of related metal dimers, the assignment of related ionizations in the photoelectron spectra becomes apparent. Changes in ligand π accepting ability and changes in metal and formal oxidation states are also probed. Addition information is provided by vibrational fine structure in Cp₂Os, [CpFe(NO)]₂, and [Cp*Co(CO)]₂ and spin-orbit splitting in Cp₂Os. The metal-ligand backbonding combinations are found to be the most stable interactions and are responsible for the stability of the metal dimers. Metal-metal interactions are found to be relatively unimportant. Ligands with stronger π accepting abilities allow for more stabilized supported metal dimer complexes.

Non-covalent interactions are of great importance in biology, chemistry, and material sciences. Although much information about different types of non-covalent interactions is available, incorporating them in a molecular design to generate a molecule that can undergo association to form a molecular assembly with bulk properties of interest is a challenge. To understand and harness intermolecular interactions, we have designed an indane 2,5-diketopiperazine (DKP) scaffold. Crystal engineering studies with this scaffold show that the molecules assemble into one dimensional tapes via reciprocal amide hydrogen bonds, tapes assemble into two dimensional sheets via arene-arene interactions, and sheets assemble into three dimensional solids via van der Waals contacts. A series of tetraalkoxy-substituted DKPs previously investigated exhibited liquid crystalline behavior. A new class of DKPs with one alkoxy substituent, rather than two, on each benzene ring has been synthesized. Thermochemical studies of the new DKPs by differential scanning calorimetry and polarized optical microscopy show that they are not liquid crystalline as expected. However, in the process of making the DKPs, conformationally constrained tyrosine analogues, (R)- and (S)-5-hydroxy-2-aminoindan- 2-carboxylic acids, were prepared by chromatographic separation of diastereomeric dipeptide derivatives formed from N-Boc-L-phenylalanine. Absolute configurations were assigned by X-ray crystallographic analysis. The series of tetraalkoxy-substituted DKPs showed a remarkable trend in freezing point. The freezing point for the series decreases with an increase in alkyl chain length. To understand the relationship between the crystal packing interactions and the freezing point trend, a study of the association of DKPs in solution by NMR was initiated. An Nmethylated 2,5-diketopiperazine was previously synthesized and studied by NMR using chloroform as solvent to obtain equilibrium constants for self association. Attempted multi-step syntheses of a more lipophilic N-3,7-dimethyloctyl 2,5-diketopiperazine, which was expected to have solubility in non-interfering solvents such as carbon disulfide, benzene, and carbon tetrachloride, failed. In response, a direct and concise method for accessing N-alkyl DKPs was developed, and an N-decyl 2,5-diketopiperazine was synthesized. X-ray crystallographic analysis of the N-decyl 2,5-diketopiperazine reveals formation of dimers via hydrogen bonding in the solid state.

No description available.