Isotopes, wool, and rangeland monitoring: Let the sheep do the sampling

Stable carbon isotope analyses of wool staples provided insight into the vegetation consumed by sheep at a temporal resolution not previously studied. Contemporary Australian and historic South African samples dating back to 1916 were analyzed for their stable carbon isotope ratio, a proxy for the proportion of C-3 and C-4 plant species consumed by animals. Sheep sample vegetation continuously throughout a year, and as their wool grows it integrates and stores information about their diet. In subtropical and tropical rangelands the majority of grass species are C-4. Since sheep prefer to graze, and their wool is an isotopic record of their diet, we now have the potential to develop a high resolution index to the availability of grass from a sheep's perspective. Isotopic analyses of wool suggest a new direction for monitoring grazing and for the reconstruction of past vegetation changes, which will make a significant contribution to traditional rangeland ecology and management. It is recommended that isotopic and other analyses of wool be further developed for use in rangeland monitoring programs to provide valuable feedback for land managers.

cis-3-hydroxy-N-methyl-L-proline: a new amino acid from a southern Australian marine sponge, Dendrilla sp.

A specimen of the sponge Dendrilla sp. collected during commercial trawling operations in the Great Australian Eight, Australia, analyses for a very high natural abundance of the new amino acid cis-3-hydroxy-N-methyl-L-proline (1). The complete stereostructure for (1) was determined by spectroscopic analysis and chemical derivatization.

Similar Intracellular Peptide Profile of TAP1/beta 2 Microglobulin Double-Knockout Mice and C57BL/6 Wild-Type Mice as Revealed by Peptidomic Analysis

Cells produce and use peptides in distinctive ways. In the present report, using isotope labeling plus semi-quantitative mass spectrometry, we evaluated the intracellular peptide profile of TAP1/beta 2m(-/-) (transporter associated with antigen-processing 1/beta 2 microglobulin) double-knockout mice and compared it with that of C57BL/6 wild-type animals. Overall, 92 distinctive peptides were identified, and most were shown to have a similar concentration in both mouse strains. However, some peptides showed a modest increase or decrease (similar to 2-fold), whereas a glycine-rich peptide derived from the C-terminal of neurogranin (KGPGPGGPGGAGGARGGAGGGPSGD) showed a substantial increase (6-fold) in TAP1/beta 2m(-/-) mice. Thus, TAP1 and beta 2microglobulin have a small influence on the peptide profile of neuronal tissue, suggesting that the presence of peptides derived from intracellular proteins in neuronal tissue is not associated with antigens of the class I major histocompatibility complex. Therefore, it is possible that these intracellular peptides play a physiological role.

Soil carbon and nitrogen in pasture soil reforested with eucalyptus and guachapele

In spite of the normally low content of organic matter found in sandy soils, it is responsible for almost the totality of cation exchange capacity (CEC), water storage and availability of plant nutrients. It is therefore important to evaluate the impact of alternative forest exploitation on the improvement of soil C and N accumulation on these soils. This study compared pure and mixed plantations of Eucalyptus grandis and Pseudosamanea guachapele, a N2-fixing leguminous tree, in relation to their effects on soil C and N stocks. The studied Planosol area had formerly been covered by Panicum maximum pasture for at least ten years without any fertilizer addition. To estimate C and N contents, the soil was sampled (at depths of 0-2.5; 2.5-5.0; 5.0-7.5; 7.5-10.0; 10.0-20.0 and 20.0-40.0 cm), in pure and mixed five-year-old tree plantations, as well as on adjacent pasture. The natural abundance 13C technique was used to estimate the contribution of the soil organic C originated from the trees in the 0-10 cm soil layer. Soil C and N stocks under mixed plantation were 23.83 and 1.74 Mg ha-1, respectively. Under guachapele, eucalyptus and pasture areas C stocks were 14.20, 17.19 and 24.24 Mg ha-1, respectively. For these same treatments, total N contents were 0.83; 0.99 and 1.71 Mg ha-1, respectively. Up to 40 % of the soil organic C in the mixed plantation was estimated to be derived from trees, while in pure eucalyptus and guachapele plantations these same estimates were only 19 and 27 %, respectively. Our results revealed the benefits of intercropped leguminous trees in eucalyptus plantations on soil C and N stocks.

Isotope determination of sulfur by mass spectrometry in soil samples

Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S) with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS) in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-)), which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2-) concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms) was carried out by isotope ratio mass spectrometry (IRMS). In this work, the labeled material (K2(34)SO4) was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

Nitrogen fixation by groundnut and velvet bean and residual benefit to a subsequent maize crop

Chemical fertilisers are rarely avaiable to poor farmers, for whom the nitrogen (N) is often the most limiting element for cereal grain production. The objective of this study was to quantify the contribution of biological nitrogen fixation (BNF) to groundnut (Arachis hypogaea) and velvet bean (Mucuna pruriens) crops using the 15N natural abundance (delta15N) technique and to determine their residual effect and that of a natural fallow, on growth and N accumulation by two rustic maize varieties. The contribution of BNF calculated from delta15N data was 40.9, 59.6 and 30.9 kg ha-1, for groundnut, velvet bean and the natural fallow, respectively. The only legume grain harvested was from the groundnut, which yielded approximately 1.000 kg ha-1. The subsequent maize varieties ("Sol de Manhã" and "Caiana Sobralha") yielded between 1.958 and 2.971 kg ha-1, and were higher after velvet bean for both maize varieties and "Sol da Manhã" groundnut, followed by "Caiana" after groundnut and, finally, the natural fallow. For a small-holder producer the most attractive system is the groundnut followed by maize, as, in this treatment, both groundnut and maize grain harvest are possible. However, a simple N balance calculation indicated that the groundnut-maize sequence would, in the long term, deplete soil N reserves, while the velvet bean-maize sequence would lead to a build up of soil nitrogen.

Nitrogen symbiotically fixed by cowpea and gliricidia in traditional and agroforestry systems under semiarid conditions

The objective of this work was to estimate the amounts of N fixed by cowpea in a traditional system and by cowpea and gliricidia in an agroforestry system in the Brazilian Northeast semiarid. The experiment was carried out in a randomized complete block design, in a split-plot arrangement, with four replicates, in the semiarid region of the state of Paraíba, Brazil. Plots consisted of agroforestry and traditional systems (no trees), and split-plots of the three crops planted between the tree rows in the agroforestry system. To estimate N fixation, plant samples were collected in the fourth growth cycle of the perennial species and in the fourth planting cycle of the annual species. In the agroforestry system with buffel grass and prickly-pear cactus, gliricidia plants symbiotically fix high proportions of N (>50%) and contribute with higher N amounts (40 kg ha-1 in leaves) than in the traditional system (11 kg ha-1 in grain and 18 kg ha-1 in straw). In the agroforestry system with maize and cowpea, gliricidia plants do not fix nitrogen, and N input is limited to the fixation by cowpea (2.7 kg ha-1), which is lower than in the traditional system due to its lower biomass production.

Conservative nutrient use by big-leaf mahogany (Swietenia macrophylla king) planted under contrasting environmental conditions

We analyzed the nutritional composition and isotope ratios (C and N) of big-leaf mahogany (Swietenia macrophylla King) leaves in plantations established on contrasting soils and climates in Central America (State of Quintana Roo, Yucatán, México) and South America (State of Pará, Brazil). The objective was to determine the adaptability of this species to large differences in nutrient availability and rainfall regimes. Nutrient concentrations of leaves and soils were determined spectrophotometrically, and isotope ratios were measured using mass spectrometric techniques.In Pará soils were sandier, and acidic, receiving above 2000 mm of rain, whereas in Quintana Roo soils were predominantly clayey, with neutral to alkaline pH due to the underlying calcareous substrate, with about 1300 mm of rain. Leaf area/weight ratio was similar for both sites, but leaves from Quintana Roo were significantly smaller. Average N and K concentrations of adult leaves were similar, whereas Ca concentration was only slightly lower in Pará in spite of large differences in Ca availability. Leaves from this site had slightly higher P and lower Al concentrations. Differences in water use efficiency as measured by the natural abundance of 13C were negligible, the main effect of lower rainfall in Quintana Roo seemed to be a reduction in leaf area. The N isotope signature (δ15N) was more positive in Pará than in Quintana Roo, suggesting higher denitrification rates in the former. Results reveal a calciotrophic behavior and a remarkable capacity of mahogany to compensate for large differences in soil texture and nutrient availability.

Understanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Study

The natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.

In vivo phosphorus spectroscopy in human subjects on a clinical 3T MRI system

Alors que l’Imagerie par résonance magnétique (IRM) permet d’obtenir un large éventail de données anatomiques et fonctionnelles, les scanneurs cliniques sont généralement restreints à l’utilisation du proton pour leurs images et leurs applications spectroscopiques. Le phosphore jouant un rôle prépondérant dans le métabolisme énergétique, l’utilisation de cet atome en spectroscopie RM présente un énorme avantage dans l’observation du corps humain. Cela représente un certain nombre de déEis techniques à relever dus à la faible concentration de phosphore et sa fréquence de résonance différente. L’objectif de ce projet a été de développer la capacité à réaliser des expériences de spectroscopie phosphore sur un scanneur IRM clinique de 3 Tesla. Nous présentons ici les différentes étapes nécessaires à la conception et la validation d’une antenne IRM syntonisée à la fréquence du phosphore. Nous présentons aussi l’information relative à réalisation de fantômes utilisés dans les tests de validation et la calibration. Finalement, nous présentons les résultats préliminaires d’acquisitions spectroscopiques sur un muscle humain permettant d’identiEier les différents métabolites phosphorylés à haute énergie. Ces résultats s’inscrivent dans un projet de plus grande envergure où les impacts des changements du métabolisme énergétique sont étudiés en relation avec l’âge et les pathologies.

Novel Strategies for Heterocyclic Constructions via 1, 4-Dipolar Intermediates

In the thesis entitled " Novel Strategies for Heterocyclic Constructions via 1 ,4-Dipolar Intermediates"Synthesis of a complex organic molecules essentially involves the formation of carbon-carbon and carbon-heteroatom bonds. Various synthetic methods are available for these processes involving ionic, pericyclic and radical reactions. Among the pericyclic reactions, dipolar cycloaddition reactions, introduced by Huisgen, have emerged as a very powerful tool for heterocyclic construction. Heterocyclic compounds remain an important class of organic molecules due to their natural abundance and remarkable biological activity, thus constituting an intergral part of pharmaceutical industry. In this respect, developing newer synthetic methodology for heterocyclic construction has been an area of immense interest. In recent years, 1,3-dipolar cycloaddition reactions proved to be efficient routes to a wide variety of five membered heterocycles, as attested by their application in the total synthesis of various complex organic molecules. However, the potential application of similar 1,4- dipolar cycloaddition reactions for the construction of six memebered heterocycles remained underexploited. In this context, a systematic investigation of the reactivity of 1,4-dipoles generated from nitrogen heterocycles (pyridine and its analogues) and dimethyl acetylenedicarboxy!ate (DMAD) towards various dipolarophiles has been carried out and the results are embodied.

Leguminous cover crops differentially affect maize yields in three contrasting soil types of Kakamega, Western Kenya

Maize production in smallholder farming systems in Kenya is largely limited by low soil fertility. As mineral fertilizer is expensive, green manuring using leguminous cover crops could be an alternative strategy for farmers to enhance farm productivity. However due to variability in soil type and crop management, the effects of green manure are likely to differ with farms. The objectives of this study were to evaluate Mucuna pruriens and Arachis pintoi on (i) biomass and nitrogen fixation (^15N natural abundance), (ii) soil carbon and nitrogen stocks and (iii) their effects on maize yields over two cropping seasons in Kakamega, Western Kenya. Mucuna at 6 weeks accumulated 1–1.3 Mg ha^{-1} of dry matter and 33–56 kg ha^{-1} nitrogen of which 70% was nitrogen derived from the atmosphere (Ndfa). Arachis after 12 months accumulated 2–2.7 Mg ha^{-1} of dry matter and 51–74 kg N ha^{-1} of which 52-63 % was from Ndfa. Soil carbon and nitrogen stocks at 0–15 cm depth were enhanced by 2-4 Mg C ha^{-1} and 0.3–1.0 Mg N ha^{-1} under Mucuna and Arachis fallow, irrespective of soil type. Maize yield increased by 0.5-2 Mg ha^{-1} in Mucuna and 0.5–3 Mg ha^{-1} in Arachis and the response was stronger on Nitisol than on Acrisol or Ferralsol. We concluded that leguminous cover crops seem promising in enhancing soil fertility and maize yields in Kenya, provided soil conditions and rainfall are suitable.

Efficacy of condensed tannins against larval Hymenolepis diminuta (Cestoda) in vitro and in the intermediate host Tenebrio molitor (Coleoptera) in vivo

Natural anti-parasitic compounds in plants such as condensed tannins (CT) have anthelmintic properties against a range of gastrointestinal nematodes, but for other helminths such effects are unexplored. The aim of this study was to assess the effects of CT from three different plant extracts in a model system employing the rat tapeworm, Hymenolepis diminuta, in its intermediate host, Tenebrio molitor. An in vitro study examined infectivity of H. diminuta cysticercoids (excystation success) isolated from infected beetles exposed to different concentrations of CT extracts from pine bark (PB) (Pinus sps), hazelnut pericarp (HN) (Corylus avellana) or white clover flowers (WC) (Trifolium repens), in comparison with the anthelmintic drug praziquantel (positive control). In the in vitro study, praziquantel and CT from all three plant extracts had dose-dependent inhibitory effects on cysticercoid excystation. The HN extract was most effective at inhibiting excystation, followed by PB and WC. An in vivo study was carried out on infected beetles (measured as cysticercoid establishment) fed different doses of PB, HN and praziquantel. There was a highly significant inhibitory effect of HN on cysticercoid development (p = 0.0002). Overall, CT showed a promising anti-cestodal effect against the metacestode stage of H. diminuta.

Structural-electronic aspects related to the near-infrared light emission of Fe-doped silicon films

The need of efficient (fast and low consumption) optoelectronic devices has always been the driving force behind the investigation of materials with new or improved properties. To be commercially attractive, however, these materials should be compatible with our current micro-electronics industry and/or telecommunications system. Silicon-based compounds, with their matured processing technology and natural abundance, partially comply with such requirements-as long as they emit light. Motivated by these issues, this work reports on the optical properties of amorphous Si films doped with Fe. The films were prepared by sputtering a Si+Fe target and were investigated by different spectroscopic techniques. According to the experimental results, both the Fe concentration and the thermal annealing of the samples induce changes in their atomic structure and optical-electronic properties. In fact, after thermal annealing at similar to 750 degrees C, the samples partially crystallize with the development of Si and/or beta-FeSi(2) crystallites. In such a case, certain samples present light emission at similar to 1500 nm that depends on the presence of beta-FeSi(2) crystallites and is very sensitive to the annealing conditions. The most likely reasons for the light emission (or absence of it) in the considered Fe-doped Si samples are presented and discussed in view of their main structural-electronic characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of root surface treatment with propolis and fluoride in delayed tooth replantation in rats

Replantation is an acceptable option for treatment of an avulsed permanent tooth. Nevertheless, an extended extraoral period damages the periodontal ligament and results in external root resorption. The purpose of this study was to assess by histologic and histometric analysis, the influence of propolis 15% (natural resinous substance collected by Apis mellifera bees from various plants) and the fluoride solution used as root surface treatment on the healing process after delayed tooth replantation. Thirty Wistar (Rattus norvegicus albinus) rats were submitted to extraction of their upper right incisor. The teeth were maintained in a dry environment for 60 min. After this, the pulp was extirpated and the papilla, enamel organ and periodontal ligament were removed with scalpel. The teeth were divided into three experimental groups: Group I - teeth immersed in 20 ml of physiologic saline; Group II - teeth immersed in 20 ml of 2% acidulated phosphate sodium fluoride; Group III - teeth immersed in 20 ml of 15% propolis. After 10 min of immersion in the solutions, the root canals were dried and filled with calcium hydroxide paste and the teeth were replanted. The animals were euthanized 60 days after replantation. The results showed that similar external root resorption was seen in the propolis and fluoride groups. Teeth treated with physiologic saline tended to have more inflammatory root resorption compared with those treated with fluoride or propolis. However, the comparative analysis did not reveal statistically significant differences (P > 0.05) between the treatment modalities when used for delayed tooth replantation.