1000 resultados para 4-29A


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Las nuevas tecnologías están a la orden del día. Cualquier persona, sea de la edad que sea, dispone de un terminal móvil. Además, en los últimos años, se han desarrollado dispositivos cada vez más sofisticados y con ello un gran número de aplicaciones móviles que pueden tener como finalidad ayudarnos en tareas de la vida cotidiana, enseñarnos o simplemente entretenernos. ¿Quién no espera a su tren jugando con el móvil? ¿Quien no está en la consulta del dentista y ameniza la espera con las redes sociales desde su móvil? Es por ello, que en este proyecto se ha desarrollado una aplicación móvil para el sistema operativo en auge, Android. Se trata de un juego educativo para niños en el que se les mostrará una imagen y deberán adivinar de que se trata. De este modo, podrán adquirir y ampliar sus conocimientos sobre los números, los colores, las profesiones, las partes del cuerpo, etc, mientras se divierten. Al estar destinado para niños en proceso de aprendizaje de escritura y lectura, con este juego, mejorarán estas habilidades. Además podrán practicar idiomas ya que el juego está disponible en castellano, inglés y euskera.

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The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

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Esta es una colección de 10 vídeos tutoriales que pueden ser empleados como material educativo en los cursos de fonética básica en el ámbito universitario. Los vídeos 1-3 tratan aspectos relacionados con la grabación: el tipo de micrófonos que se emplean, las clases de espacios en las que se suelen llevar a cabo la captura de señales de audio y las grabadoras que se suelen emplear. El vídeo 4 explora técnicas de captura y observación de datos de flujo y presión en fonética aerodinámica. Los vídeos 5-10 presentan información sobre los principales usos que se le brindan al programa Praat (Boersma y Weenink, 2014) en los estudios actuales de fonética acústica, desde la clase de información sobre modos de articulación de las consonantes que se puede identificar en oscilogramas hasta la creación de señales sonoras sintetizadas por medio de unos procedimientos que tiene el programa para tal propósito, los cuales son susceptibles de ser empleados en experimentos de percepción auditiva.

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Esta es una colección de 10 vídeos tutoriales que pueden ser empleados como material educativo en los cursos de fonética básica en el ámbito universitario. Los vídeos 1-3 tratan aspectos relacionados con la grabación: el tipo de micrófonos que se emplean, las clases de espacios en las que se suelen llevar a cabo la captura de señales de audio y las grabadoras que se suelen emplear. El vídeo 4 explora técnicas de captura y observación de datos de flujo y presión en fonética aerodinámica. Los vídeos 5-10 presentan información sobre los principales usos que se le brindan al programa Praat (Boersma y Weenink, 2014) en los estudios actuales de fonética acústica, desde la clase de información sobre modos de articulación de las consonantes que se puede identificar en oscilogramas hasta la creación de señales sonoras sintetizadas por medio de unos procedimientos que tiene el programa para tal propósito, los cuales son susceptibles de ser empleados en experimentos de percepción auditiva.

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The first synthesis of the cembranoid natural product (±)-7,8-epoxy-4-basmen-6- one (1) is described. Key steps of the synthetic route include the cationic cyclization of the acid chloride from 15 to provide the macrocycle 16, and the photochemical transannular radical cyclization of the ester 41 to form the tricyclic product 50. Product 50 was transformed into 1 in ten steps. Transition-state molecular modeling studies were found to provide accurate predictions of the structural and stereochemical outcomes of cyclization reactions explored experimentally in the development of the synthetic route to 1. These investigations should prove valuable in the development of transannular cyclization as a strategy for synthetic simplification.

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This report contains results from the fourth cruise of the MODIS Optical Characterization Experiment (MOCE). Also resented are oceanographic data from two MOBY maintenance cruises L-20 and L-25. The MOCE4 cruise was the first NOAAINESDIS-Ied SeaWiFS Initialization cruise during which a variety ofspectroradiometric observations ofthe upper water column and atmosphere were made by investigators from NOAA, the University of Miami, CHORS and MLML. Data presented in this report were obtained by oceanographic CTD profiler: salinity, temperature, dissolved oxygen, beam attenuation and chlorophyll-a fluorescence~ and by water samplers: total suspended matter and suspended organic carbon and nitrogen, salinity and dissolved oxygen. (PDF contains 142 pages).

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Nivel educativo: Grado. Duración (en horas): Más de 50 horas

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A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H2) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C12 and C18 alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

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Gradu amaierako lan honetan, “Utxintxa 4 urte” testuliburuaren azterketa egin da. Ikerketaren helburua: generoaren trataera ikertzea testuliburuko ikonografian eta idatzizkoan. Alde batetik, Haur Hezkuntzako testuliburuetan, emakumeen eta gizonezkoen arteko berdintasunari erreparatu zaio. Eta, horretarako, marrazkiak, argazkiak eta bertan agerturiko testu idatziak izan dira kontuan hartuak, besteak beste, emakumezkoen eta gizonezkoen presentzia eta maiztasuna, pertsona eta pertsonaien garrantzia eta orrialde mistoen agerpena. Bestetik, testuliburuan agertzen diren lanbideei dagokienez, emakumeen eta gizonen arteko berdintasuna, lanbide motak eta lan eremua aztertu dira. Azkenik, generoari loturiko testua ikertu da. Horiek horrela, haurren ikasketa prozesuan testuliburuek daukaten garrantzia kontuan hartuta, nabarmendu da, eta nahitaezkoa ikusten da, batetik, edukien eta balioen eguneratzea eta, bestetik, aldaketarako urratsak ematea, testuliburuen bidez sexu bazterketarik eman ez dadin.