The different reproductive strategies of males and females underlie differences in behavior that may also lead to differences in nutrient use between the two sexes. We studied sex differences in the utilization of two essential amino acids (EAAs) and one non-essential amino acid (NEAA) by the Carolina sphinx moth (Manduca sexta). On day one post-eclosion from the pupae, adult male moths oxidized greater amounts of larva-derived AAs than females, and more nectar-derived AAs after feeding. After 4 days of starvation, the opposite pattern was observed: adult females oxidized more larva- derived AAs than males. Adult males allocated comparatively small amounts of nectar-derived AAs to their first spermatophore, but this allocation increased substantially in the second and third spermatophores. Males allocated significantly more adult-derived AAs to their flight muscle than females. These outcomes indicate that adult male and female moths employ different strategies for allocation and oxidation of dietary AAs.

<p> The c^13 isotope effect in acid and alkaline hydrolysis of both ethyl and tertiary butyl benzoate-carboxyl-c^14 have been measured. Significant isotope effects were found in all the hydrolyses except acid hydrolysis of the tertiary butyl oster. These results are additional evidence for the suggestion of Choen and Schneider that alkyl oxygen rather than normal acyl oxygen bond cleavage occurs when tertiary butyl benzoate is hydrolyzed in acid solution. No appreciable c^13 isotope effect was found to occur in thermal, aqueous, or acid-catalysed decarboxylation of anthranilic acid. From this observation and other experimental evidence, it is concluded that anthranilic acid decarboxylates by a bimolecular process in which the attack of the hydrogen ion is rate controlling. It is further suggested that the hydrogen ion attack is on the zwitterion at the c carbon position. Both the c^13 and the c^14 isotope effect in the decarboxylation of mesitoic acid were measured using a mass spectrometer. The c^14 isotope effect was found to be two and one half times the magnitude of the c^13 isotope effect instead of twice as present theory predicts. </p> / Thesis / Doctor of Philosophy (PhD)

Non-covalent bonds are an important class of intermolecular interactions, which result in the ordering of atoms and molecules on the supramolecular scale. One such type of interaction is brought about by the bond formation between a region of positive electrostatic potential (σ-hole) interacts and a Lewis base. Previously, the halogen bond has been extensively studied as an example of a σ-hole interaction, where the halogen atom acts as the bond donor. Similarly, carbon, and the other tetrel elements can participate in σ-hole bonds. This thesis explores the nature of the carbon tetrel bond through the use of computational chemistry and solid state nuclear magnetic resonance (NMR) spectroscopy. The results of calculations of interaction energies and NMR parameters are reported for a series of model compounds exhibiting tetrel bonding from a methyl carbon to the oxygen and nitrogen atoms in a range of functional groups. The ¹³C chemical shift (𝛿iso) and the ¹ᶜ𝐽(¹³C,¹⁷O/¹⁵N) coupling across the tetrel bond are recorded as a function of geometry. The sensitivity of the NMR parameters to the non-covalent interaction is demonstrated via an increase in 𝛿iso and in |¹ᶜ𝐽(¹³C,¹⁷O/¹⁵N)| as the tetrel bond strengthens. There is no direct correlation between the NMR trends and the interaction energy curves; the energy minimum does not appear to correspond to a maximum or minimum chemical shift or J-coupling value. Gauge-including projector-augmented wave density functional theory (DFT) calculations of 𝛿iso are reported for crystals which exhibit tetrel bonding in the solid state. Experimental 𝛿iso values for sarcosine, betaine and caffeine and their tetrel-bonded salts generally corroborate the computational findings. This work offers new insights into tetrel bonding and facilitates the incorporation of tetrel bonds as restraints in NMR crystallographic structure refinement.

No description available.

No / Traditional methods of dietary reconstruction do not allow the investigation of dietary variability within the lifetimes of individual hominins. However, laser ablation stable isotope analysis reveals that the ¿13C values of Paranthropus robustus individuals often changed seasonally and interannually. These data suggest that Paranthropus was not a dietary specialist and that by about 1.8 million years ago, savanna-based foods such as grasses or sedges or animals eating these foods made up an important but highly variable part of its diet.

O estudo de um testemunho coletado às margens de uma lagoa situada em meio a vegetação de Mata Atlântica no Parque Estadual Turístico do Alto Ribeira, sul do estado de São Paulo, permitiu a reconstituição da história da vegetação local ao longo dos últimos 2500 anos. Para isso, foram realizadas análises elementares, isotópicas e palinológicas. Também a partir de material retirado deste testemunho procedeu-se a comparação entre dois protocolos de tratamento químico para análises palinológicas do Quaternário. Os protocolos utilizados seguiram as metodologias propostas por Faegri e Iversen, 1989 (Protocolo 2) e por Colinvaux et al., 1999 (Protocolo 1). Foi desenvolvido um método de comparação que envolveu a quantidade de palinomorfos e a quantidade de matéria orgânica amorfa encontrados em 450 pontos escolhidos aleatoriamente em lâminas de ambos os protocolos e também foram levados em consideração o tempo, a praticidade de aplicação em rotina laboratorial, os custos e as quantidades e tipos de resíduos para cada protocolo. Cinco amostras de sedimento foram utilizadas para comparação e o Protocolo 1 apresentou em média 10% menos matéria orgânica amorfa e quase três vezes mais palinomorfos que o Protocolo 2. Os resultados das análises isotópicas e da palinologia mostraram que a vegetação da área em estudo teve uma fisionomia florestal pelo menos desde os últimos 2550 anos. Os valores de \'delta\'13C, em torno de - 29%o, indicaram a presença de plantas C3 em todo o período estudado e registraram um enriquecimento isotópico (-24,9%o) entre aproximadamente 1650 e 1480 anos AP. A análise palinológica apontou para a ocorrência de um clima mais frio que o atual entre 2550 anos AP e 2000 anos AP, com aumento na freqüência de Araucaria e diminuição de Arecaceae. Também foi detectada a ocorrência de um período de clima mais quente e mais úmido entre aproximadamente 1000 anos AP e 680 anos AP, com desaparecimento de Araucaria e aumento de Arecaceae, Weinmannia e de pteridófitas. A maior umidade deste período também é apontada pelos valores de C/N que indicam aumento de influência terrestre no sedimento e pelo aumento de Botryococcus. Em todas as camadas foram encontradas partículas carbonizadas, indicando períodos de ocorrência de paleoincêndios e de abertura florestal provavelmente associados à presença humana na região / One sediment core collected at the margins of a lake surrounded by Atlantic rainforest vegetation at Parque Estadual do Alto Ribeira (PETAR), southern São Paulo state (Brazil), was analyzed, in order to reconstruct the history of the local vegetation over the last 2500 years. Elemental (Total Organic Carbon TOC and Total Organic Nitrogen), isotopic (C and N), pollen analysis and radiocarbon dating were integrated on this work. Also was made a comparison of two protocols for Quaternary pollen chemical treatment. The tested protocols were proposed by Faegri and Iversen, 1989 (Protocol 2) and by Colinvaux et al., 1999 (Protocol 1). The comparison methods developed in this study checked the protocols performance on the quantity of palinomorphs and of organic matter found in 450 random areas of microscope slides of each protocol. The time consuming, laboratory routine, costs and residue production by the protocols were considered for comparison. Five samples were used for comparison and the Protocol 1 showed an average of 10% less organic matter and more palinomorphs than Protocol 2. According to the isotopic and pollen results, the study area vegetation maintained as a forest for the last 2500 years BP. \'delta\'13C values of -29%o indicated the presence of C3 plants during all the sediment study and a isotopic enrichment (- 24,9%o) was observed between 1650 and 1480 yrs BP. Pollen analysis suggested the occurrence of colder climatic conditions between 2550 and 2000 yrs BP and a warmer and humid period was suggested between 1000 and 680 yrs BP. Charcoal particles were found since 2550 yrs BP indicating paleofire probably associated to the human activities

O estudo de um testemunho coletado às margens de uma lagoa situada em meio a vegetação de Mata Atlântica no Parque Estadual Turístico do Alto Ribeira, sul do estado de São Paulo, permitiu a reconstituição da história da vegetação local ao longo dos últimos 2500 anos. Para isso, foram realizadas análises elementares, isotópicas e palinológicas. Também a partir de material retirado deste testemunho procedeu-se a comparação entre dois protocolos de tratamento químico para análises palinológicas do Quaternário. Os protocolos utilizados seguiram as metodologias propostas por Faegri e Iversen, 1989 (Protocolo 2) e por Colinvaux et al., 1999 (Protocolo 1). Foi desenvolvido um método de comparação que envolveu a quantidade de palinomorfos e a quantidade de matéria orgânica amorfa encontrados em 450 pontos escolhidos aleatoriamente em lâminas de ambos os protocolos e também foram levados em consideração o tempo, a praticidade de aplicação em rotina laboratorial, os custos e as quantidades e tipos de resíduos para cada protocolo. Cinco amostras de sedimento foram utilizadas para comparação e o Protocolo 1 apresentou em média 10% menos matéria orgânica amorfa e quase três vezes mais palinomorfos que o Protocolo 2. Os resultados das análises isotópicas e da palinologia mostraram que a vegetação da área em estudo teve uma fisionomia florestal pelo menos desde os últimos 2550 anos. Os valores de \'delta\'13C, em torno de - 29%o, indicaram a presença de plantas C3 em todo o período estudado e registraram um enriquecimento isotópico (-24,9%o) entre aproximadamente 1650 e 1480 anos AP. A análise palinológica apontou para a ocorrência de um clima mais frio que o atual entre 2550 anos AP e 2000 anos AP, com aumento na freqüência de Araucaria e diminuição de Arecaceae. Também foi detectada a ocorrência de um período de clima mais quente e mais úmido entre aproximadamente 1000 anos AP e 680 anos AP, com desaparecimento de Araucaria e aumento de Arecaceae, Weinmannia e de pteridófitas. A maior umidade deste período também é apontada pelos valores de C/N que indicam aumento de influência terrestre no sedimento e pelo aumento de Botryococcus. Em todas as camadas foram encontradas partículas carbonizadas, indicando períodos de ocorrência de paleoincêndios e de abertura florestal provavelmente associados à presença humana na região / One sediment core collected at the margins of a lake surrounded by Atlantic rainforest vegetation at Parque Estadual do Alto Ribeira (PETAR), southern São Paulo state (Brazil), was analyzed, in order to reconstruct the history of the local vegetation over the last 2500 years. Elemental (Total Organic Carbon TOC and Total Organic Nitrogen), isotopic (C and N), pollen analysis and radiocarbon dating were integrated on this work. Also was made a comparison of two protocols for Quaternary pollen chemical treatment. The tested protocols were proposed by Faegri and Iversen, 1989 (Protocol 2) and by Colinvaux et al., 1999 (Protocol 1). The comparison methods developed in this study checked the protocols performance on the quantity of palinomorphs and of organic matter found in 450 random areas of microscope slides of each protocol. The time consuming, laboratory routine, costs and residue production by the protocols were considered for comparison. Five samples were used for comparison and the Protocol 1 showed an average of 10% less organic matter and more palinomorphs than Protocol 2. According to the isotopic and pollen results, the study area vegetation maintained as a forest for the last 2500 years BP. \'delta\'13C values of -29%o indicated the presence of C3 plants during all the sediment study and a isotopic enrichment (- 24,9%o) was observed between 1650 and 1480 yrs BP. Pollen analysis suggested the occurrence of colder climatic conditions between 2550 and 2000 yrs BP and a warmer and humid period was suggested between 1000 and 680 yrs BP. Charcoal particles were found since 2550 yrs BP indicating paleofire probably associated to the human activities

Le travail de cette thèse a consisté à concevoir, réaliser et optimiser un montage expérimental de Polarisation Dynamique Nucléaire multi-échantillons pour des applications biomédicales en Imagerie Spectroscopique par Résonance Magnétique. Ce montage est constitué d'un aimant à fort champ magnétique (3,35T), dans lequel se place un système cryogénique à bain d'hélium (He$^4$) liquide pompé pouvant atteindre des températures inférieures à 1,2K. Un ensemble d'inserts permet d'effectuer les différentes étapes du processus PDN dont l'irradiation des échantillons par un champ micro-onde (f=94GHz et P=50mW) et le suivi de leur polarisation par Résonance Magnétique Nucléaire. Ce système permet de polariser jusqu'à trois échantillons, de volume proche de 1mL, à des taux de polarisation de quelques pourcents. Il présente une forte autonomie supérieure à quatre heures, autorisant ainsi la polarisation de molécules à longues constantes de temps de polarisation. La possibilité de disposer quasi-simultanément, après dissolution, de plusieurs échantillons fortement polarisés ouvre la voie à de nouvelles applications dans le domaine de l'imagerie biomédicale.

L'étude de la géochimie des particules exportées par les rivières himalayennes ainsi que la chimie des éléments dissous ont permis de préciser la quantification du couplage entre la tectonique active, caracteristique de l'Himalaya et le climat ainsi que de définir les principaux processus qui caractérisent l'érosion actuelle de la chaîne himalayenne. Les caractéristiques principales de l'érosion de la chaîne himalayenne sont: - Un important fractionnement minéralogique entre la matière en suspension et la charge de fond des rivières. Pour l'ensemble du Gange-Brahmapoutre (G-B), le transport par les MES est < 50 % de l'érosion totale qui est de 2.4 ± 0.5 10' tonnes/an pour le bassin du G-B. - La corrélation entre le taux d'érosion et l'intensité annuelle des précipitations, tant a l'échelle des larges bassins (G-B) qu'à l'intérieur de la chaîne. Le taux d'érosion de la chaîne est de 2.3 ± 0.6 mm/an pour la partie drainée par le Gange et de 3.4 ± 0.7 mm/an pour celle drainée par le Brahmapoutre alors que les écoulements spécifiques des parties himalayennes de ces fleuves sont respectivement de 1.2 et 2.1 m/an. Au Népal central,le flanc sud, soumis aux précipitations de mousson, s'érode plus de 6 fois plus vite que le flanc nord, soumis à un climat aride et sec. - Un taux maximal d'érosion physique localisée à l'endroit où la surrection tectonique, les précipitations et les glaciers sont les plus importants. C'est à l'aplomb de la rampe crustale du chevauchement himalayen (MHT) que se trouve la haute chaîne, les plus fortes précipitations et les glaciers. A cet endroit, l'érosion physique est au moins 2 fois plus élevée que dans le reste de la chaîne. - Une érosion dominée par le broyage mécanique et non l'altération et la pédogenèse. Pour l'ensemble du G-B, plus de 55% des carbonates sont érodés et transportes sous forrne particulaire et seulement 1.3% des silicates sont dissous. - La limitation de l'altération par la forte érosion physique. Le flanc sud de la haute chaîne est caractérisé par la plus faible altération et la plus forte érosion. Dans la chaîne, le couplage tectonique-altération montre un seuil au delà duquel la tectonique limite l'altération. L'altération du matériel himalayen a principalement lieu dans le bassin d'avant chaîne. - Le flux d'alcalinité liée a l'altération des silicates est de 2.7 10" mol/an ce qui représente 2.3% du flux global. Le bilan de l'altération implique une forte dominance de l'altération des carbonates et un caractère surtout sodique des silicates dissous. La consommation à long terme de CO2 atmosphérique par l'altération dans le bassin du G-B est de 6.4 1010 mol/an. - Une altération abiotique qui représente 14 Eq% de l'alcalinité. L'oxydation des sulfures des séries sédimentaires, principalement, dans la partie tibétaine de la chaîne produit 70% des sulfates dissous du G-B. Des émanations de CO, métamorphique, lié à la décarbonatation en profondeur, peuvent localement contribuer à l'altération. - Le découplage du budget du Sr dissout et celui de l'alcalinité liée aux silicates. L'altération des carbonates dans la partie aride de la chaîne est incongruente et libère une quantité importante de Sr faiblement radiogénique alors qu'une faible altération des terrains silicates anciens (> 2Ga) joue le rôle de spike de 87Sr. Ainsi le G-B (6.5 10.8 mol/an de Sr et un 87Sr/86Sr - 0.730) a un impact primordial sur le budget océanique du Sr. - La prépondérance de l'enfouissement de C organique par rapport à l'altération vis à vis du cycle du carbone. L'érosion .physique de l'orogenèse maintient des taux de sédimentation très élevés dans le bassin d'avant chaîne et le cône du Bengale. L'enfouissement et la préservation de carbone organique actuel est d'un ordre de grandeur plus élevée que la consommation de CO2 atmosphérique via l'altération. Elle représente une faible quantité (5%) de l'enfouissement global, cependant suffisante pour engendrer une perturbation dans le cycle naturel du carbone.

No description available.