Study of ionizable drugs transfer across the water/1,2-dichloroethane interface with phase volume ratio equal to unity using a three-electrode system

The electrochemical behavior of ionizable drugs (Amitriptyline, Diphenhydramine and Trihexyphenedyl) at the water/1,2-dichloroethane interface with the phase volume ratio (r = V-o/V-w) equal to 1 are investigated by cyclic voltammetry. The system is composed of an aqueous droplet supported at an Ag/AgCl disk electrode and it was covered with an organic solution. In this manner, a conventional three-electrode potentiostat can be used to study the ionizable drugs transfer process at a liquid/liquid interface. Physicochemical parameters such as the formal transfer potential, the Gibbs energy of transfer and the standard partition coefficients of the ionized forms of these drugs can be evaluated from cyclic voltammograms obtained. The obtained results have been summarized in ionic partition diagrams, which are a useful tool for predicting and interpreting the transfer mechanisms of ionizable drugs at the liquid/liquid interfaces and biological membranes.

Per-unit royalty and fixed-fee licensing in a differentiated Stackelberg model

In the present paper we consider a differentiated Stackelberg model, when the leader firm engages in an R&D process that gives an endogenous cost-reducing innovation. The aim is to study the licensing of the cost-reduction by a per-unit royalty and a fixed-fee. We analyse the implications of these types of licensing contracts over the R&D effort, the profits of the firms, the consumer surplus and the social welfare. By using comparative static analysis, we conclude that the degree of the differentiation of the goods plays an important role in the results.

Reaccions de cicloaddició [2+2+2] catalitzades per Rh(I)

The development of new chemical processes and efficient catalysts for the formation of carbon-carbon bonds is an important topic in organic chemistry. In particular, the [2+2+2] cycloaddition reaction involving different insaturations mainly alkynes, alkenes and nitriles is a highly efficient synthetic tool that allows polysubstituted benzenic, cyclohexadienic and pyridinic compounds to be obtained in one reaction step and in an atom economy process, resulting in the simultaneous formation of three new bonds in the formed ring. In recent years, research to produce new catalysts that can work effectively in mild reaction conditions has attracted great interest, as has the use of these processes in the synthesis of products of potential biological interest. This doctoral thesis is based on the methodological study of the rhodium(I)-catalyzed [2+2+2] cycloaddition reaction.

Comparison between univariate and bivariate geostatistical models for estimating catch per unit of effort (cpue): A simulation study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Comparing three indices of catch per unit effort using Bayesian geostatistics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Progettazione e sviluppo di una SDK in swift 2.1 per la piattaforma "Marketcloud"

Lo scopo di questa tesi di laurea è di presentare e documentare i risultati della tesi svolta in contesto aziendale presso la start-up "Marketcloud". L’obiettivo è stato quello di progettare, sviluppare e documentare una SDK REST in linguaggio Swift 2.1 per interfacciare eventuali future applicazioni iOS con le API Marketcloud. Viene fornita una panoramica sulla start-up in questione, sul linguaggio Swift, sulle motivazioni dietro lo sviluppo dell’SDK e sulle varie fasi di progettazione e sviluppo di quest’ultima. Tutto il lavoro in questione è documentato e reperibile sul repository Github di riferimento all'indirizzo https://github.com/Marketcloud/marketcloud-swift-sdk.

Sea ice cover, and bottom water and sediment characteristics at stations in the Amundsen Gulf, Canada

Seasonal dynamics in the activity of Arctic shelf benthos have been the subject of few local studies, and the pronounced among-site variability characterizing their results makes it difficult to upscale and generalize their conclusions. In a regional study encompassing five sites at 100-595 m water depth in the southeastern Beaufort Sea, we found that total pigment concentrations in surficial sediments, used as proxies of general food supply to the benthos, rose significantly after the transition from ice-covered conditions in spring (March-June 2008) to open-water conditions in summer (June-August 2008), whereas sediment Chl a concentrations, typical markers of fresh food input, did not. Macrobenthic biomass (including agglutinated foraminifera >500 µm) varied significantly among sites (1.2-6.4 g C/m**2 in spring, 1.1-12.6 g C/m**2 in summer), whereas a general spring-to-summer increase was not detected. Benthic carbon remineralisation also ranged significantly among sites (11.9-33.2 mg C/m**2/day in spring, 11.6-44.4 mg C/m**2/day in summer) and did in addition exhibit a general significant increase from spring-to-summer. Multiple regression analysis suggests that in both spring and summer, sediment Chl a concentration is the prime determinant of benthic carbon remineralisation, but other factors have a significant secondary influence, such as foraminiferan biomass (negative in both seasons), water depth (in spring) and infaunal biomass (in summer). Our findings indicate the importance of the combined and dynamic effects of food supply and benthic community patterns on the carbon remineralisation of the polar shelf benthos in seasonally ice-covered seas.

Detailed analysis of the organic carbon content in sediment cores M0002 and M0004

During IODP Expedition 302 (Arctic Coring Expedition-ACEX), the first scientific drilling campaign in the permantly ice-covered central Arctic Ocean, a 430 m thick sequence of upper Cretaceaous to Quaternary sediments has been drilled. The lower half of this sequence is composed of organic-carbon-rich (black shale-type) sediments with total organic carbon contents of about 1-14%. Significant amounts of the organic matter preserved in these sediments is of algae-type origin and accumulated under anoxic/euxinic conditions. Here, for the first time detailed data on the source-rock potential of these black shales are presented, indicating that most of the Eocene sediments have a (fair to) good source-rock potential, prone to generate a gas/oil mixture. The source-rock potential of the Campanian and upper Paleocene sediments, on the other hand, is rather low. The presence of oil or gas already generated in situ, however, can be ruled out due to the immaturity of the ACEX sediments.

Age determination of sediment cores off western Spitsbergen

The Late Weichselian glacial history of the continental shelf off western Spitsbergen is discussed, based on acoustic sub-bottom records and sediment cores. The outer part of Isfjorden and the inner shelf to the west of this fjord are characterized by a thin veneer (10-20 m) of glacigenic sediments and absence of ice-marginal features. Towards the outer shelf the sediment thickness increases significantly, and exceeds 500 m at the shelf edge. Possible moraine complexes were identified in this outer part. Sediment cores from the inner shelf sampled a firm diamicton, interpreted as till, beneath soft glaciomarine sediments. Radiocarbon dates on shells from the clay resting directly on the till, suggest an age of around 12,500 yrs B.P. for the base of the marine sequence. We argue that grounded ice covered the sites shortly before. In contrast to suggestions that the fjords and coast were partly ice free during the Late Weischselian, we conclude that the ice must have reached out onto the continental shelf.

Particle flux measurements from moorings and surface sediment studies of sediment cores in the SE Pacific Ocean

Flux of siliceous plankton and taxonomic composition of diatom and silicoflagellate assemblages were determined from sediment trap samples collected in coastal upwelling-influenced waters off northern Chile (30°S, CH site) under "normal" or non-El Niño (1993-94) and El Niño conditions (1997-98). In addition, concentration of biogenic opal and siliceous plankton, and diatom and silicoflagellate assemblages preserved in surface sediments are provided for a wide area between 27° and 43°S off Chile. Regardless of the year, winter upwelling determines the maximum production pattern of siliceous microorganisms, with diatoms numerically dominating the biogenic opal flux. During the El Niño year the export is markedly lower: on an annual basis, total mass flux diminished by 60%, and diatom and silicoflagellate export by 75%. Major components of the diatom flora maintain much of their regular seasonal cycle of flux maxima and minima during both sampling periods. Neritic resting spores (RS) of Chaetoceros dominate the diatom flux, mirroring the influence of coastal-upwelled waters at the CH trap site. Occurrence of pelagic diatoms species Fragilariopsis doliolus, members of the Rhizosoleniaceae, Azpeitia spp. and Nitzschia interruptestriata, secondary components of the assemblage, reflects the intermingling of warmer waters of the Subtropical Gyre. Dictyocha messanensis dominates the silicoflagellate association almost year-around, but Distephanus pulchra delivers ca. 60% of its annual production in less than three weeks during the winter peak. The siliceous thanatocoenosis is largely dominated by diatoms, whose assemblage shows significant qualitative and quantitative variations from north to south. Between 27° and 35°S, the dominance of RS Chaetoceros, Thalassionema nitzschioides var. nitzschioides and Skeletonema costatum reflects strong export production associated with occurrence of coastal upwelling. Both highest biogenic opal content and diatom concentration at 35° and 41°-43°S coincide with highest pigment concentrations along the Chilean coast. Predominance of the diatom species Thalassiosira pacifica and T. poro-irregulata, and higher relative contribution of the silicoflagellate Distephanus speculum at 41°-43°S suggest the influence of more nutrient-rich waters and low sea surface temperatures, probably associated with the Antarctic Circumpolar Water.

Age determination, foraminiferal abundance and stable isotope ratios of sediment core CH82-20

A core from the Mid-Atlantic Ridge at 43.5°N and ~3 km water depth shows distinct evidence of the deglacial events known as Heinrich event 1 (probably the marine equivalent of Oldest Dryas cooling in Europe) and the Younger Dryas. The Heinrich event, dated at three levels to between 14.3 and 15.0 ka, is marked by a minimum in foraminifera per gram, by maxima in rates of sedimentation, ice rafted debris per gram, and relative abundance of N. pachyderma (s.), and by a delta18O minimum in planktonic foraminifera. The Younger Dryas event is marked by peak abundance of N. pachyderma (s.) and a planktonic delta18O maximum. Benthic foraminiferal delta13C reaches minimum values during both the Heinrich event and the Younger Dryas. Our data indicate pronounced changes in surface water properties were coupled with reduced production of North Atlantic Deep Water at each of these times.