Mixed Layer formation and restratification in presence of mesoscale and submesoscale turbulence

Recent realistic high resolution modeling studies show a net increase of submesoscale activity in fall and winter when the mixed layer depth is at its maximum. This submesoscale activity increase is associated with a reduced deepening of the mixed layer. Both phenomena can be related to the development of mixed layer instabilities, which convert available potential energy into submesoscale eddy kinetic energy and contribute to a fast restratification by slumping the horizontal density gradient in the mixed layer. In the present work, the mixed layer formation and restratification was studied by uniformly cooling a fully turbulent zonal jet in a periodic channel at different resolutions, from eddy resolving (10 km) to submesoscale permitting (2 km). The effect of the submesoscale activity, highlighted by these different horizontal resolutions, was quantified in terms of mixed layer depth, restratification rate and buoyancy fluxes. Contrary to many idealized studies focusing on the restratification phase only, this study addresses a continuous event of mixed layer formation followed by its complete restratification. The robustness of the present results was established by ensemble simulations. The results show that, at higher resolution, when submesoscale starts to be resolved, the mixed layer formed during the surface cooling is significantly shallower and the total restratification almost three times faster. Such differences between coarse and fine resolution models are consistent with the submesoscale upward buoyancy flux, which balances the convection during the formation phase and accelerates the restratification once the surface cooling is stopped. This submesoscale buoyancy flux is active even below the mixed layer. Our simulations show that mesoscale dynamics also cause restratification, but on longer time scales. Finally, the spatial distribution of the mixed layer depth is highly heterogeneous in the presence of submesoscale activity, prompting the question of whether it is possible to parameterize submesoscale effects and their effects on the marine biology as a function of a spatially-averaged mixed layer depth.

Working with Student Teachers: A Mixed Methods Study to Examine the Roles and Self-Identified Dispositions of Cooperating Teachers

A critical component of teacher education is the field experience during which candidates practice under the supervision of experienced teachers. Programs use the InTASC Standards to define the requisite knowledge, skills, and dispositions for teaching. Practicing teachers are familiar with the concepts of knowledge and skills, but they are less familiar with dispositions. Practicing teachers who mentor prospective teachers are underrepresented in the literature, but they are critical to teacher preparation. The research goals were to describe the self-identified dispositions of cooperating teachers, identify what cooperating teachers consider their role in preparing prospective teachers, and explain challenges that cooperating teachers face. Using a mixed methods design, I conducted a quantitative survey followed by a qualitative case study. When I compared survey and case study data, cooperating teachers report possessing InTASC critical dispositions described in Standard 2: Learning Differences, Standard 3: Learning Environments, and Standard 9: Professional Learning and Ethical Practice, but not Standard 6: Assessment and Standard 10: Leadership and Collaboration. Cooperating teachers assume the roles of modeler, mentor and advisor, and informal evaluator. They explain student teachers often lack skills and dispositions to assume full teaching responsibilities and recommend that universities better prepare candidates for classrooms. Cooperating teachers felt university evaluations were not relevant to teaching reality. I recommend modifying field experiences to increase the quantity and duration of classroom placements. I suggest further research to detail cooperating teacher dispositions, compare cooperating teachers who work with different universities, and determine if cooperating teacher dispositions influence student teacher dispositions.

Project work in a Basque L2 classroom: students’ perceptions

[EN] Project Work has been acknowledged as an efficient medium for language learning for more than two decades (Stoller, 2006) according to the numerous successful applications of project-based programmes that have been reported. In spite of the lack of sufficient controlled studies to assess the benefits of project work, and the existence of some studies giving evidence of students discontent with project work, the reports given by second language (SL) and foreign language students (FL) who have experienced project based instruction give support to the success attributed to project-based learning, as they recognised having improved language skills, learnt content, developed real life skills, as well as gained in self-confidence and motivation (Sierra, 2008 and 2011; Stoller, 2006). The aim of the present study is to explore some key issues involved in implementing a project-based programme focusing on the students’ perceptions of learning gains, their views on the collaborative assessment scheme used in the programme, and the students’ overall evaluations of the implementation of project work in a post-compulsory secondary education context in Navarre, Spain, with students learning Basque as a second language. A group of 12 students enrolled in a project work based programme participated in the study. Results showed that the students’ perceptions were very positive concerning doing projects, learning gains and group work, although more grammar instruction and teacher-fronted activities were requested by the students. However, the collaborative assessment process and the use of a Notebook/Diary as a reflection tool bore mixed evaluations.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Work-related discussions between French rheumatologists and their rheumatoid arthritis patients

International audience

Integrating Architecture for a Live-Work Lifestyle

Urban centers all around the world are striving to re-orient themselves to promoting ideals of human engagement, flexibility, openness and synergy, that thoughtful architecture can provide. From a time when solitude in one’s own backyard was desirable, today’s outlook seeks more, to cater to the needs of diverse individuals and that of collaborators. This thesis is an investigation of the role of architecture in realizing how these ideals might be achieved, using Mixed Use Developments as the platform of space to test these designs ideas on. The author also investigates, identifies, and re-imagines how the idea of live-work excites and attracts users and occupants towards investing themselves in Mixed Used Developments (MUD’s), in urban cities. On the premise that MUDs historically began with an intention of urban revitalization, lying in the core of this spatial model, is the opportunity to investigate what makes mixing of uses an asset, especially in the eyes to today’s generation. Within the framework of reference to the current generation, i.e. the millennial population and alike, who have a lifestyle core that is urban-centric, the excitement for this topic is in the vision of MUD’s that will spatially cater to a variety in lifestyles, demographics, and functions, enabling its users to experience a vibrant 24/7 destination. Where cities are always in flux, the thesis will look to investigate the idea of opportunistic space, in a new MUD, that can also be perceived as an adaptive reuse of itself. The sustainability factor lies in the foresight of the transformative and responsive character of the different uses in the MUD at large, which provides the possibility to cater to a changing demand of building use over time. Delving into the architectural response, the thesis in the process explores, conflicts, tensions, and excitements, and the nature of relationships between different spatial layers of permanence vs. transformative, public vs. private, commercial vs. residential, in such an MUD. At a larger scale, investigations elude into the formal meaning and implications of the proposed type of MUD’s and the larger landscapes in which they are situated, with attempts to blur the fine line between architecture and urbanism. A unique character of MUD’s is the power it has to draw in people at the ground level and lead them into exciting spatial experiences. While the thesis stemmed from a purely objective and theoretical standpoint, the author believes that it is only when context is played into the design thinking process, that true architecture may start to flourish. The unique The significance of this thesis lies on the premise that the author believes that this re-imagined MUD has immense opportunity to amplify human engagement with designed space, and in the belief that it will better enable fostering sustainable communities and in the process, enhance people’s lives.

Mesoporous mixed Nb2O5-ZrO2 catalysts for dehydration of glucose into 5-hydroxymethylfurfural

Biomass is the world’s most important renewable carbon source, whose major component, carbohydrates, can be valorized by transformation into biofuels and high value-added chemicals. Among the latter, 5-hydroxymethylfurfural (HMF), obtained by C6 carbohydrates dehydration, is a versatile and key intermediate for the production of a large spectrum of biobased chemicals. Different catalytic systems have been evaluated for HMF production, mostly based on heterogeneous catalysis as alternative to the use of conventional mineral acids [1]. Moreover, niobium oxide has shown interesting properties as acid catalyst for dehydration of sugars [2-3]. On the other hand, the high surface area and large pore size of mesoporous solids make them suitable for many catalytic processes. In the present work, the dehydration of glucose to HMF has been evaluated by using different mesoporous mixed Nb2O5-ZrO2 in a biphasic water–Methyl Isobutyl Ketone (MIBK) solvent system to avoid the HMF degradation. Different experimental parameters, such as reaction temperature and time, as well as the addition of CaCl2 have been studied in order to maximize the HMF yield.N2 adsorption-desorption isotherms have corroborated the mesostructured character of catalysts, being all isotherms of Type IV according to the IUPAC classification. BET surface area decreases for catalysts with higher Zr content (Table 1). Likewise, pore volume and average pore diameter values diminish after Zr incorporation. Concerning the acid properties, a clear correlation between Nb and acidity can be observed, in such a way that total acidity, as deduced from NH3-TPD, decreases when the Zr content rises, and consequently the amount of Nb is reduced.These mesoporous Nb-Zr catalysts have been tested in the dehydration of glucose to HMF at 175 ºC under batch operation in aqueous solution, using MIBK as co-solvent. It can be observed that both glucose conversion and HMF yield increase with the Nb content, being maximum (90% and 36%, respectively) after 90 minutes for Nb2O5. This trend changes when CaCl2 is added to the reaction medium, improving the catalytic performance of mixed oxides and ZrO2, but Nb2O5 maintains similar results than without salt addition. This could be justified by the interaction between CaCl2 and Lewis acid sites, since zirconium oxide possesses a higher amount of this acid sites type.

Peer interaction in mixed age groups: a study in the computer area of an early childhood education center in Portugal

The study was developed as a teacher-research project during initial teacher education – Masters Degree of Early Childhood and Primary Education, in Portugal. It analysed the interactions between children of 3 to 6 years old, during the use of the computer as a free choice activity, confronting situations between peers of the same age and situations between peers of different ages. The focus of the analysis was the collaborative interactions. This was a qualitative study. Children could choose the computer, amongst other interest areas, and work for around an hour in pairs. In the computer, children used mainly educational games. During four weeks, the interactions between the pairs were audio recorded. Field notes and informal interviews to the children were also used to collect data. Eleven children were involved in the study with ages ranging from 3 to 6 years old. Baseline data on children’s basic computer proficiency was collected using the Individualized Computer Proficiency Checklist (ICPC) by Hyun. The recorded interactions were analysed using the types of talk offered by Scrimshaw and Perkins and Wegerif and Scrimshaw: cumulative talk, exploratory talk, disputational talk, and tutorial talk. This framework was already used in a study in an early childhood education context in Portugal by Amante. The results reveal differences in computer use and characterize the observed interactions. Seven different pairs of children's interactions were analysed. More than a third of the interactions were cumulative talk, followed by exploratory talk, tutorial talk and disputational talk. Comparing same and mixed age pairs, we observed that cumulative talk is the more present interaction, but in same age pairs this is followed by exploratory talk whereas in the mixed age pairs it is tutorial talk that has the second largest percentage. The pairs formed by the children were very asymmetrical in terms of age and computer proficiency. This lead to the more tutorial interactions, where one children showed the other or directed him/her on how to play. The results show that collaboration is present during the use of a computer area in early childhood education. The free choice of the children means the adults can only suggest pairing suited to specific interactions between the children. Another way to support children in more exploratory talk interactions could be by discussing the way the older children can help the younger ones beyond directing or correcting their work.

Semi-implicit finite strain constitutive integration and mixed strain/stress control based on intermediate configurations

A new semi-implicit stress integration algorithm for finite strain plasticity (compatible with hyperelas- ticity) is introduced. Its most distinctive feature is the use of different parameterizations of equilibrium and reference configurations. Rotation terms (nonlinear trigonometric functions) are integrated explicitly and correspond to a change in the reference configuration. In contrast, relative Green–Lagrange strains (which are quadratic in terms of displacements) represent the equilibrium configuration implicitly. In addition, the adequacy of several objective stress rates in the semi-implicit context is studied. We para- metrize both reference and equilibrium configurations, in contrast with the so-called objective stress integration algorithms which use coinciding configurations. A single constitutive framework provides quantities needed by common discretization schemes. This is computationally convenient and robust, as all elements only need to provide pre-established quantities irrespectively of the constitutive model. In this work, mixed strain/stress control is used, as well as our smoothing algorithm for the complemen- tarity condition. Exceptional time-step robustness is achieved in elasto-plastic problems: often fewer than one-tenth of the typical number of time increments can be used with a quantifiable effect in accuracy. The proposed algorithm is general: all hyperelastic models and all classical elasto-plastic models can be employed. Plane-stress, Shell and 3D examples are used to illustrate the new algorithm. Both isotropic and anisotropic behavior is presented in elasto-plastic and hyperelastic examples.

New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.