The gas-phase hydrogen/deuterium (H/D) exchange of protonated di- and tripeptides containing a basic amino acid residue has been studied with a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Bimolecular reactions are monitored as a function of time providing exchange efficiencies and temporal distributions for the peptide ions. Results from these experiments indicated that position of the basic residue within the peptide (i.e. N-terminal, internal, or C-terminal) influences gas-phase H/D exchange, suggesting unique peptide ion conformations. The FT-ICR mass spectrometer employed for these gas-phase H/D exchange studies was modified from its original design. Instrument modifications include development of an internal matrix assisted laser desorption ionization (MALDI) source for peptide protonation. In addition, a two-section cell was utilized, allowing control of ion motion and factors affecting gas-phase ion molecule reactions. Systems investigated in these gas-phase H/D exchange studies are peptides containing the same amino acid residues but different sequences. These sequence isomers display dissimilar reaction efficiencies and temporal distributions for deuterium incorporation depending on the primary structure of the peptide ion. Specifically, [M+H]+ peptide ions containing a N-terminal basic residue demonstrate unique H/D exchange behavior when compared to their internal and C-terminal counterparts. These differences are attributed to dissimilar intramolecular bridging interactions involved with inductive stabilization of the charge site. Gas-phase H/D exchange of peptide sequence isomers was also probed with various deuterium reagents. Findings suggest that different reagents also influence H/D exchange reaction rate efficiencies and temporal distributions. These dissimilarities are ascribed to relative gas-phase basicity and proposed mechanistic exchange differences for the deuterium reagents.

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 203-213).

Typescript. Includes vita and abstract. Discusses the poetry of H.D., Gwendolyn Brooks, Louise Glück, and Anne Carson. Includes bibliographical references (leaves 261-267). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

Thesis (Ph. D.)--Ohio State University, 2006. / Available online via OhioLINK's ETD Center; full text release delayed at author's request until 2011 May 19

M.A. (African Languages) / Please refer to full text to view abstract

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22701号 / 工博第4748号 / 新制||工||1742(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 大塚 浩二, 教授 松原 誠二郎, 教授 秋吉 一成 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

To determine the susceptibility of developing brain and other tissues to accumulate zinc, rats were exposed to zinc at different periods of ontogeny. For the prenatal group, pregnant Wistar rats received 50 ppm of zinc (ZnSO4 · 7H2O) in drinking for the entire duration of pregnancy. On the day of delivery zinc was removed from the drinking water. Another group, dams, received 50 ppm of zinc in drinking water only during the suckling period (from delivery until the 21st day of postnatal life). Their offspring were weaned on the 21st day, at which time zinc was removed from the drinking water. The control group drank tap water only. At 3 weeks after birth, the level of zinc was estimated in the brain, liver, mandibular bone and kidney of offspring from all groups. At 8 weeks after birth 6-[3H]D-glucose (500 μCi/kg) was administered IP to male offspring, 15 minutes before sacrifice. By liquid scintillation spectroscopy, 3H-activity (expressed as disintegrations per minute [DPM]) was determined in discrete parts of the brain and some peripheral tissues, and expressed as DPM/100 mg of tissue, wet weight. It was found that the highest amount of zinc was accumulated in the brain and liver of rat offspring that were exposed to zinc postnatally. [3H]-activity was at lower levels, in comparison, in nearly all other parts of the brain of rats exposed to zinc postnatally. In offspring receiving zinc prenatally, zinc levels were at similar or lower amounts in the brain and peripheral tissues, vs. the group with postnatal exposure. From this study in rats we conclude that zinc accumulates to the highest extent in brain, following a later ontogenetic (postnatal) exposure period, and by this, there is also greater disturbance of metabolic processes associated with glucose utilization.

In Attention Deficit Hyperactivity Disorder (AD(H)D), treatments using methylphenidate (MPH) and behavioralinterventions like neurofeedback (NF) reflect major therapeutic options. These treatments also ameliorate ex-ecutive dysfunctions in AD(H)D. However, the mechanisms underlying effects of MPH and NF on executivefunctions in AD(H)D (e.g. the ability to inhibit prepotent responses) are far from understood. It is particularlyunclear whether these interventions affect similar or dissociable neural mechanisms and associated functionalneuroanatomical structures. This, however, is important when aiming to further improve these treatments. Wecompared the neurophysiological mechanisms of MPH and theta/beta NF treatments on inhibitory control on the basis of EEG recordings and source localization analyses. The data show that MPH and theta/beta NF bothincrease the ability to inhibit pre-potent responses to a similar extent. However, the data suggest that MPH andNF target different neurophysiological mechanisms, especially when it comes to functional neuroanatomicalstructures associated with these effects. Both treatments seem to affect neurophysiological correlates of a‘braking function’ in medial frontal areas. However, in case of the NF intervention, inferior parietal areas are alsoinvolved. This likely reflects the updating and stabilisation of efficient internal representations in order to in-itiate appropriate actions. No effects were seen in correlates of perceptual and attentional selection processes.Notably, reliable effects were only obtained after accounting for intra-individual variability in the neurophy-siological data, which may also explain the diversity of findings in studies on treatment effects in AD(H)D,especially concerning neurofeedback.

My dissertation examines the correlations between the natural and supernatural, agency and authority, and meaning and language in the work of the modernist American writers H.D. (Hilda Doolittle) and Djuna Barnes. Using the psychoanalytic theory of Jacques Lacan, Melanie Klein, and Nicholas Abraham and Maria Torok, I argue that the different kinds of spectral and otherworldly figures that appear in these works – ghosts, the living dead, divinities, individuals who are also amorphous multiplicities – correlate to the modes of negation of parental imperatives that structure the language-use of their authors. I contrast H.D.‘s and Barnes‘s visions of the relation of language to meaning and the personal to the social using Lacan‘s delineation of the different modes of psychic negation that enable or disable language use: repression, disavowal, and foreclosure. According to this model, H.D.‘s work evidences foreclosure: a mode of thought and language that fails to differentiate words, thoughts, and people from one another. This incapacity endangers the psyche with the hallucinatory return of or haunting by what cannot be symbolized. In contrast, Barnes‘s work suggests disavowal, and her language renders experience in distorted forms. She repudiates power figures and the unspeakable meanings associated with them, but her work portrays the spectral, surreptitious return of these figures and meanings. Writing that witnesses or stages a return to a state of non-difference between symbol and symbolized, as Barnes‘s and H.D.‘s work does, calls for different interpretative and methodological strategies than those usual in literary criticism. To read such work primarily as symbolic communication is to lose perspective on the structures of thought and language that it grapples with. A perspective that is rigorous and radically different from the works‘ own is necessary to produce readings of it that make symbolic ―sense,‖ though it is unable to fully account for experiences that are not conceivable. To this end, I describe ―disorders,‖ types of thought and language that psychoanalysis implicates in interminable human suffering, without drawing conclusions about the range of experiences that might be concurrent with asymbolic or anti-symbolic thought and writing. / Graduate / 2019-08-31 / 0298 / 0591

Resumo: Neste trabalho estudou-se a estrutura, função e mecanismo de ação do peptídeo antibacteriano Protonectarina-MP (isolado de veneno da vespa social Protonectarina sylveirae) tendo seu resíduo C-terminal nas formas ácida (-OH) e amidada (-NH2). Os peptídeos foram sintetizados, utilizando-se a estratégia Fmoc, purificados por cromatografia líquida de alta performance. O monitoramento do material sintético foi feito por espectrometria de massas ESI-MS e por seqüenciamento através de Química Degradativa de Edman. A estrutura secundária foi investigada pelo uso de espectroscopia de dicroísmo circular e modelagem molecular. Atividade lítica (extravasamento) e interação do resíduo de triptofano em vesículas foram investigadas pelo uso de espectrômetro de fluorescência. Foram realizados ensaios sobre as interações desses peptídeos em meio de vesículas zwitteriônicas e aniônica, formando complexos proteolipossomos que foram submetidos à troca isotópica H/D monitorada por espectrometria de massas ESI-MS e MS/MS. Além disso, foram realizados ensaios biológicos de atividade hemolítica, de desgranulação de mastócito, de liberação da enzima citoplasmática Lactato Desidrogenase e de atividade antimicrobianas. Os dados de CD revelam uma tendência dos peptídeos se estruturarem em hélice-α em ambiente hidrofóbico e em ambiente de membranas. Porém, o mesmo não pode ser observado em meio aquoso. Os modelos obtidos para ambos os peptídeos por modelagem molecular mostram uma estruturação em hélice-α anfipática. Nos ensaios de atividade lítica em vesículas, os peptídeos apresentaram um processo com cooperatividade positiva, com curvas de dose-resposta que mostram uma dependência sigmoidal com a concentração do peptídeo. Os resultados da fluorescência do triptofanos mostram um deslocamento da emissão para a região de onda do azul para o peptídeo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In the present work was studied the structure, function and mechanism of action of the antibacterial peptide Protonectarina-MP (isolated from venom of social wasp Protonectarina sylveirae) with its carboxyamidation (-NH2) and carboxyl-free (-OH) Cterminal forms. The peptides were manually synthesized on-solid phase by using Fmoc strategy and purified under HPLC. The homogeneity of the synthetic material was analyzed by ESI mass spectrometry and Edman Degradation Chemistry. The secondary structure was investigated through circular dichroism (CD) spectroscopy and molecular modeling. Lytic activity and peptides interaction with the membranes was also investigated through tryptophan emission, by fluorescence spectrometry. The interaction of peptides with zwitterionic and anionic vesicles was investigated through the combination of H/D exchange and ESI-mass spectrometry. Some biological activities, like: mast cell degranulation, release of cytoplasmic enzyme lactate dehydrogenase, hemolysis and antibiosis were investigated for both peptides. The CD spectra revealed that the peptides in hydrophobic environments or in presence of biological membranes have the tendency to form helix conformations; however, organized structures were not observed in aqueous or buffer solutions. The models obtained by molecular modeling show that both peptides form an amphipathic α-helix. The peptides presented a positive cooperative process in the lytic activity of vesicles, with dose-response curves presenting a sigmoidal dependence with the peptide concentration. The results of the fluorescence of tryptophans showed a shift of the emission wavelength to the blue region of the peptide Protonectarina-MP (-NH2), which was not observed for its analogue presenting the C-terminal residue in free acid form. This is indicating a greater interaction of the amidated peptide in membranes, when compared to the peptide... (Complete abstract click electronic access below) / Orientador: Mario Sergio Palma / Coorientador: João Ruggiero Neto / Banca: Ivo Lebrun / Banca: Pietro Ciancaglini / Mestre