The aim of this diploma thesis is to prove that augmentative and diminutive suffixes are not always just bearers of senses "big" / "of big size", in the case of augmentative suffixes, and "small" / "of small size", in the case of diminutive suffixes, and that they can also be accompanied by various connotations. The thesis is divided into several parts. The first part is concentrated on the topic of the morpheme in Portuguese in general. The next two parts are dedicated to particular augmentative and diminutive suffixes, concretely to their origin and especially to their specifics. Fundamental is the last part which focuses on the systematization of the senses of suffixes mentioned in previous chapters. Key words: word-formation, derivation, suffixes, augmentative suffixes, diminutive suffixes, connotation

(in English) The aim of the diploma thesis is to reveal the particularities in the derivation of hypocorisms from names of foreign origin in Czech and in Russian on websites, related to films, TV-series and fanfiction. The first part of the diploma thesis is dedicated to the theoretical questions such as the difference in the semantics of hypocorisms and official personal names, the methods of derivation, typical for hypocorisms in Czech and in Russian and their usage. In the second part, the derivation of hypocorisms from names of foreign origin in Czech and in Russian on websites, related to films, TV-series and fanfiction is revealed.

This thesis studies grammar systems whose components use sequences of productions whose left-hand sides are formed by nonterminal strings, not just single nonterminals. It introduces three restrictions on the derivations in these grammar systems. The first restriction requires that all rewritten symbols occur within the first l symbols of the first continuous block of nonterminals in the sentential form during every derivation step. The second restriction defines derivations over sentential forms containing no more than m continuous blocks of nonterminals. The third restriction extends the second in the way that each sequence of nonterminals must be of length h or less. As its main result, the thesis demonstrates that two of these restrictions decrease the generative power of grammar systems.

This work introduces and discusses generalized scattered context grammars that are based upon sequences of productions whose left-hand sides are formed by nonterminal strings, not just single nonterminals. It places two restrictions on the derivations in these grammars. More specifically, let k be a constant. The first restriction requires that rewriting all symbols occurs within the first k symbols of the first continuous block of nonterminals in the sentential form during every derivation step. The other restriction defines the derivations over sentential forms containing no more than k occurrences of nonterminals. As its main result, the thesis demonstrates that both restrictions decrease the generative power of these grammars to the power of context-free grammars.

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A full understanding of chemical reaction dynamics at the gas/organic-surface interface requires knowledge of energy-transfer processes that happen during the initial gas/surface collision. We have examined the influence of mass and rovibrational motion on the energy-transfer dynamics of gas-phase species scattering from model organic surfaces using theory and experiment. Molecular-beam scattering techniques were used to investigate the rare gases, Ne, Ar, Kr, and Xe, and the diatomics, N₂ and CO, in collisions with CH₃- and CF₃-terminated self-assembled monolayer (SAM) surfaces. Complementary molecular-dynamics simulations were employed to gain an atomistic view of the collisions and elucidate mechanistic details not observable with our current experimental apparatus. We developed a systematic approach for obtaining highly accurate analytic intermolecular potential-energy surfaces, derived from high-quality ab initio data, for use in our classical-trajectory simulations. Results of rare gas scattering experiments and simulations indicate mass to be the determining factor in the energy-transfer dynamics, while other aspects of the potential-energy surface play only a minor role. Additionally, electronic-structure calculations were used to correlate features of the potential-energy surface with the energy-transfer behavior of atoms and small molecules scattering from polar and non-polar SAM surfaces. Collisions of diatomic molecules with SAMs are seen to be vibrationally adiabatic, however translational energy transfer to and from rotational modes of the gas species, while relatively weak, is readily apparent. Examination of the alignment and orientation of the final rotational angular momentum of the gas species reveals that the collisions induce a stereodynamic preference for the expected "cartwheel" motion, as well as a surprising propensity for "corkscrew" or "propeller" motion. The calculated stereodynamic trends suggest that the CH₃-SAM is effectively more corrugated than the CF₃-SAM. Finally, the feasibility for collisional-energy promoted, direct gas/organic-surface reactions was interrogated using the 1,3-dipolar azide-alkyne cycloaddition reaction. We found that geometrical constraints prevented the reaction from proceeding at the probed conditions. / Ph. D.

Comprehension of reactive chemical dynamics in the gas phase and at the gas/organic-surface interface and non-reactive dynamics at the interface between hydrophobic surfaces and water requires an understanding of the fundamental atomic and molecular interactions that undergird these important phenomena. In an effort to study these regimes of chemical interaction, we have performed computational simulations that probe the dynamics of chemical systems that exemplify each of these domains. To study gas-phase chemical dynamics, we reparametrized semiempirical Hamiltonians so that they can accurately describe the potential energy surfaces for two distinct atom+alkane reactions. In addition to their demonstrated accuracy, these methods possess the attractive quality of being computationally inexpensive enough to afford extensive direct-dynamics trajectory studies. Our results on the dynamics of atom+alkane hydrogen-abstraction reactions have shown good agreement with experimental metrics that are as diverse as product velocity distributions, excitation functions, angular distributions and rovibrational state distributions for diatomic products of the abstraction. We have demonstrated that our reparametrized Hamiltonians are suitable for investigating gas-phase reactions with up to 15 (5 heavy) atoms and that they are appropriate for studying reactions beyond the gas phase, especially gas/surface reactions. By employing our semiempirical methods within a quantum-mechanics/molecular-mechanics hybrid scheme we are able to examine hydrogen-abstraction reactions of fluorine atoms with alkanethiolate self-assembled monolayers. Our simulations reproduce the general trends of experimental results for the cousin F+squalane reaction. Our simulations also probe the role that secondary collisions play in determining the final internal and translational energy of the product HF molecules. For instance, we determined that very few interactions with the SAM surface were required to cool rotational and translational modes of the HF product, while its vibrational energy remains unchanged on the time scale that HF molecules trap on the SAM surface. Moving beyond the gas/organic surface interface, we have also performed molecular-dynamics simulations of thin water films confined between hydrophobic SAM surfaces. These simulations illuminated the structural and dynamics behavior induced in the water films by confinement in hydrophobic environments. While most effects of the surface do not penetrate deep into the water layers we have noted that enhanced lateral diffusion of water molecules can persist in these films with > 1 nm length scales. We have elucidated a possible mechanistic precursor for the attractive forces seen in experimental measurement of the hydrophobic effect. / Ph. D.

1 Summary The thesis entitled Diminutives and Augmentatives in Contemporary Romanian Language and their Stylistic Use is focused on determining a classification which could describe every stylistic function of expressive words. The method I chose was to analyze three stylistic areas, create lists of expressive words with context and evaluate the results. From the beginning, it was evident that there were many connections between diminutives, augmentatives on one part and pejoratives on the other. That is a reason why I extended this thesis to cover also pejorative words. Firstly, I would like to describe the structure of this study. I decided to divide it into two parts. The first one is theoretical (1.0), and its aim is to synthesize information about suffix derivation and about diminutives, augmentatives and pejoratives in the Romanian language. In different linguistic studies, we find different classifications of observed suffixes and also their different quantities. Having reviewed these linguistic studies, I chose one which I found the best organized and, based on my own analysis, I also added some observations regarding the theory (2.4.5). Basically, there are two more suffixes which should be classified as diminutive (-ež, -uşă) and two as augmentative (-ime, - andru). Next theoretical topic to...

A determinação do excesso enantiomérico (ee) em compostos quirais por ressonância magnética nuclear (RMN) foi descoberta há mais de meio século por Raban e Mislow e permanece bastante atual e importante. Uma das formas de quantificar o ee consiste em formar diastereoisômeros através de agentes quirais de derivação (AQD). AQDs com a função aldeído tem sido amplamente usados na discriminação de aminas quirais devido a fácil formação de iminas em condições brandas. Existe uma preferência pelo uso de aldeídos cíclicos como AQD, uma vez que sua menor flexibilidade conformacional favorece a diferenciação dos derivados diastereoisoméricos. Até o momento, não havia estudos de AQD utilizando compostos acíclicos. Desta forma, o objetivo desse trabalho foi utilizar o terpeno acíclico (S)-citronelal como AQD para a determinação do excesso enantiomérico de aminas primárias, através da RMN de 1H e 13C. Inicialmente, nós conseguimos observar uma preferência por conformações dobradas do (S)-citronelal por NOE e pela comparação entre os deslocamentos químicos teóricos, obtidos a partir da otimização com a correção de dispersão D3, e experimentais de RMN de 1H. Em seguida, nossos resultados sugeriram que a causa do dobramento molecular do citronelal estaria baseada em interações de London e HOMO-LUMO. Após a análise conformacional do (S)-citronelal, nós reagimos este composto dentro do tubo de RMN (\"mix and shake\") com misturas racêmica e escalêmicas das aminas sec-butilamina, 1-(fenil)etanamina e anfetamina, do amino-álcool 2-aminobutan-1-ol e dos amino-ácidos metionina e fenilalanina. Em todos os casos foi possivel fazer a determinação do ee e da configuração absoluta com grande eficácia. Os resultados mostraram que a metila ligada ao centro estereogênico do (S)-citronelal é um sinal conveniente para se determinar o ee de aminas quirais por ser facilmente reconhecido no espectro, uma vez que esse sinal já faz parte do agente quiral de derivação e também por estar em uma região bastante blindada do espectro tanto no RMN de 1H como no de 13C. Com isso, a completa e minuciosa elucidação estrutural torna-se desnecessária. Posteriormente, as conformações das iminas formadas mostraram, através de estudos teórico e experimental (NOE), um dobramento molecular semelhante ao encontrado no citronelal. O motivo para esse efeito também se encontra nas interações de London e nas interações de orbitais moleculares adequadas. / The determination of enantiomeric excess (ee) in chiral compounds by nuclear magnetic resonance (NMR) was discovered more than half a century ago by Raban and Mislow and remains quite current and important. One of the ways of quantify the ee is to form diastereoisomers via chiral derivatizing agents (CDA). CDA with the aldehyde function has been widely used in discriminating chiral amines because of easy formation of the imines under mild conditions. There is a preference for the use of cyclic aldehydes as CDA since their lower conformational flexibility favors the differentiation of the diastereoisomeric derivatives. As far as we are aware, there were no studies of CDA using acylic compounds. Thus, the goal of this work was to use acylic terpene (S)-citronellal as CDA for the determination of the ee of primary amines, through 1H and 13C NMR. Initially, we observed the preference for a folded conformations of the (S)-citronellal by NOE and by comparing the theoretical chemical shifts obtained from the optimization with the D3 dispersion correction, and experimental 1H NMR. Next, our results suggested that the cause of the citronelal molecular folding could be attributed to London and HOMO-LUMO interactions. After the conformational analysis of the (S)-citronellal, we reacted this compound within the NMR tube (\"mix and shake\") with racemic and scalemic mixtures of the sec-butylamine, 1-(phenyl) ethanamine, amphetamine, 2-aminobutan-1-ol, methionine and phenylalanine. In all cases, it was possible to make the determination of the ee and absolute configuration with great effectiveness. The results showed that methyl group attached to the stereogenic center of the (S)-citronelal is a convenient signal to determine the ee of chiral amines, because it is easily recognized in the spectrum, since that signal is already part of the CDA and also for being in a fairly shielded region of the spectrum in both 1H and 13C NMR. With this, complete and rigorous structural elucidation becomes unnecessary. Subsequently, the conformations of the imines formed showed, by theoretical and experimental (NOE) studies, the same molecular folding similar to that found in citronellal. The reason for this effect is also found in the interactions of London and in the interactions of suitable molecular orbitals.

Este trabalho tem um caráter multidisciplinar; faz parte de uma pesquisa mais extensa, cujo objetivo principal é o de estudar, diacronicamente, a formação de palavras do português, com ênfase no processo de sufixação. Direciona-se ao estudo morfológico-diacrônico do sufixo MENTO, precisamente na formação de palavras, por meio do processo derivacional de sufixação; observamos as palavras portuguesas formadas pelo sufixo derivacional MENTO (do latim MEN, MENTUM). Nosso objetivo foi o de identificar os substantivos deverbais, formados por meio de um verbo unido ao sufixo MENTO, e seus significados, para então podermos afirmar a hipótese de todos se originarem de uma ação, construídos pelo modelo verbo + sufixo MENTO. Além disso, também consideramos as acepções semânticas desse sufixo, a fim de apresentarmos algumas formações parafrásticas que denotam um significado no morfema sufixal e não na base das palavras. Com o objetivo de pesquisarmos diacronicamente, como corpus adotamos o Dicionário Houaiss da Língua Portuguesa em duas versões: publicado em livro e em arquivo digital. Também utilizamos o Corpus do Português e as Cantigas de Santa Maria como corpora para acrescentarmos e alterarmos as datações do dicionário utilizado, além de incluirmos palavras não registradas naquele. A aplicação deste trabalho dá-se no campo da educação superior por meio do estudo da mudança gramatical e da história social do português, com organização simultânea de um corpus de análise. / The present work has a multidisciplinary character and finds its justification before the challenges faced by the contemporary world educational institutions; it is part of a more extensive research, which main objective is to diachronically study the formation of words in Portuguese, with emphasis in the process of suffixation. This work is directed to the diachronic morphological study of the suffix MENTO, more specifically in the formation of words, by means of the derivational process of suffixing; we will observe the Portuguese words formed by the derivational suffix MENTO (from the Latin, MEN, MENTUM). Our objective is to observe the deverbal nouns formed by a verb connected to the suffix MENTO, and its meanings, so we can state the hypothesis that they all origin from an action, formed by the model verb + suffix MENTO. Moreover, we will also research the semantic meanings of this suffix, in order to present some paraphrastic formations that denote a meaning in the suffix morpheme, and not in the base of the word. In order to search diachronically we adopted as corpus the Dicionário Houaiss da Língua Portuguesa in two versions: as published and in its digital archive. We have also used the Corpus do Português and the Cantigas de Santa Maria as corpora to add and alter the datings of the adopted dictionary, and furthermore, to include words that do not figure in it. The area of application of this work is higher education by means of study of grammatical change and the social history of Portuguese, with the simultaneous organization of an analysis corpus.