942 resultados para Co(II) and Ni(II) pyrazolyl complexes


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Higher education is faced with the challenge of strengthening students competencies for the constantly evolving technology-mediated practices of knowledge work. The knowledge creation approach to learning (Paavola et al., 2004; Hakkarainen et al., 2004) provides a theoretical tool to address learning and teaching organized around complex problems and the development of shared knowledge objects, such as reports, products, and new practices. As in professional work practices, it appears necessary to design sufficient open-endedness and complexity for students teamwork in order to generate unpredictable and both practically and epistemologically challenging situations. The studies of the thesis examine what kinds of practices are observed when student teams engage in knowledge creating inquiry processes, how the students themselves perceive the process, and how to facilitate inquiry with technology-mediation, tutoring, and pedagogical models. Overall, 20 student teams collaboration processes and productions were investigated in detail. This collaboration took place in teams or small groups of 3-6 students from multiple domain backgrounds. Two pedagogical models were employed to provide heuristic guidance for the inquiry processes: the progressive inquiry model and the distributed project model. Design-based research methodology was employed in combination with case study as the research design. Database materials from the courses virtual learning environment constituted the main body of data, with additional data from students self-reflections and student and teacher interviews. Study I examined the role of technology mediation and tutoring in directing students knowledge production in a progressive inquiry process. The research investigated how the scale of scaffolding related to the nature of knowledge produced and the deepening of the question explanation process. In Study II, the metaskills of knowledge-creating inquiry were explored as a challenge for higher education: metaskills refers to the individual, collective, and object-centered aspects of monitoring collaborative inquiry. Study III examined the design of two courses and how the elaboration of shared objects unfolded based on the two pedagogical models. Study IV examined how the arranged concept-development project for external customers promoted practices of distributed, partially virtual, project work, and how the students coped with the knowledge creation challenge. Overall, important indicators of knowledge creating inquiry were the following: new versions of knowledge objects and artifacts demonstrated a deepening inquiry process; and the various productions were co-created through iterations of negotiations, drafting, and versioning by the team members. Students faced challenges of establishing a collective commitment, devising practices to co-author and advance their reports, dealing with confusion, and managing culturally diverse teams. The progressive inquiry model, together with tutoring and technology, facilitated asking questions, generating explanations, and refocusing lines of inquiry. The involvement of the customers was observed to provide a strong motivation for the teams. On the evidence, providing team-specific guidance, exposing students to models of scientific argumentation and expert work practices, and furnishing templates for the intended products appear to be fruitful ways to enhance inquiry processes. At the institutional level, educators do well to explore ways of developing collaboration with external customers, public organizations or companies, and between educational units in order to enhance educational practices of knowledge creating inquiry.

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Use of natural xanthine derivates in medicine is complicated with their physical properties. Theobromine is poorly soluble while theophylline is highly sensitive to hydration. The aim of this study was to improve bioavailability of xanthines by co-crystallization, theophylline was also cocrystallized with carboxylic acids (capric, citric, glutaric, malenic, malonic, oxalic, stearic, succinic) and HPMC. Co-crystallization was performed by slow evaporation and ball milling. Physical stability was checked by wet granulation and water sorption methods, solubility was measured by intrinsic tablet dissolution. Theobromine formed co-crystal with other xanthines and theophylline interacted with all acids except stearic and HPMC, the latter showed alternative interactions based on hydrogen bonding. Hydration resistance was good in theophylline:succinic acid co-crystal and excellent in complexes containing capric, stearic acids and HPMC. Theophylline:HPMC showed improved solubility. The reported approach can promote use of xanthines and can be recommended for other compounds with similar problems.

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In order to further develop the logic of service, value creation, value co-creation and value have to be formally and rigorously defined, so that the nature, content and locus of value and the roles of service providers and customers in value creation can be unambiguously assessed. In the present article, following the underpinning logic of value-in-use, it is demonstrated that in order to achieve this, value creation is best defined as the customer’s creation of value-in-use. The analysis shows that the firm’s and customer’s processes and activities can be divided into a provider sphere, closed for the customer, and a customer sphere, closed for the firm. Value creation occurs in the customer sphere, whereas firms in the provider sphere facilitate value creation by producing resources and processes which represent potential value or expected value-in use for their customers. By getting access to the closed customer sphere, firms can create a joint value sphere and engage in customers’ value creation as co-creators of value with them. This approach establishes a theoretically sound foundation for understanding value creation in service logic, and enables meaningful managerial implications, for example as to what is required for co-creation of value, and also further theoretical elaborations.

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Ab initio MO calculations are performed on a series of ion-molecular and ion pair-molecular complexes of H2O + MX (MX = LiF, LiCl, NaCl, BeO and MgO) systems. BSSE-corrected stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies have been evaluated for all the structures of interest. The trends observed in the geometrical parameters and other properties calculated for the mono-hydrated contact ion pair complexes parallel those computed for the complexes of the individual ions. The bifurcated structures are found to be saddle points with an imaginary frequency corresponding to the rocking mode of water molecules. The solvent-shared ion pair complexes have high interaction energies. Trends in the internal force constant and harmonic frequency values are discussed in terms of ion-molecular and ion-pair molecular interactions.

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The reactions of (amino)spirocyclotriphosphazenes, N3P3(NMe2)4(NHCH2CH2NH) (1) and N3P3(NMe2)4(NHCH2CH2CH2NH) (2) with molybdenum- and tungsten-hexacarbonyls give complexes of the type [M(CO)4(L)] (L = 1 or 2) in which the phosphazenes act as bidentate chelating ligands via one of the phosphazene ring nitrogen atoms and one of the nitrogen atoms of the diaminoalkane moiety.

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The hydrolysis of beta-lactam antibiotics using zinc-containing metallo-beta-lactamases (m beta l) is one of the major bacterial defense systems. These enzymes can catalyze the hydrolysis of a variety of antibiotics including the latest generation of cephalosporins, cephamycins, and imipenem. It is shown in this paper that the cephalosporins having heterocyclic - SR side chains are less prone to m beta l-mediated hydrolysis than the antibiotics that do not have such side chains. This is partly due to the inhibition of enzyme activity by the thione moieties eliminated during hydrolysis. When the enzymatic hydrolysis of oxacillin was carried out in the presence of heterocyclic thiones such as MU, MDT, DMETT, and MMA, the catalytic activity of the enzyme was inhibited significantly by these compounds. Although the heterocyclic - SR moieties eliminated from the beta-lactams upon hydrolysis undergo a rapid tautomerism between thione and thiol forms, these compounds act as thiolate ligands toward zinc(II) ions. The structural characterization of two model tetranuclear zinc(II) thiolate complexes indicates that the -SR side chains eliminated from the antibiotics may interact with the zinc(II) metal center of m beta l through their sulfur atoms.

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Are evaporation of graphite with Fe, Co and Ni yields two distinct types of metal nanoparticles, wrapped in graphitic layers and highly resistant to oxidation. Electron microscopy shows that the metal particles (10-40 nm) in the stub region are encapsulated in carbon onions, the particles in the soot being considerably smaller (2-15 nm). The metal particles in the soot are either ferromagnetic with lowered Curie temperatures or superparamagnetic.

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Synthesis of the free-base tetrakis (3'-nitro/aminophenyl), (H2TNP/H(2)TAP) has been accomplished and its coordination behaviour towards Mg(II), Co(II), Zn(II) and Ag(II) ions is investigated. Optical and magnetic resonance properties of the metal derivatives MTNP and MTAP reveal that the aminoporphyrins exist as aggregates in solution. The aggregation is promoted by the coordination of the peripheral amino groups to neighbouring metalloporphyrins. Possible structures of aggregated species are proposed from the model studies.

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Zinc oxide ceramic varistors with simplified compositions of ZnO+Bi2O3+Co3O4+M(2)O (M=K or Na) show nonlinearity coefficients (alpha) of 40-75. The electron paramagnetic resonance spectra and optical reflectance spectra show that there is a direct interdependence between the oxidation state of transition metals and the alkali ions. The X-ray photoelectron spectra indicate that the alkali ions preserve a higher oxidation state of cobalt, Co(III), in the grain boundary regions than in the grain interiors having more Co(II). Admittance spectroscopy shows that, while the nature of traps remains unaltered, the trap density increases with the concentration of alkali ions near the interface. The observed defect states are associated with the grain bulk than with the grain boundary interfaces, as indicated by the isothermal capacitance transient signals

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An extensive search of the structural landscape of orcinol, 5-methyl-1,3-dihydroxybenzene, has been carried out with high throughput techniques. Polymorphs, pseudopolymorphs (solvates), and co-crystals are described. Several packing modes driven by O-H center dot center dot center dot N hydrogen bonds were identified for the orcinol N-base co-crystals and their hydrates. In these several structural variations, the OH group conformations in the orcinol molecule were found to depend on the choice of co-formers and the crystallization conditions employed. The structural landscape of a molecule is properly described by a sufficiently large number of related crystal structures, and high throughput crystallization followed by rapid structure determinations enables one to access these structures efficiently. Any understanding of this landscape would enable the crystal engineer to reasonably anticipate crystal structures of benzene-1,3-diol co-crystals with N-bases.

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New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magnetic resonance and electronic spectral data.Infrared spectra indicate the coordination of all the available ether oxygens and the amide carbonyls in each of the ligands, to the metal ions. IR and conductance data show that the perchlorate groups in all the complexes are ionic.1H and13C NMR data support the IR data regarding the mode of coordination of ligands to the metal ions. Electronic spectral shapes have been interpreted in terms of nine, eight and ten coordination in DiGA, TriGA and TetGA complexes respectively.

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The Ag-Ni system is characterized by large differences in atomic sizes (14%) and a positive heat of mixing (+23 kJ mol(-1)). The binary equilibrium diagram for this system therefore exhibits a large miscibility gap in both solid and liquid state. This paper explores the size-dependent changes in microstructure and the suppression of the miscibility gap which occurs when free alloy particles of nanometer size are synthesized by co-reduction of Ag and Ni metal precursors. The paper reports that complete mixing between Ag and Ni atoms could be achieved for smaller nanoparticles (<7 nm). These particles exhibit a single-phase solid solution with face-centered cubic (fcc) structure. With increase in size, the nanoparticles revealed two distinct regions. One of the regions is composed of pure Ag. This region partially surrounds a region of fcc solid solution at an early stage of decomposition. Experimental observations were compared with the results obtained from the thermodynamic calculations, which compared the free energies corresponding to a physical mixture of pure Ag and Ni phases and a fcc Ag-Ni solid solution for different particle sizes. Results from the theoretical calculations revealed that, for the Ag-Ni system, solid solution was energetically preferred over the physical mixture configuration for particle sizes of 7 nm and below. The experimentally observed two-phase microstructure for larger particles was thus primarily due to the growth of Ag-rich regions epitaxially on initially formed small fcc Ag-Ni nanoparticles. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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A solid state e.m.f. cell with yttria-doped thoria as the electrolyte and a mixture of Cr + Cr sub 2 O sub 3 as the reference electrode, was employed for the measurement of the activity of manganese in the Co--Mn system at 1760 deg K, for 0.3 > X sub Mn > 0.05. The liquid alloy was contained in an alumina crucible and saturated with MnAl sub 2+2x O sub 4+3x . The cell can be represented by Pt, W, (Co--Mn) + MnAl sub 2+2x O sub 4+3x + Al sub 2 O sub 3 /ThO sub 2 --Y sub 2 O sub 3 /Cr + Cr sub 2 O sub 3 , Pt. The activity of manganese shows negative deviations from Raoult's law. The activities in the Co--Mn system are intermediate between those in the Fe--Mn and Ni--Mn systems. The Gibbs' energies of mixing in these systems follow the trends given by Miedema's model. 14 ref.--AA.

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Ternary phase relations in the Co-Cr-S system at 1223 K were determined using microprobe analysis of quenched samples. The results are consistent with the data available on the binary systems. A complete solid solution exists between cobalt monosulfide and chromium monosulfide. The CoCr2S4 thiospinel is the only ternary compound formed. A sulfur potential diagram was constructed for the region involving equilibrium between alloy and monosulfide based on thermodynamic data on the Co-Cr, Co-S, and Cr-S binary systems and the ternary information obtained in this study. The sulfidation behavior of Co-Cr alloys reported in the literature is discussed in light of the sulfur potential diagram.