Ruthenium complexes of the 1,4-bis(diphenylphosphino)-1,3-butadiene-bridged diphosphine 1,2,3,4-Me-4-NUPHOS: Solvent-dependent interconversion of four- and six-electron donor coordination and transfer hydrogenation activity

In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.

Study of the transamidative ring expansion of N--halogenoalkyl--lactams of alkyl chain lengths 2–12 in liquid ammonia and other liquid amines: syntheses of 7-, 8- and 9-membered 1,5-diaza cyclic ketones, including routes to (±)-dihydroperiphylline and (±)-celabenzine

N-(3-Halogenopropyl)-4-phenylazetidin-2-ones undergo amination in liquid ammonia followed by transamidative ring expansion to give the eight-membered 4-phenyl -1,5-diazacyclooctan-2-one in excellent yield. Ring expansion of the amines in liquid ammonia is found to be much more effective than in hydrocarbon solvents. Formation of 7-, 8-, and 9-membered azalactams from the requisite -halogenoalkyl--lactams is an excellent synthetic process, though it is not applicable to 10membered rings. In the cases of rings of 13-, 15- and 17-members, although amination and apparent expansion takes place, the large rings appear not to be stable to ammonia and the final products are acyclic amides. N-[4-Halogenobut-2(Z)-enyl]-4-phenylazetidin-2-one satisfactorily forms a 9-membered (Z)-olefinic azalactam, but the (E)-isomer gives an acyclic amino amide. By using alkyl-substituted -lactam side-chains, C-substituted medium rings can be obtained; the relative instability of N-acyl -lactams to ammonia, however, leads to acylamino amides rather than expanded rings.Employing ethylamine in place of ammonia, it is shown that N-ethylated azalactams are formed satisfactorily, and using allylamine, N-allyl medium rings capable of further elaboration are obtained. The chemistry of these systems is discussed. Using transamidation in liquid ammonia, a short synthesis of the 9-membered spermidine alkaloid (±)-dihydroperiphylline is reported. Synthesis of key intermediates, whose transformation into the 13-membered alkaloids of the celabenzine group has already been effected, has been carried out.X-Ray single-crystal structure determinations for 4-phenyl-1,5-diazacyclononan-2-one, trans-4-phenyl-8-methyl-1,5-diazacyclooctan-2-one and (Z)-4-phenyl-1,5-diazacyclonon-7-en-2-one are reported, and comment is made on certain conformational features.

A new route to 1-substituted 2,2,3,3-tetracyanocyclopropanes

2,2,3,3-Tetracyanocyclorpropyl ketones were prepared by reaction of tetracyanoethylene with a-chloro ketones.

Altered basal cortisol levels at 3, 6, 8 and 18 months in infants born at extremely low gestational age

Little is known about the developmental trajectory of cortisol levels in preterm infants after hospital discharge.

The persistent activity of Jupiter-family comets at 3-7 AU

We present an analysis of comet activity based on the Spitzer Space Telescope component of the Survey of the Ensemble Physical Properties of Cometary Nuclei. We show that the survey is well suited to measuring the activity of Jupiter-family comets at 3-7 AU from the Sun. Dust was detected in 33 of 89 targets (37 ± 6%), and we conclude that 21 comets (24 ± 5%) have morphologies that suggest ongoing or recent cometary activity. Our dust detections are sensitivity limited, therefore our measured activity rate is necessarily a lower limit. All comets with small perihelion distances (q <1.8 AU) are inactive in our survey, and the active comets in our sample are strongly biased to post-perihelion epochs. We introduce the quantity ɛfρ, intended to be a thermal emission counterpart to the often reported Afρ, and find that the comets with large perihelion distances likely have greater dust production rates than other comets in our survey at 3-7 AU from the Sun, indicating a bias in the discovered Jupiter-family comet population. By examining the orbital history of our survey sample, we suggest that comets perturbed to smaller perihelion distances in the past 150 yr are more likely to be active, but more study on this effect is needed.

Efficient, Scalable, and Solvent-free Mechanochemical Synthesis of the OLED Material Alq(3) (q=8-Hydroxyquinolinate)

The aluminum complex Alq(3) (q = 8-hydroxyquinolinate), which has important applications in organic light-emitting diode materials, is shown to be readily synthesized as a pure phase under solvent-free mechanochemical conditions from Al(OAc)(2)OH and 8-hydroxyquinoline by ball milling. The initial product of the mechanochemical synthesis is a novel acetic acid solvate of Alq(3), and the alpha polymorph of Alq(3) is obtained on subsequent heating/desolvation of this phase. The structure of the mechanochemically prepared acetic acid solvate of Alq(3) has been determined directly from powder X-ray diffraction data and is shown to be a different polymorph from the corresponding acetic acid solvate prepared by solution-state crystallization of Alq(3) from acetic acid. Significantly, the mechanochemical synthesis of Alq(3) is shown to be fully scalable across two orders of magnitude from 0.5 to 50 g scale. The Alq(3) sample obtained from the solvent-free mechanochemical synthesis is analytically pure and exhibits identical photoluminescence behavior to that of a sample prepared by the conventional synthetic route.

Abordagens didáticas dos conteúdos de Física e Química dos 8º e 10º anos na escola EB 2,3/s Dr. João de Brito Camacho em Almodôvar

Este relatório foi elaborado no âmbito do Mestrado em Ensino de Física e Química para o 3º ciclo do Ensino Básico e Secundário, e refere-se à Unidade Curricular Prática de Ensino Supervisionada (PES), iniciada em setembro de 2011, na Escola E B 2,3 Dr. João de Brito Camacho em Almodôvar. A disciplina de PES decorreu sob orientação dos seguintes elementos: Orientadora Científica da Componente de Química (Professora Doutora Maria de Lurdes Cristiano), Orientadora Científica da Componente da Física (Professor Doutor Rui Guerra) e Orientadora Cooperante (Dr.ª Raquel Forca). Contempla o desenvolvimento de diferentes atividades letivas, nas Componentes de Química e de Física, aplicadas nas turmas do 8º e do 10º ano, este do curso Científico – Humanístico de Ciências e Tecnologias. A componente de Química foi lecionada de setembro de 2011 a janeiro de 2012, a componente de Física foi lecionada de fevereiro de 2012 a julho de 2012. A prática de ensino supervisionada, contou com um total de vinte e três aulas, catorze da componente de Química e nove da componente de Física. Durante o ano letivo foram realizadas diversas atividades/projetos, nomeadamente uma visita de estudo aos “Dias Abertos” do Instituto Superior Técnico, onde os alunos para além de participarem em diversos workshops, puderam ainda assistir a diversas palestras sobre temas relacionados com a Física. O estagiário participou nas atividades do Plano Anual, dinamizando o projeto do Laboratório de Instrumentação e Física Experimental (LIP), designado por Radiação e Ambiente onde os alunos realizaram tarefas de investigação sobre os efeitos da radiação. Participou também no projeto financiado pela Fundação Calouste Gulbenkian “Podíamos ler mais”, que envolveu a leitura de obras de divulgação científica e contou com um contato via skype com autores como David Bodanis e Michaell Guillian. A entrevista a estes autores foi realizada no “II Encontro aqui há ciência, arte e palavras” que contou ainda com palestras de divulgação científica por parte dos orientadores deste estágio e pelo Professor Doutor Paulo Crawford do departamento de Física da Faculdade de Ciências da Universidade de Lisboa. Este projeto foi convidado pelo Plano Nacional de Leitura a representar o mesmo na Futurália 2012. Os alunos dinamizaram um workshop intitulado “Livros sem resistência” onde apresentaram as experiências que leram nas obras inerentes a este projeto. O Relatório de Estágio compreende seis capítulos, referências bibliográficas e apêndices. No capítulo I é feita uma introdução onde são apresentados os objetivos do trabalho, as unidades de Física e de Química focadas e a metodologia seguida. No capítulo II é efetuado o enquadramento geral, do qual faz parte uma descrição das condições de trabalho, da turma, alvo da prática de ensino supervisionada e das disciplinas / turmas da responsabilidade da Orientadora Cooperante. O capítulo III (Química – 8º e 10º ano) e o capítulo IV (Física – 8º e 10ºano) contêm a análise da bibliografia oficial associada, as planificações, as metodologias, os instrumentos de avaliação e as atividades extracurriculares realizadas. No capítulo V o mestrando dá a conhecer os projetos que foram realizados, presentes no Plano Anual de Atividades. O capítulo VI e último, proporciona uma análise reflexiva de todo o trabalho desenvolvido, associada a sugestões futuras, eventualmente mais eficazes para a aprendizagem da Física e da Química, pelos alunos.

CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering

We report the results of the growth of Cu-Sn-S ternary chalcogenide compounds by sulfurization of dc magnetron sputtered metallic precursors. Tetragonal Cu2SnS3 forms for a maximum sulfurization temperature of 350 ºC. Cubic Cu2SnS3 is obtained at sulfurization temperatures above 400 ºC. These results are supported by XRD analysis and Raman spectroscopy measurements. The latter analysis shows peaks at 336 cm-1, 351 cm-1 for tetragonal Cu2SnS3, and 303 cm-1, 355 cm-1 for cubic Cu2SnS3. Optical analysis shows that this phase change lowers the band gap from 1.35 eV to 0.98 eV. At higher sulfurization temperatures increased loss of Sn is expected in the sulphide form. As a consequence, higher Cu content ternary compounds like Cu3SnS4 grow. In these conditions, XRD and Raman analysis only detected orthorhombic (Pmn21) phase (petrukite). This compound has Raman peaks at 318 cm-1, 348 cm-1 and 295 cm-1. For a sulfurization temperature of 450 ºC the samples present a multi-phase structure mainly composed by cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4. For higher temperatures, the samples are single phase and constituted by orthorhombic (Pmn21) Cu3SnS4. Transmittance and reflectance measurements were used to estimate a band gap of 1.60 eV. For comparison we also include the results for Cu2ZnSnS4 obtained using similar growth conditions.

[Journal du Camp de Gray commandé par M. Le duc de Randan]. Ordre du 2. au 3. 7.bre 1754

Ancien possesseur : Argenson, Antoine-René de Voyer (1722-1787 ; marquis de Paulmy d')

Pièces intéressantes et peu connues, pour servir à l'histoire et à la littérature. Tome 2 / . Par M. D. L. P. Tome premier [-septième]

Comprend : Pensées de Montesquieu adressées à son fils, tirées d'un manuscrit que l'on dit être original ; Madrigal et épigramme sur la Troade de Pradon

LE || TIERS LIVRE || Des Faicts et Dicts || Heroïques du bon Pantagruel : || Composé par M. Fran. || Rabelais docteur || en Medi- || cine. || Reueu, & corrigé par l'Autheur, sus || la censure antique. || L'Autheur susdict || supplie les Lecteurs beneuoles, soy || reseruer a rire au soixante || & dixhuytiesme || Liure. || A Paris, || De l'imprimerie de Michel Fezandat, au mont || S. Hilaire, a l'hostel d'Albret. || 1552. Il Auec priuilege du Roy. In-8 de 160 f. inexactement chiffr. (le dernier coté 170), 3 f. non chiffr. et 1 f. blanc. — LE || QVART LIVRE || des faicts et || dicts Heroiques du bon || Pantagruel. || Composé par M. François Rabelais || docteur en Medicine. || A Paris, || De l'imprimerie de Michel Fezandat, au mont || S. Hilaire, a l'hostel d'Albret. || 1552. || Auec priuilege du Roy. — [A la fin de la Table :] Acheué d'imprimer le XXVIII. de || Ianuier M.D.LII [1552]. In-8 de 19 f. non chiffr., 144 f. chiffr. et 14 f. non chiffr. — Ensemble 2 vol. in-8, mar. citr., fil., dos ornés, tr. dor. (Anc. rel.). Rothschild 1514 (2)

Rabelais (François). Tiers Livre (1552)

Catalogue des auteurs classiques, grecs & latins, des plus belles & des meilleurs éditions, & très-bien conditionnés, faisant partie du cabinet de livres du citoyen *** [Firmin Didot]. Dont la vente se fera les 17 & 18 brumaire an 6, (les 7 & 8 novembre 1797, v. st.), à quatre heures de relevée, en l'une des salles du Musée, rue de Thionville, ci-devant Dauphine.

[Catalogue de libraire. Paris. Didot, Firmin. 1797]

Compact Planar Multiband Antenna for GPS, DCS, 2.4/5.8 GHz WLAN Applications

A compact single –feed multiband planar antenna configuration Suitable for GPS, DCS. 2.4/5.8 GHz WLAN applications are presented. The antenna has dimensions 38 x 3 x 1.6 mm and offers good radiation and reflection characteristics in the above frequency bands. The antenna has a simple geometry and can be easily fed using a 50 coaxial probe

Compact Planar Multiband Antenna for GPS,DCS 2.4/5.8 GHz WLAN Applications

A compact single - feed muttiband planar antenna configuration suitable for GPS, DCS. 2.4/5.8 GHz WLAN applications is presented. The antenna has dimensions 38 x 3 x 1.6 mm and offers good radiation and reflection characteristics in the above frequency bands. The antenna has a simple geometry and can be easily fed using a 50 coaxial probe.

Thermochemistry of Charge-Transfer Complexes of 7,7,8,8-Tetracyanoquinodimethane with Benzene and Its Chloro Derivatives

The enthalpies of formation of charge-transfer complexes of benzene, chlorobenzene, and 1,3-dichlorobenzene as donors with 7,7,8,8-tetracyanoquinodimethane as acceptor were determined. The thermochemical data show an increased stability of charge-transfer complexes of donors with permanent dipole moment. The results confirm the importance of electrostatic forces in bonding and stabilizing weak complexes. The approximate formation constants of the complexes are also reported.