Relations between soil surface roughness, tortuosity, tillage treatments, rainfall intensity and soil and water losses from a red yellow latosol

The soil surface roughness increases water retention and infiltration, reduces the runoff volume and speed and influences soil losses by water erosion. Similarly to other parameters, soil roughness is affected by the tillage system and rainfall volume. Based on these assumptions, the main purpose of this study was to evaluate the effect of tillage treatments on soil surface roughness (RR) and tortuosity (T) and to investigate the relationship with soil and water losses in a series of simulated rainfall events. The field study was carried out at the experimental station of EMBRAPA Southeastern Cattle Research Center in São Carlos (Fazenda Canchim), in São Paulo State, Brazil. Experimental plots of 33 m² were treated with two tillage practices in three replications, consisting of: untilled (no-tillage) soil (NTS) and conventionally tilled (plowing plus double disking) soil (CTS). Three successive simulated rain tests were applied in 24 h intervals. The three tests consisted of a first rain of 30 mm/h, a second of 30 mm/h and a third rain of 70 mm/h. Immediately after tilling and each rain simulation test, the surface roughness was measured, using a laser profile meter. The tillage treatments induced significant changes in soil surface roughness and tortuosity, demonstrating the importance of the tillage system for the physical surface conditions, favoring water retention and infiltration in the soil. The increase in surface roughness by the tillage treatments was considerably greater than its reduction by rain action. The surface roughness and tortuosity had more influence on the soil volume lost by surface runoff than in the conventional treatment. Possibly, other variables influenced soil and water losses from the no-tillage treatments, e.g., soil type, declivity, slope length, among others not analyzed in this study.

Comparison of epifaunal assemblages between Cymodocea nodosa and Caulerpa prolifera meadows in Gran Canaria (eastern Atlantic)

Máster en Oceanografía

Computational studies on the structure and stabilities of magnetic inter-metallic compounds

The purpose of this thesis is to further the understanding of the structural, electronic and magnetic properties of ternary inter-metallic compounds using density functional theory (DFT). Four main problems are addressed. First, a detailed analysis on the ternary Heusler compounds is made. It has long been known that many Heusler compounds ($X_2YZ$; $X$ and $Y$ transition elements, $Z$ main group element) exhibit interesting half-metallic and ferromagnetic properties. In order to understand these, the dependence of magnetic and electronic properties on the structural parameters, the type of exchange-correlation functional and electron-electron correlation was examined. It was found that almost all Co$_2YZ$ Heusler compounds exhibit half-metallic ferromagnetism. It is also observed that $X$ and $Y$ atoms mainly contribute to the total magnetic moment. The magnitude of the total magnetic moment is determined only indirectly by the nature of $Z$ atoms, and shows a trend consistent with Slater-Pauling behaviour in several classes of these compounds. In contrast to experiments, calculations give a non-integer value of the magnetic moment in certain Co$_2$-based Heusler compounds. To explain deviations of the calculated magnetic moment, the LDA+$U$ scheme was applied and it was found that the inclusion of electron-electron correlation beyond the LSDA and GGA is necessary to obtain theoretical description of some Heusler compounds that are half-metallic ferromagnets. The electronic structure and magnetic properties of substitutional series of the quaternary Heusler compound Co$_2$Mn$_{1-x}$Fe$_x$Si were investigated under LDA+$U$. The calculated band structure suggest that the most stable compound in a half-metallic state will occur at an intermediate Fe concentration. These calculated findings are qualitatively confirmed by experimental studies. Second, the effect of antisite disordering in the Co$_2$TiSn system was investigated theoretically as well as experimentally. Preservation of half-metallicity for Co$_2$TiSn was observed with moderate antisite disordering and experimental findings suggest that the Co and Ti antisites disorder amounts to approximately 10~% in the compound. Third, a systematic examination was carried out for band gaps and the nature (covalent or ionic) of bonding in semiconducting 8- and 18-electron or half-metallic ferromagnet half-Heusler compounds. It was found that the most appropriate description of these compounds from the viewpoint of electronic structures is one of a $YZ$ zinc blende lattice stuffed by the $X$ ion. Simple valence rules are obeyed for bonding in the 8- and 18-electron compounds. Fourth, hexagonal analogues of half-Heusler compounds have been searched. Three series of compounds were investigated: GdPdSb, GdAutextit{X} (textit{X} = Mn, Cd and In) and EuNiP. GdPdSb is suggested as a possible half-metallic weak ferromagnet at low temperature. GdAutextit{X} (textit{X} = Mn, Cd and In) and EuNiP were investigated because they exhibit interesting bonding, structural and magnetic properties. The results qualitatively confirm experimental studies on magnetic and structural behaviour in GdPdSb, GdAutextit{X} (textit{X} = Mn, Cd and In) and EuNiP compounds. ~

Structural and strain analysis in the Late Paleozoic coastal accretionary wedge of central Chile

Abstract In this study structural and finite strain data are used to explore the tectonic evolution and the exhumation history of the Chilean accretionary wedge. The Chilean accretionary wedge is part of a Late Paleozoic subduction complex that developed during subduction of the Pacific plate underneath South America. The wedge is commonly subdivided into a structurally lower Western Series and an upper Eastern Series. This study shows the progressive development of structures and finite strain from the least deformed rocks in the eastern part of the Eastern Series of the accretionary wedge to higher grade schist of the Western Series at the Pacific coast. Furthermore, this study reports finite-strain data to quantify the contribution of vertical ductile shortening to exhumation. Vertical ductile shortening is, together with erosion and normal faulting, a process that can aid the exhumation of high-pressure rocks. In the east, structures are characterized by upright chevron folds of sedimentary layering which are associated with a penetrative axial-plane foliation, S1. As the F1 folds became slightly overturned to the west, S1 was folded about recumbent open F2 folds and an S2 axial-plane foliation developed. Near the contact between the Western and Eastern Series S2 represents a prominent subhorizontal transposition foliation. Towards the structural deepest units in the west the transposition foliation became progressively flat lying. Finite-strain data as obtained by Rf/Phi and PDS analysis in metagreywacke and X-ray texture goniometry in phyllosilicate-rich rocks show a smooth and gradual increase in strain magnitude from east to west. There are no evidences for normal faulting or significant structural breaks across the contact of Eastern and Western Series. The progressive structural and strain evolution between both series can be interpreted to reflect a continuous change in the mode of accretion in the subduction wedge. Before ~320-290 Ma the rocks of the Eastern Series were frontally accreted to the Andean margin. Frontal accretion caused horizontal shortening and upright folds and axial-plane foliations developed. At ~320-290 Ma the mode of accretion changed and the rocks of the Western Series were underplated below the Andean margin. This basal accretion caused a major change in the flow field within the wedge and gave rise to vertical shortening and the development of the penetrative subhorizontal transposition foliation. To estimate the amount that vertical ductile shortening contributed to the exhumation of both units finite strain is measured. The tensor average of absolute finite strain yield Sx=1.24, Sy=0.82 and Sz=0.57 implying an average vertical shortening of ca. 43%, which was compensated by volume loss. The finite strain data of the PDS measurements allow to calculate an average volume loss of 41%. A mass balance approximates that most of the solved material stays in the wedge and is precipitated in quartz veins. The average of relative finite strain is Sx=1.65, Sy=0.89 and Sz=0.59 indicating greater vertical shortening in the structurally deeper units. A simple model which integrates velocity gradients along a vertical flow path with a steady-state wedge is used to estimate the contribution of deformation to ductile thinning of the overburden during exhumation. The results show that vertical ductile shortening contributed 15-20% to exhumation. As no large-scale normal faults have been mapped the remaining 80-85% of exhumation must be due to erosion.

Design and synthesis of multipotent drugs: application to Alzheimer's disease and benign prostatic hyperplasia

The aim of this thesis was to synthesize multipotent drugs for the treatment of Alzheimer’s disease (AD) and for benign prostatic hyperplasia (BPH), two diseases that affect the elderly. AD is a neurodegenerative disorder that is characterized, among other factors, by loss of cholinergic neurons. Selective activation of M1 receptors through an allosteric site could restore the cholinergic hypofunction, improving the cognition in AD patients. We describe here the discovery and SAR of a novel series of quinone derivatives. Among them, 1 was the most interesting, being a high M1 selective positive allosteric modulator. At 100 nM, 1 triplicated the production of cAMP induced by oxotremorine. Moreover, it inhibited AChE and it displayed antioxidant properties. Site-directed mutagenesis experiments indicated that 1 acts at an allosteric site involving residue F77. Thus, 1 is a promising drug because the M1 activation may offer disease-modifying properties that could address and reduce most of AD hallmarks. BPH is an enlargement of the prostate caused by increased cellular growth. Blockade of α1-ARs is the predominant form of medical therapy for the treatment of the symptoms associated with BPH. α1-ARs are classified into three subtypes. The α1A- and α1D-AR subtypes are predominant in the prostate, while α1B-ARs regulate the blood pressure. Herein, we report the synthesis of quinazoline-derivatives obtained replacing the piperazine ring of doxazosin and prazosin with (S)- or (R)-3-aminopiperidine. The presence of a chiral center in the 3-C position of the piperidine ring allowed us to exploit the importance of stereochemistry in the binding at α1-ARs. It turned out that the S configuration at the 3-C position of the piperidine increases the affinity of the compounds at all three α1-AR subtypes, whereas the configuration at the benzodioxole ring of doxazosin derivatives is not critical for the interaction with α1-ARs.

Soil application of Meliaceae derivatives: effect on carbon and nitrogen dynamics in the soil-plant system

The effect of soil incorporation of 7 Meliaceae derivatives (6 commercial neem cakes and leaves of Melia azedarach L.) on C and N dynamics and on nutrient availability to micropropagated GF677 rootstock was investigated. In a first laboratory incubation experiment the derivatives showed different N mineralization dynamics, generally well predicted by their C:N ratio and only partly by their initial N concentration. All derivatives increased microbial biomass C, thus representing a source of C for the soil microbial population. Soil addition of all neem cakes (8 g kg-1) and melia leaves (16 g kg-1) had a positive effect on plant growth and increased root N uptake and leaf green colour of micropropagated plants of GF677. In addition, the neem cakes characterized by higher nutrient concentration increased P and K concentration in shoot and leaves 68 days after the amendment. In another experiment, soil incorporation of 15N labeled melia leaves (16 g kg-1) had no effect on the total amount of plant N, however the percentage of melia derived-N of treated plants ranged between 0.8% and 34% during the experiment. At the end of the growing season, about 7% of N added as melia leaves was recovered in plant, while 70% of it was still present in soil. Real C mineralization and the priming effect induced by the addition of the derivatives were quantified by a natural 13C abundance method. The real C mineralization of the derivatives ranged between 22% and 40% of added-C. All the derivatives studied induced a positive priming effect and, 144 days after the amendment, the amount of C primed corresponded to 26% of added-C, for all the derivatives. Despite this substantial priming effect, the C balance of the soil, 144 days after the amendment, always resulted positive.

The atmospheric stable boundary layer: Data analysis and comparison with similarity theories

The objective of this dissertation is to study the structure and behavior of the Atmospheric Boundary Layer (ABL) in stable conditions. This type of boundary layer is not completely well understood yet, although it is very important for many practical uses, from forecast modeling to atmospheric dispersion of pollutants. We analyzed data from the SABLES98 experiment (Stable Atmospheric Boundary Layer Experiment in Spain, 1998), and compared the behaviour of this data using Monin-Obukhov's similarity functions for wind speed and potential temperature. Analyzing the vertical profiles of various variables, in particular the thermal and momentum fluxes, we identified two main contrasting structures describing two different states of the SBL, a traditional and an upside-down boundary layer. We were able to determine the main features of these two states of the boundary layer in terms of vertical profiles of potential temperature and wind speed, turbulent kinetic energy and fluxes, studying the time series and vertical structure of the atmosphere for two separate nights in the dataset, taken as case studies. We also developed an original classification of the SBL, in order to separate the influence of mesoscale phenomena from turbulent behavior, using as parameters the wind speed and the gradient Richardson number. We then compared these two formulations, using the SABLES98 dataset, verifying their validity for different variables (wind speed and potential temperature, and their difference, at different heights) and with different stability parameters (zita or Rg). Despite these two classifications having completely different physical origins, we were able to find some common behavior, in particular under weak stability conditions.

Synthesis of new bioactive β-lactam compounds

New biologically active β-lactams were designed and synthesized, developing novel antibiotics and enzymatic inhibitors directed toward specific targets. Within a work directed to the synthesis of mimetics for RGD (Arg-Gly-Asp) sequence able to interact with αvβ3 and α5β1-type integrins, new activators were developed and their Structure-Activity Relationships (SAR) analysis deepened, enhancing their activity range towards the α4β1 isoform. Moreover, to synthesize novel compounds active both against bacterial infections and pulmonary conditions of cystic fibrosis patients, new β-lactam candidates were studied. Among the abundant library of β-lactams prepared, mainly with antioxidant and antibacterial double activities, it was identified a single lead to be pharmacologically tested in vivo. Its synthesis was optimized up to the gram-scale, and pretreatment method and HPLC-MS/MS analytical protocol for sub-nanomolar quantifications were developed. Furthermore, replacement of acetoxy group in 4-acetoxy-azetidinone derivatives was studied with different nucleophiles and in aqueous media. A phosphate group was introduced and the reactivity exploited using different hydroxyapatites, obtaining biomaterials with multiple biological activities. Following the same kind of reactivity, a small series of molecules with a β-lactam and retinoic hybrid structure was synthesized as epigenetic regulators. Interacting with HDACs, two compounds were respectively identified as an inhibitor of cell proliferation and a differentiating agent on steam cells. Additionally, in collaboration with Professor L. De Cola at ISIS, University of Strasbourg, some new photochemically active β-lactam Pt (II) complexes were designed and synthesized to be used as bioprobes or theranostics. Finally, it was set up and optimized the preparation of new chiral proline-derived α-aminonitriles through an enantioselective Strecker reaction, and it was developed a chemo-enzymatic oxidative method for converting alcohols to aldehydes or acid in a selective manner, and amines to relative aldehydes, amides or imines. Moreover, enzymes and other green chemistry methodologies were used to prepare Active Pharmaceutical Ingredients (APIs).

The importance of visual and olfactory stimuli during flower visits in Apis mellifera

Flowers attract honeybees using colour and scent signals. Bimodality (having both scent and colour) in flowers leads to increased visitation rates, but how the signals influence each other in a foraging situation is still quite controversial. We studied four basic questions: When faced with conflicting scent and colour information, will bees choose by scent and ignore the “wrong” colour, or vice versa? To get to the bottom of this question, we trained bees on scent-colour combination AX (rewarded) versus BY (unrewarded) and tested them on AY (previously rewarded colour and unrewarded scent) versus BX (previously rewarded scent and unrewarded colour). It turned out that the result depends on stimulus quality: if the colours are very similar (unsaturated blue and blue-green), bees choose by scent. If they are very different (saturated blue and yellow), bees choose by colour. We used the same scents, lavender and rosemary, in both cases. Our second question was: Are individual bees hardwired to use colour and ignore scent (or vice versa), or can this behaviour be modified, depending on which cue is more readily available in the current foraging context? To study this question, we picked colour-preferring bees and gave them extra training on scent-only stimuli. Afterwards, we tested if their preference had changed, and if they still remembered the scent stimulus they had originally used as their main cue. We came to the conclusion that a colour preference can be reversed through scent-only training. We also gave scent-preferring bees extra training on colour-only stimuli, and tested for a change in their preference. The number of animals tested was too small for statistical tests (n = 4), but a common tendency suggested that colour-only training leads to a preference for colour. A preference to forage by a certain sensory modality therefore appears to be not fixed but flexible, and adapted to the bee’s surroundings. Our third question was: Do bees learn bimodal stimuli as the sum of their parts (elemental learning), or as a new stimulus which is different from the sum of the components’ parts (configural learning)? We trained bees on bimodal stimuli, then tested them on the colour components only, and the scent components only. We performed this experiment with a similar colour set (unsaturated blue and blue-green, as above), and a very different colour set (saturated blue and yellow), but used lavender and rosemary for scent stimuli in both cases. Our experiment yielded unexpected results: with the different colours, the results were best explained by elemental learning, but with the similar colour set, bees exhibited configural learning. Still, their memory of the bimodal compound was excellent. Finally, we looked at reverse-learning. We reverse-trained bees with bimodal stimuli to find out whether bimodality leads to better reverse-learning compared to monomodal stimuli. We trained bees on AX (rewarded) versus BY (unrewarded), then on AX (unrewarded) versus BY (rewarded), and finally on AX (rewarded) and BY (unrewarded) again. We performed this experiment with both colour sets, always using the same two scents (lavender and rosemary). It turned out that bimodality does not help bees “see the pattern” and anticipate the switch. Generally, bees trained on the different colour set performed better than bees trained on the similar colour set, indicating that stimulus salience influences reverse-learning.

The Arabidopsis PHYTOCHROME KINASE SUBSTRATE2 protein is a phototropin signaling element that regulates leaf flattening and leaf positioning

In Arabidopsis (Arabidopsis thaliana), the blue light photoreceptor phototropins (phot1 and phot2) fine-tune the photosynthetic status of the plant by controlling several important adaptive processes in response to environmental light variations. These processes include stem and petiole phototropism (leaf positioning), leaf flattening, stomatal opening, and chloroplast movements. The PHYTOCHROME KINASE SUBSTRATE (PKS) protein family comprises four members in Arabidopsis (PKS1-PKS4). PKS1 is a novel phot1 signaling element during phototropism, as it interacts with phot1 and the important signaling element NONPHOTOTROPIC HYPOCOTYL3 (NPH3) and is required for normal phot1-mediated phototropism. In this study, we have analyzed more globally the role of three PKS members (PKS1, PKS2, and PKS4). Systematic analysis of mutants reveals that PKS2 (and to a lesser extent PKS1) act in the same subset of phototropin-controlled responses as NPH3, namely leaf flattening and positioning. PKS1, PKS2, and NPH3 coimmunoprecipitate with both phot1-green fluorescent protein and phot2-green fluorescent protein in leaf extracts. Genetic experiments position PKS2 within phot1 and phot2 pathways controlling leaf positioning and leaf flattening, respectively. NPH3 can act in both phot1 and phot2 pathways, and synergistic interactions observed between pks2 and nph3 mutants suggest complementary roles of PKS2 and NPH3 during phototropin signaling. Finally, several observations further suggest that PKS2 may regulate leaf flattening and positioning by controlling auxin homeostasis. Together with previous findings, our results indicate that the PKS proteins represent an important family of phototropin signaling proteins.

Channels and transporters. Mini-symposium of the Division of Medicinal Chemistry (DMC) of the Swiss Chemical Society (SCS) at the Department of Chemistry, University of Basel, May 27, 2010

During a half-day symposium, the topic 'Channels and Transporters' was covered with five lectures, including a presentation on 'Introduction and Basics of Channels and Transporters' by Beat Ernst, lectures on structure, function and physiology of channels and transporters ('The Structural Basis for Ion Conduction and Gating in Pentameric Ligand-Gated Ion Channels' by Raimund Dutzler and 'Uptake and Efflux Transporters for Endogenous Substances and for Drugs' by Dietrich Keppler), and a case study lecture on 'Avosentan' by Werner Neidhart. The program was completed by Matthias Hediger who introduced to the audience the National Center of Competence in Research (NCCR)-TransCure in his lecture entitled 'From Transport Physiology to Identification of Therapeutic Targets'.

Circulation dynamics and its influence on European and Mediterranean January-April climate over the past half millennium: results and insights from instrumental data, documentary evidence and coupled climate models

We use long instrumental temperature series together with available field reconstructions of sea-level pressure (SLP) and three-dimensional climate model simulations to analyze relations between temperature anomalies and atmospheric circulation patterns over much of Europe and the Mediterranean for the late winter/early spring (January–April, JFMA) season. A Canonical Correlation Analysis (CCA) investigates interannual to interdecadal covariability between a new gridded SLP field reconstruction and seven long instrumental temperature series covering the past 250 years. We then present and discuss prominent atmospheric circulation patterns related to anomalous warm and cold JFMA conditions within different European areas spanning the period 1760–2007. Next, using a data assimilation technique, we link gridded SLP data with a climate model (EC-Bilt-Clio) for a better dynamical understanding of the relationship between large scale circulation and European climate. We thus present an alternative approach to reconstruct climate for the pre-instrumental period based on the assimilated model simulations. Furthermore, we present an independent method to extend the dynamic circulation analysis for anomalously cold European JFMA conditions back to the sixteenth century. To this end, we use documentary records that are spatially representative for the long instrumental records and derive, through modern analogs, large-scale SLP, surface temperature and precipitation fields. The skill of the analog method is tested in the virtual world of two three-dimensional climate simulations (ECHO-G and HadCM3). This endeavor offers new possibilities to both constrain climate model into a reconstruction mode (through the assimilation approach) and to better asses documentary data in a quantitative way.

Adsorption behavior of redox-active suppressor additives: Combined electrochemical and STM studies

The redox chemistry and the related surface phase behavior of Safranine (SAF) and Janus Green B (JGB) have been studied by means of cyclic voltammetry in combination with in situ Scanning Tunneling Microscopy using HOPG (Highly Oriented Pyrolytic Graphite) and single crystalline Cu(1 0 0) as model substrates, both revealing different widths of the accessible potential windows. JGB and SAF serve as prototypical heterocyclic suppressor/leveler additives that are used for the metallization of 3D-TSVs (3D Through Silicon Vias) following a classical "leveling" concept. SAF can be considered as the reductive decomposition product of JGB that is formed at the copper/electrolyte interface upon electroplating. Both additives reveal a pronounced pH-dependent redox-chemistry with redox-transitions lying close to or even beyond the anodic limit of the copper potential window. Affected by these redox-processes are in particular the aromatic cores of those heterocycles that can be (quasi)reversibly reduced by a two electron transfer process within the potential window of copper. Therefore we identify the reduced form of those dyes as the active components for the suppressing/leveling effect in copper plating. STM data clearly shows a dye surface phase behavior that is crucially determined by its potential-dependent redox-chemistry. This will be exemplarily discussed for the SAF dye. On chloride-modified Cu(1 0 0) mono-reduced SAF forms a structurally well-defined monolayer of cationic stacking polymers. However, this coupled anion/cation layer reveals only minor suppressing capabilities with respect to the copper dissolution and deposition processes. Complete reduction of the aromatic heterocycle finally leads to the 3D precipitation of hydrophobic reaction products. 3D clusters of this SAF precipitate are discussed as the active structural motif for the suppressing effect of these dyes. (C) 2011 Elsevier Ltd. All rights reserved.