Expanded porphyrins and their evaluation as anion chemosensors

Expanded porphyrins are synthetic analogues of porphyrins, differing from the last ones and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core, with a minimum of 17 atoms, while retaining the extended conjugation features that are a tremendous feature of these biological pigments. The core expansion results in various systems with novel spectral and electronic features, often uniques. Most of these systems can also coordinate cations and/or anions, and in some cases they can bind more than one of these species. In many cases, these molecules display structural features, such as non-planar structures, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. This work will discuss several synthetic approaches for the synthesis of expanded porphyrins, namely the construction of new building blocks by Michael addition, as well as potential synthetic routes towards expanded porphyrins. The synthesis of smaller oligopyrrolic compounds namely, bipyrroles and dipyrromethanes, not only were developed for the synthesis of expanded porphyrins as they were also used in Knoevenagel condensations furnishing chromogenic compounds able to recognize different anions in solution. Also, an approach to the synthesis of novel expanded porphyrins namely sapphyrins has been done by aza-Michael additions. Several synthetic routes towards the synthesis of pyridyl and pyridinium N-Fused pentaphyrins and hexaphyrins have been explored in order to achieve compounds with potential applications in catalysis and PDI, respectively. Studies on the synthesis of compounds with potential anion binding properties, led to the structural characterization and NMR anion binding studies of [28]hexaphyrins functionalized with several diamines in the para position of their pentafluorophenyl groups. These compounds allow NH hydrogen bond interactions with various anions. All synthesized compounds were fully characterized by modern spectroscopic techniques.

"Man of science, man of faith" : Lost, consumer agency and the fate/free will binary in the post-9/11 context

In 2004, Lost debuted on ABC and quickly became a cultural phenomenon. Its postmodem take on the classic Robinson Crusoe desert island scenario gestures to a variety of different issues circulating within the post-9II1 cultural consciousness, such as terrorism, leadership, anxieties involving air travel, torture, and globalization. Lost's complex interwoven flashback and flash-forward narrative structure encourages spectators to creatively hypothesize solutions to the central mysteries of the narrative, while also thematically addressing archetypal questions of freedom of choice versus fate. Through an examination of the narrative structure, the significance of technological shifts in television, and fan cultures in Lost, this thesis discusses the tenuous notion of consumer agency within the current cultural context. Furthermore, I also explore these issues in relation to the wider historical post-9/II context.

Women in Post –1961 Goa : Problems and Challenges

When the women of Goa begin to reminiscence about the last four and a half decades of Goan history it will be a journey of mixed responses, for the women’s movement has witnessed gains and losses, successes and failures, times of expression and times of being silenced, times of vibrant activity and times of lulls and importantly, times of prolonged protests against markets and developmental forces, and media projections. For decades the women of Goa have taken a vociferous stand against arbitrary Development practices that the Government has attempted to foist upon the people of the State and especially its women. For decades the women of Goa have demanded for a gendered perspective and an equal representation in the development processes in the State.

ICOM Switzerland implication in training matters: last news

The presentation will focus on ICOM Switzerland‘s works concerning training designed for museums professionals. Its implication in this field is increasing, within the framework of its own offer of continuous education, as well as within partnerships with other external institutions (for example universities).In September 2008, the first Master in Museology in Switzerland (Master en études muséales) will be launched, as a result of the cooperation of ICOM Switzerland, the University of Neuchâtel and l‘Association des musées suisses (the National Swiss Museums Association).ICOM Switzerland is involved in reflections with museum professionnals. For instance, it collaborated with Swiss museum educators (the médiateurs culturels) in order to define quality standards for their working areas. This year also, a certification has also been set up, regarding training for museums professionals. The project has been presented in Vienna last year and it is now operational.

Pricing short leases and break clauses using simulation methodology

This paper examines the changes in the length of commercial property leases over the last decade and presents an analysis of the consequent investment and occupational pricing implications for commercial property investmentsIt is argued that the pricing implications of a short lease to an investor are contingent upon the expected costs of the letting termination to the investor, the probability that the letting will be terminated and the volatility of rental values.The paper examines the key factors influencing these variables and presents a framework for incorporating their effects into pricing models.Approaches to their valuation derived from option pricing are critically assessed. It is argued that such models also tend to neglect the price effects of specific risk factors such as tenant circumstances and the terms of break clause. Specific risk factors have a significant bearing on the probability of letting termination and on the level of the resultant financial losses. The merits of a simulation methododology are examined for rental and capital valuations of short leases and properties with break clauses.It is concluded that in addition to the rigour of its internal logic, the success of any methodology is predicated upon the accuracy of the inputs.The lack of reliable data on patterns in, and incidence of, lease termination and the lack of reliable time series of historic property performance limit the efficacy of financial models.

Related changes in biodiversity, insolation and climate in the Atlantic rainforest since the last interglacial

The long-term Colonia record is located in the Atlantic rainforest domain in Brazil (23 degrees 52`S 46 degrees 42`20 `` W 900 m a.s.l.). The 780 cm long core CO3 provides a coverage of a complete interglacial/glacial cycle for the first time in a neotropical rainforest. Information on the behavior of tropical climates compared to global changes in temperatures indicates specific climate responses in terms of precipitation at these latitudes. Winter extratropical circulation was very active during the last interglacial and most of the glacial. Floristic composition of the rainforest changed several times in each phase of expansion, twice during the interglacial, and three times during glacial episodes. Araucaria was well developed in the area of Sao Paulo until the beginning of the first dry phase of the glacial at ca. 50,000 yr B.P. Changes in insolation controlled the expansion of the rainforest and the tropical hydrological cycle as evidenced by a strong precession signal. However precession had no impact on regional climatic features. The two interglacials (MIS 5e and Holocene) showed completely different patterns attesting to the continuous evolution of the forest. The biodiversity index (Shannon-Wiener Index) remained high during both the interglacial and glacial attesting to the permanence of small patches of rainforest refugia during drier phases. The lowest Shannon-Wiener Indexes were recorded between 23,000 and 12,000 yr B.P. and 40,000 and 30,000 yr B.P. and characterize two marked phases of stress for the rainforest. (C) 2008 Elsevier B.V. All rights reserved.

Synergies and price trends in sequential auctions

In this paper we consider sequential auctions where an individual’s value for a bundle of objects is either greater than the sum of the values for the objects separately (positive synergy) or less than the sum (negative synergy). We show that the existence of positive synergies implies declining expected prices. When synergies are negative, expected prices are increasing. There are several corollaries. First, the seller is indi¤erent between selling the objects simultaneously as a bundle or sequentially when synergies are positive. Second, when synergies are negative, the expected revenue generated by the simultaneous auction can be larger or smaller than the expected revenue generated by the sequential auction. In addition, in the presence of positive synergies, an option to buy the additional object at the price of the …rst object is never exercised in the symmetric equilibrium and the seller’s revenue is unchanged. Under negative synergies, in contrast, if there is an equilibrium where the option is never exercised, then equilibrium prices may either increase or decrease and, therefore, the net e¤ect on the seller’s revenue of the introduction of an option is ambiguous. Finally, we examine two special cases with asymmetric players. In the …rst case, players have distinct synergies. In this example, even if one player has positive synergies and the other has negative synergies, it is still possible for expected prices to decline. In the second case, one player wants two objects and the remaining players want one object each. For this example, we show that expected prices may not necessarily decrease as predicted by Branco (1997). The reason is that players with singleunit demand will generally bid less than their true valuations in the …rst period. Therefore, there are two opposing forces; the reduction in the bid of the player with multiple-demand in the last auction and less aggressive bidding in the …rst auction by the players with single-unit demand.

Último Desejo e Testamento de Wilhelm Reich

O objetivo desta tradução é contribuir para a divulgação do pensamento do médico psiquiatra e inicialmente, psicanalista, Wilhelm Reich. Nascido em 24 de março de 1897, em parte da Galícia pertencente ao Império austro-húngaro, Reich morreu na prisão em 03 de novembro de 1957 nos Estados Unidos da América. Contudo, poucos meses antes do ataque cardíaco que o levou à morte, Reich legou sua obra às crianças do futuro em testamento assinado em 08 de março de 1957, onde registrou seus últimos desejos sob o testemunho de Willian Moise, Michael Silvert e Willian Steig, temendo possíveis distorções, difamações, adulterações e destruição de seus escritos após a sua morte.

Hepatic gluconeogenesis in rats trained to eat a single meal daily. Role of eating periodicity and the amount of food ingested in the last meal

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

ECLAC and the sociology of development

Includes bibliography

Characterization of the variable cow's age at last calving as a measurement of longevity by using the Kaplan-Meier estimator and the Cox model

In most studies on beef cattle longevity, only the cows reaching a given number of calvings by a specific age are considered in the analyses. With the aim of evaluating all cows with productive life in herds, taking into consideration the different forms of management on each farm, it was proposed to measure cow longevity from age at last calving (ALC), that is, the most recent calving registered in the files. The objective was to characterize this trait in order to study the longevity of Nellore cattle, using the Kaplan-Meier estimators and the Cox model. The covariables and class effects considered in the models were age at first calving (AFC), year and season of birth of the cow and farm. The variable studied (ALC) was classified as presenting complete information (uncensored = 1) or incomplete information (censored = 0), using the criterion of the difference between the date of each cow's last calving and the date of the latest calving at each farm. If this difference was >36 months, the cow was considered to have failed. If not, this cow was censored, thus indicating that future calving remained possible for this cow. The records of 11 791 animals from 22 farms within the Nellore Breed Genetic Improvement Program ('Nellore Brazil') were used. In the estimation process using the Kaplan-Meier model, the variable of AFC was classified into three age groups. In individual analyses, the log-rank test and the Wilcoxon test in the Kaplan-Meier model showed that all covariables and class effects had significant effects (P < 0.05) on ALC. In the analysis considering all covariables and class effects, using the Wald test in the Cox model, only the season of birth of the cow was not significant for ALC (P > 0.05). This analysis indicated that each month added to AFC diminished the risk of the cow's failure in the herd by 2%. Nonetheless, this does not imply that animals with younger AFC had less profitability. Cows with greater numbers of calvings were more precocious than those with fewer calvings. Copyright © The Animal Consortium 2012.

Construction and preliminary characterization of a river buffalo bacterial artificial chromosome library

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Characterization and application of nanostructured films containing Au and TiO2 nanoparticles supported in bacterial cellulose

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sediment core fossils in ancient Lake Ohrid: testing for faunal change since the Last Interglacial

Ancient Lake Ohrid is probably of early Pleistocene or Pliocene origin and amongst the few lakes in the world harbouring an outstanding degree of endemic biodiversity. Although there is a long history of evolutionary research in Lake Ohrid, particularly on molluscs, a mollusc fossil record has been missing up to date. For the first time, gastropod and bivalve fossils are reported from the basal, calcareous part of a 2.6 m long sediment succession (core Co1200) from the north-eastern part of Lake Ohrid. Electron spin resonance (ESR) dating of mollusc shells from the same stratigraphic level yielded an age of 130 ± 28 ka. Lithofacies III sediments, i.e. a stratigraphic subdivision comprising the basal succession of core Co1200 between 181.5–263 cm, appeared solid, greyish-white, and consisted almost entirely of silt-sized endogenic calcite (CaCO3>70%) and intact and broken mollusc shells. Here we compare the faunal composition of the thanatocoenosis with recent mollusc associations in Lake Ohrid. A total of 13 mollusc species (9 gastropod and 4 bivalve species) could be identified within Lithofacies III sediments. The value of sediment core fossils for reconstructing palaeoenvironmental settings was evaluated and the agreement between sediment and palaeontological proxies was tested. The study also aims at investigating major faunal changes since the Last Interglacial and searching for signs of extinction events. The combined findings of the ecological study and the sediment characteristics suggest deposition in a shallow water environment during the Last Interglacial. The fossil fauna exclusively included species also found in the present fauna, i.e. no extinction events are evident for this site since the Last Interglacial. The thanatocoenosis showed the highest similarity with recent Intermediate Layer (5–25 m water depth) mollusc assemblages. The demonstrated existence of a mollusc fossil record in Lake Ohrid sediment cores also has great significance for future deep drilling projects. It can be hoped that a more far reaching mollusc fossil record will then be obtained, enabling insight into the early evolutionary history of Lake Ohrid.

Comparative carbon cycle dynamics of the present and last interglacial

Changes in temperature and carbon dioxide during glacial cycles recorded in Antarctic ice cores are tightly coupled. However, this relationship does not hold for interglacials. While climate cooled towards the end of both the last (Eemian) and present (Holocene) interglacials, CO₂ remained stable during the Eemian while rising in the Holocene. We identify and review twelve biogeochemical mechanisms of terrestrial (vegetation dynamics and CO₂ fertilization, land use, wild fire, accumulation of peat, changes in permafrost carbon, subaerial volcanic outgassing) and marine origin (changes in sea surface temperature, carbonate compensation to deglaciation and terrestrial biosphere regrowth, shallow-water carbonate sedimentation, changes in the soft tissue pump, and methane hydrates), which potentially may have contributed to the CO₂ dynamics during interglacials but which remain not well quantified. We use three Earth System Models (ESMs) of intermediate complexity to compare effects of selected mechanisms on the interglacial CO₂ and δ¹³ CO₂ changes, focusing on those with substantial potential impacts: namely carbonate sedimentation in shallow waters, peat growth, and (in the case of the Holocene) human land use. A set of specified carbon cycle forcings could qualitatively explain atmospheric CO₂ dynamics from 8ka BP to the pre-industrial. However, when applied to Eemian boundary conditions from 126 to 115 ka BP, the same set of forcings led to disagreement with the observed direction of CO₂ changes after 122 ka BP. This failure to simulate late-Eemian CO₂ dynamics could be a result of the imposed forcings such as prescribed CaCO₃ accumulation and/or an incorrect response of simulated terrestrial carbon to the surface cooling at the end of the interglacial. These experiments also reveal that key natural processes of interglacial CO₂ dynamics eshallow water CaCO₃ accumulation, peat and permafrost carbon dynamics are not well represented in the current ESMs. Global-scale modeling of these long-term carbon cycle components started only in the last decade, and uncertainty in parameterization of these mechanisms is a main limitation in the successful modeling of interglacial CO₂ dynamics.