Mechanism of Alkyl Migration in Diorganomagnesium 2,6-Bis(imino)pyridine Complexes: Formation of Grignard-Type Complexes with Square-Planar Mg(II) Centers

Dialkylmagnesium compounds [MgR2L2] (R = n-Bu, L = none or R = Bn, L = THF) react with 2,6-bis(imino)pyridines (BIP) to afford different types of Mg(II) alkyl complexes, depending on the nature of R. For R = n-Bu, thermally stable products resulting from selective alkyl transfer to the pyridine nitrogen (N1) atom are obtained. However, NMR studies showed that the reaction of [Mg(Bn)2THF2] with iPrBIP at −65 °C leads to a thermally unstable product arising from benzyl migration to position C2 in the pyridine ring. Above +5 °C, this compound rearranges, cleanly yielding a mixture of two isomeric complexes, in which the benzyl group has migrated to positions C3 or C4 of the central ring, respectively. Similar isomeric mixtures were obtained when [Mg(Bn)2THF2] was reacted with iPrBIP or MesBIP at room temperature. Such mixtures are thermally stable below 80 °C, but at this temperature, the 3-benzyl isomer converts into the thermodynamically favored 4-benzyl product, albeit not quantitatively. An alternate route was devised for the selective syntheses of the latter type of compounds. The X-ray diffraction structure of one of them provided an unusual example of a square-planar alkylmagnesium(II) center.Ministerio de Economía e Innovación CTQ2015-68978-

Oxygen-Induced Dimerization of Alkyl-Manganese(II) 2,6-Bisiminopyridine Complexes: Selective Synthesis of a New Ditopic NNN-Pincer Ligand

The outcome of the reaction of manganese(II) dialkyls with 2,6-bisiminopyridine (BIP) ligands is dramatically altered by the presence of very small amounts of oxygen (< 0.5 mol %), leading to binuclear species. These arise from the dimerization of the initial product, a Mn(II) 4-alkyl-2,6-bisiminodihydropyridinate alkyl complex. Cleavage of the binuclear Mn products with methanol affords the free dimeric bases, which can be regarded as a special type of ditopic NNN pincer ligand with an unusual tricyclic framework. The coordinative ability of the new ligands has been probed with the syntheses of Zn and Pd organometallic derivativesMinisterio de Economía e Innovación TQ2015- 68978-

Modeling the Prospects for Hydrogen Powered Transportation Through 2100

Abstract in HTML and technical report in PDF available on the MIT Joint Program on the Science and Policy of Global Change website (http://mit.edu/globalchange/www/).Hydrogen fueled transportation has been proposed as a low carbon alternative to the current gasoline-powered fleet. Using a computable general equilibrium model of the world economy we explore the economic viability of hydrogen transportation in several different tax and carbon dioxide stabilization policy scenarios. We represent the capital, labor, fuel and other costs of hydrogen production and hydrogen powered vehicles in the economic model. We examine scenarios where the hydrogen fuel price and vehicle cost are varied over a wide range to evaluate what technology improvements would be needed, in terms of cost reductions, for hydrogen vehicles to penetrate the market. We consider scenarios with and without climate policy, and in competition with other reduced-carbon fuel substitutes, such as ethanol-blend fuels. We find that hydrogen-powered fuel-cell vehicles could make a significant contribution to de-carbonization of the transportation fuel cycle if production of hydrogen itself is not carbon-intensive. Cost targets needed for the technology to penetrate in the USA are such that the hydrogen fuel would need to be in the range of 1 to 1.7 times the 1997 price of gasoline and the vehicle mark-up above an average fuel cell automobile would need no more than 1.3 to 1.5 times an average conventional vehicle. At the lower end of these cost ranges, the vehicle fleet could be competitive by 2020 but at the upper end we would only see entry of the fleet toward the end of the century. High fuel taxes in Europe makes fuel-efficient hydrogen fuel cell technology more competitive there than in the USA. Along with cost reductions, these results assume that technical issues are solved and that market hurdles of establishing the fuel distribution system are overcome. For those involved in hydrogen vehicle research this analysis provides cost targets that would need to met and, given they are achieved, an idea of when vehicles could be competitive and under what conditions.The authors gratefully acknowledge the financial support for this work provided by the MIT Joint Program on the Science and Policy of Global Change through a consortium of industrial sponsors, Federal grants that have supported the development of the modeling framework, especially the US Department of Energy, Integrated Assessment Program in the Office of Biological and Environmental Research (BER) grant DE-FG02-94ER61937 and US EPA agreement XA- 83344601-0 and XA-83240101, and an anonymous donor

Analogue mouse pointer control via an online steady state visual evoked potential (SSVEP) brain-computer interface

The steady state visual evoked protocol has recently become a popular paradigm in brain–computer interface (BCI) applications. Typically (regardless of function) these applications offer the user a binary selection of targets that perform correspondingly discrete actions. Such discrete control systems are appropriate for applications that are inherently isolated in nature, such as selecting numbers from a keypad to be dialled or letters from an alphabet to be spelled. However motivation exists for users to employ proportional control methods in intrinsically analogue tasks such as the movement of a mouse pointer. This paper introduces an online BCI in which control of a mouse pointer is directly proportional to a user's intent. Performance is measured over a series of pointer movement tasks and compared to the traditional discrete output approach. Analogue control allowed subjects to move the pointer faster to the cued target location compared to discrete output but suffers more undesired movements overall. Best performance is achieved when combining the threshold to movement of traditional discrete techniques with the range of movement offered by proportional control

Deweyan tools for inquiry and the epistemological context of critical pedagogy

This article develops the notion of resistance as articulated in the literature of critical pedagogy as being both culturally sponsored and cognitively manifested. To do so, the authors draw upon John Dewey\u27s conception of tools for inquiry. Dewey provides a way to conceptualize student resistance not as a form of willful disputation, but instead as a function of socialization into cultural models of thought that actively truncate inquiry. In other words, resistance can be construed as the cognitive and emotive dimensions of the ongoing failure of institutions to provide ideas that help individuals both recognize social problems and imagine possible solutions. Focusing on Dewey\u27s epistemological framework, specifically tools for inquiry, provides a way to grasp this problem. It also affords some innovative solutions; for instance, it helps conceive of possible links between the regular curriculum and the study of specific social justice issues, a relationship that is often under-examined. The aims of critical pedagogy depend upon students developing dexterity with the conceptual tools they use to make meaning of the evidence they confront; these are background skills that the regular curriculum can be made to serve even outside social justice-focused curricula. Furthermore, the article concludes that because such inquiry involves the exploration and potential revision of students\u27 world-ordering beliefs, developing flexibility in how one thinks may be better achieved within academic subjects and topics that are not so intimately connected to students\u27 current social lives, especially where students may be directly implicated

Enteroaggregative Escherichia coli as a Major Etiologic Agent in Traveler's Diarrhea in 3 Regions of the World

Enteroaggregative Escherichia coli (EAEC) has been reported to cause traveler's diarrhea and persistent diarrhea in children in developing countries and in immunocompromised patients. To clarify the prevalence of EAEC in traveler's diarrhea, we studied 636 US, Canadian, or European travelers with diarrhea: 218 in Guadalajara, Mexico (June-August 1997 and 1998), 125 in Ocho Rios, Jamaica (September 1997-May 1998), and 293 in Goa, India (January 1997-April 1997 and October 1997-February 1998). Stool samples were tested for conventional enteropathogens. EAEC strains were identified by use of the HEp-2 assay. EAEC was isolated in 26% of cases of traveler's diarrhea (ranging from 19% in Goa to 33% in Guadalajara) and was second only to enterotoxigenic E. coli as the most common enteropathogen in all areas. Identification of EAEC reduced the number of cases for which the pathogen was unknown from 327 (51%) to 237 (37%) and explained 28% of cases with unknown etiology. EAEC was a major cause of traveler's diarrhea in 3 geographically distinct study area

An ‛Aukward' Tale: A Genetic Approach to Discover the Whereabouts of the Last Great Auks.

One hundred and seventy-three years ago, the last two Great Auks, Pinguinusimpennis, ever reliably seen were killed. Their internal organs can be found in the collections of the Natural History Museum of Denmark, but the location of their skins has remained a mystery. In 1999, Great Auk expert Errol Fuller proposed a list of five potential candidate skins in museums around the world. Here we take a palaeogenomic approach to test which-if any-of Fuller's candidate skins likely belong to either of the two birds. Using mitochondrial genomes from the five candidate birds (housed in museums in Bremen, Brussels, Kiel, Los Angeles, and Oldenburg) and the organs of the last two known individuals, we partially solve the mystery that has been on Great Auk scholars' minds for generations and make new suggestions as to the whereabouts of the still-missing skin from these two birds