Synthesis and crystal structure of bis (tert-butyl-cyclopentadienyl)erbium ethoxide, (t-BuCp)(2)ErOEt

The formation of ( t-BuCp)(2)ErOEt was discussed. Its single-crystal structure was determined by X-ray diffraction. The crystal is monoclinic, P2(1)/c space group, a = 1.0191(2), b = 1.6203(5), c = 1.2118(3) nm, beta = 102. 960( 10)degrees, V = 1.9500 (nm(3)), Z = 2, D-c = 1.566 mg . m(-3), R = 0.0450, R-w = 0.1363. The complex is monomeric and solvent-free in the solid state. The erbium ion is coordinated by two tert-butyl-cyclopentadienyl rings and one oxygen atom of ethoxy group to form a seven-coordinated complex.

Hymeniacidon perleve associated bioactive bacterium Pseudomonas sp NJ6-3-1

Among marine bacteria isolated from the cytotoxic sponge Hymeniacidon perleve, one strain NJ6-3-1 classified as Pseudomonas sp. showed both cytotoxic and antimicrobial activities. Fatty acid analysis indicated that the bacterial strain consists mainly of C16:1, C16:0, C18:1, C18:0, C15:0, C14:0. One unusual 9,10-cyclopropane-C17:0 fatty acid and C26:0 also constitute major components, as well as the existence of squalene, the precursor of triterpenoids. The major metabolites in the culture broth were identified as alkaloids, including diketopiperazines and indole compounds, namely 3,6-diisopropylpiperazine-2,5-dione, 3-benzyl-3-isopropylpiperazine-2,5-dione, 3,6-bis-(2-methylpropyl)-piperazine-2,5-dione, indole-3-carboxaldehyde, indole-3-carboxylic acid methyl ester, indole-3-ethanol, and quinazoline-2,4-dione.

Steam reforming of ethanol over Co₃O₄–Fe₂O₃ mixed oxides

Co3O4, Fe2O3 and a mixture of the two oxides Co–Fe (molar ratio of Co3O4/Fe2O3 = 0.67 and atomic ratio of Co/Fe = 1) were prepared by the calcination of cobalt oxalate and/or iron oxalate salts at 500 °C for 2 h in static air using water as a solvent/dispersing agent. The catalysts were studied in the steam reforming of ethanol to investigate the effect of the partial substitution of Co3O4 with Fe2O3 on the catalytic behaviour. The reforming activity over Fe2O3, while initially high, underwent fast deactivation. In comparison, over the Co–Fe catalyst both the H2 yield and stability were higher than that found over the pure Co3O4 or Fe2O3 catalysts. DRIFTS-MS studies under the reaction feed highlighted that the Co–Fe catalyst had increased amounts of adsorbed OH/water; similar to Fe2O3. Increasing the amount of reactive species (water/OH species) adsorbed on the Co–Fe catalyst surface is proposed to facilitate the steam reforming reaction rather than decomposition reactions reducing by-product formation and providing a higher H2 yield.

Étude sur l'utilisation de liquides ioniques à base imidazolium pour l'extraction sélective de phosphopeptides

La phosphorylation des protéines constitue l’une des plus importantes modifications post-traductionnelles (PTMs) et intervient dans de multiples processus physiologiques tels, la croissance, la différenciation cellulaire, l’apoptose, etc. En dépit de son importance, l’analyse des phosphoprotéines demeure une tâche difficile en raison de leur nature dynamique (car la phosphorylation des protéines est un processus réversible) et de leur faible abondance relative. En effet, la détermination des sites de phosphorylation est souvent difficile car les phosphopeptides sont souvent difficiles à détecter par des méthodes d’analyse chromatographique classique et par spectrométrie de masse (MS). De récentes études ont démontré que les nombreuses méthodes d’enrichissement de phosphopeptides existantes ne sont pas complètes, et que le nombre total de phosphopeptides détectés ne chevauchent pas complètement ces méthodes. C’est pour cela qu’il existe une nécessité de combler les lacunes des méthodes d’enrichissement existantes afin d’avoir des analyses phosphoprotéomiques plus complètes. Dans cette étude, nous avons utilisé les liquides ioniques (LI), plus particulièrement les sels d’imidazolium, comme une technique d’enrichissement alternative, dans le but de favoriser une extraction sélective de phosphopeptides présents en solution. Les sels d’imidazolium ont donc été utilisés en raison de leurs propriétés physico-chimiques "facilement" ajustables selon la nature des substituants sur le noyau imidazolium et la nature de l’anion. Les sels de monoimidazolium et de bis-imidazolium possédant respectivement des chaînes linéaires à 4, 12 et 16 atomes de carbone et ayant différents anions ont été synthétisés et utilisés pour effectuer des extractions liquide-liquide et solide-liquide des phosphopeptides en solution. Dans un premier temps, des extractions liquide-liquide ont été réalisées en utilisant un liquide ionique (LI) ayant une chaine linéaire de 4 atomes de carbone. Ces extractions réalisées avec le bis(trifluoromethanesulfonyl) amide de 3-butyl-1-methylimidazolium (BMIM-NTf2) et l’hexafluorophosphate de 3-butyl-1-methylimidazolium (BMIM-PF6) n’ont pas montré une extraction notable du PPS comparativement au PN. Dans un deuxième temps, des extractions solide-liquide ont été réalisées en fonctionnalisant des particules solides avec des sels d’imidazolium possédant des chaines linéaires de 12 ou 16 atomes de carbone. Ces extractions ont été faites en utilisant un phosphopentapeptide Ac-Ile-pTyr-Gly-Glu-Phe-NH2 (PPS) en présence de 2 analogues acides non-phosphorylés. Il a été démontré que les sels d’imidazolium à chaine C12 étaient meilleurs pour extraire le PPS que les deux autres peptides PN (Ac-Ile-Tyr-Gly-Glu-Phe-NH2) et PE (Ac-Glu-Tyr-Gly-Glu-Phe-NH2) L’électrophorèse capillaire (CE) et la chromatographie liquide à haute performance couplée à la spectrométrie de masse (LC-MS) ont été utilisées pour quantifier le mélange des trois peptides avant et après extraction ; dans le but de mesurer la sélectivité et l’efficacité d’extraction de ces peptides par rapport à la composition chimique du liquide ionique utilisé.

Estudo do comportamento térmico dos compostos de Ag+ e Pb2+ com o ligante 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno

Este trabalho reporta o estudo de compostos binários do dicarboxilato 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno, C6H4(-CH=CH-CO-COO-)2 , com os cátions metálicos Ag+ e Pb2+, obtidos a partir de soluções aquosas do ligante e dos nitratos dos cátions metálicos, em proporções estequiométricas. Para a caracterização e o estudo do processo de decomposição térmica desses compostos foram empregadas Espectrofotometria de Absorção na Região do Infravermelho com Transformada de Fourier (FT-IR), Análise Elementar (C, H), Complexometria com EDTA, Termogravimetria (TG) e Calorimetria Exploratória Diferencial (DSC).

Thermal study of cyclopalladated complexes of the type [Pd-2(dmba)(2)X-2(bpe)] - (X=NO3-, Cl-, N-3(-), NCO-, NCS-; bpe=trans-1,2-bis(4-pyridyl)ethylene)

The synthesis, characterization and thermal analysis of the novel cyclometallated compounds [Pd-2(dmba)(2)Cl-2(mu-bpe)] (1), [Pd-2(dmba)(2)(N-3)(2)(mu-bpe)] (2), [Pd-2(dmba)(2)(NCO)(2)(mu-bpe)] (3), [Pd-2(dmba)(2)(SCN)(2)(mu-bpe)] (4), [Pd-2(dmba)(2)(NO3)(2)(mu-bpe)] (5) (bpe=trans-1,2-bis(4-pyridyl)ethylene; dmba=N,N-dimethylbenzylamine) are described. The thermal stability of [Pd-2(dmba)(2)X-2(mu-bpe)] complexes varies in the sequence 1 > 4 > 3 > 2 > 5. The final residues of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.

Sílica gel organofuncionalizada com 4-amino-5-(4-piridil) 4H-1,2,4-triazol-3-tiol (aptt): Propriedades adsortivas e eletroanalíticas

Pós-graduação em Ciência dos Materiais - FEIS

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Na 1 Nachlass Max Horkheimer, 712 - Entwürfe für ein mögliches Forschungsprojekt über Liberalismus des 19. Jahrhunderts; "Untersuchung des sozialen Klimas in Stadt- und Landkreisen Hessens"; "Betriebsklime. Eine industrie-soziologische Untersuchung aus dem Ruhrgebiet"; Sardemann, Karl: Interview mit einem Juden über sein Leben 1933 bis circa 1953; "Altersbild und Altersvorsorge der Arbeiter und Angestellte" (p. IX 187 - IX 191.1-3)

Entwürfe für ein Mögliches Forschungsprojekt über Liberlaismus des 19. Jahrhunderts; 1953; 1. Typoskript mit eigenhändigen Korrekturen von Theodor W. Adorno; 7 Blatt; 2. Typoskript mit eigenhändigen Korrekturen von Theodor W. Adorno; 3 Blatt; "Untersuchungn des sozialen Klimas in Stadt- und Landkreisen Hessens"; Entwürfe für ein "Handbuch der Methoden zur Messung des sozialen Klimas", nicht veröffentlicht; 1953; 1. Pollock, Friedrich: "Einführung" zum "Handbuch" a) Typoskript mit eigenhändigen Korrekturen; 8 Blatt; b) Typoskript mit eigenhändigen Korrekturen, 5 Blatt; c) Manuskript, "Vorwort"; 5 Blatt; d) Baumert, Gerhard: Entwurf des "Vorworts"; Typoskript mit handschriftlichen Korrekturen, 2 Blatt; e) Baumert, Gerhard: "Notizen zu Vorwort und Einführung des Handbuchs"; Typoskript, 1 Blatt; 2. Inhaltsverzeichnis zum "Handbuch"; 1 Blatt; 3. Pollock, Friedrich: eigenhändige Notizen zur Einführung; 7 Blatt; 4. Pollock, Friedrich: 1 eigenhändiger Brief mit Unterschrift an Theodor W. Adorno, Santa Monica, 21.09.1953; 1 Blatt; "Betriebsklime. Eine industrie-soziologische Untersuchung aus dem Ruhrgebiet" 1954-1956 veröffentlicht als Band 3 der Frankfurter Beiträge zur Soziologie, Frankfurt 1955; 1. Druckfahnen, mit handschriftlichen Korrekturen; 38 Blatt; 2. Korrektur-Notizen zu den Druckfahnen; 4 Blatt; 3. Adorno, Theodor W. [Mitarbeit]: "Grundreiz [Betriebsumfrage)" a) Typoskript mit handschriftlichen Korrekturen, 4 Blatt; b) Typoskript, 5 Blatt; 4. Adorno, Theodor W.: 1 Brief an Max Horkheimer, ohne Ort, 30.06.1954; 1 Blatt; 5. Fragebogen- Entwurf; Typsokript, 2 Blatt; 6. Fragebogen- Entwurf; Typoskript, 2 Blatt; 7. Adorno, Theodor W.: 1 Brief an Max Horkheimer, ohne Ort, ohne Datum [1954]; 1 Blatt; 8. Dirks, Walter: "Notiz über meine Reise nach Köln, Düsseldorf und Essen", 22.02.1955. Typoskript, 2 Blatt; 9. Becker, Hellmut: "Aktennotiz, Betreff: Ersetzung der Pressekonferenz über die Mannesmann-Studie durch in den nächsten Wochen und Monaten aufeinanderfolgende Artikel qualifizierter Korrespondenten", 15.02.1955. Typoskript, 1 Blatt; 10. Adorno, Theodor W.: 1 Brief an Hermann Winkhaus, Mannesmann AG, ohne Ort, 05.03.1956; 2 Blatt; 11. Winkhaus, Hermann, Mannesmann AG: 1 Breifabschrift an das Institut für Sozialforschung, Düsseldorf, 18.07.1955; 12. Presseveröffentlichungen zur Betriebsklima-Untersuchung; 1 Ordner, 13 Blatt; 13. Zeitschriftenartikel und Abschriften von Artikeln zur Betriebsklima- Untersuchung; mit: Becker, Egon: 2 Briefe mit Unterschrift an Max Horkheimer, Frankfurt, 1955; 1 Brief von Max Horkheimer, Zürich, 25.10.1955; Sardemann, Karl: Interview mit einem Juden über sein Leben 1933 bis circa 1953, insbesondere seine Erlebnisse im Konzentrationslager; 1955; 1. Interview; Typsokript, 38 Blatt; 2. Sardemann, Karl: 1 Brief mit Unterschrift an Max Horkheimer, ohne Ort, 15.12.1955; 1 Blatt; "Altersbild und Altersvorsorge der Arbeiter und Angestellten" veröffentlicht als Sonderheft 1 der Frankfurter Beiträge zur Soziologie, Frankfurt 1958.; Zwischenbericht zum Projekt und Material, 1955; 1. Becker, Egon, u.a.: "Zwischenbericht" 10.03.1953; Typoskript, 9 Blatt; mit einem Brief mit Unterschrift von Egon Becker an Max Horkheimer, ohne Ort, 11.03.1955; 1 Blatt; 2. Fragebogen; als Typoskript vervielfältigt, 16 Blatt; 3. Fragebogen; als Typoskript vervielfältigt, 11 Blatt;

Organizational, direct support, and general support maintenance manual : water purification unit, reverse osmosis, 600 GPH trailer mounted, flatbed cargo, 5 ton 4 wheel tandem model Rowpu 600-1 (4610-01-093-2380) and 600 GPH skid mounted model Rowpu 600-3 (4610-01-113-8651).

Includes index.

1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes

Tetrazolo[1,5-a] pyridines/ 2-azidopyridines 1 undergo photochemical nitrogen elimination and ring expansion to 1,3-diazacyclohepta-1,2,4,6-tetraenes 3, which react with alcohols to afford 2-alkoxy-1H-1,3-diazepines 4 (5), with secondary amines to 2-dialkylamino-5H-1,3-diazepines 16, sometimes via isolable 2-dialkylamino-1H-1,3-diazepines 15, and with water to 1,3-diazepin-2-ones 19. The latter are also obtained by elimination of isobutene or propene from 2-tert-butoxy- or 2-isopropoxy-1H-1,3-diazepines 4 or 5. 1,3-Diazepin-2-one 22B and 1,3-diazepin-4-one 24 were obtained from hydrolysis of the corresponding 4-chlorodiazepines. Diazepinones 19 undergo photochemical ring closure to diazabicycloheptenones 25 in high yields. The 2-alkoxy-1H-1,3-diazepines 4 and 5 interconvert by rapid proton exchange between positions N1 and N3. The free energies of activation for the proton exchange were measured by the Forsen - Hoffman method as DeltaGdouble dagger(298) = 16.2 +/- 0.6 kcal mol(-1) as an average for 4a - c in CD2Cl2, acetone-d(6), and methanol-d(4), and 14.1 +/- 0.6 kcal mol(-1) for 4c in acetone/D2O. The structures of 2-methoxy-5,6-bis( trifluoromethyl)-1H-1,3-diazepine 4k, 1,2-dihydro-4-diethylamino-5H-1,3-diazepin-2-one 22bB, and diazabicycloheptanone 26 were determined by X-ray crystallography. The former represents the first reported X-ray crystal structure of any monocyclic N-unsubstituted 1H-azepine.