Chelated fluoroboron cations : synthesis and multinuclear nmr studies

The preparation of chelated difluoroboron cations (DD)BF2+, where DD is a saturated polydentate tertiary-amine or polydentate aromatic ligand, has been systematically studied by using multinuclear solution and solid state nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. Three new methods of synthesis of (DD)BF2+ cations are reported, and compared with the previous method of reacting a chelating donor with Et20.BF3. The methods most effective for aromatic donors such as 1,1O-phenanthroline are ineffective for saturated polydentate tertiary-amines like N,N,N' ,Nil ,Nil-pentamethyldiethylenetriamine. Polydentate tertiary-amine donors that form 5-membered rings upon bidentate chelation were found to chelate effectively when the BF2 source contained two leaving groups (a heavy halide and a Lewis base such as pyridine =pyr or isoxazole =ISOX), i.e., pyr.BF2X (X = CI or Br), ISOX.BF2X and (pyr)2BF2+. Those that would form 6membered rings upon chelation do not chelate by any of the four methods. Polydentate aromatic ligands chelate effectively when the BF2 source contained a weak Lewis base, e.g., ISOX.BF3, ISOX.BF2X and Et20.BF3. Bidentate chelation by polydentate tertiaryamine and aromatic donors leads to nmr parameters that are significantly different then their (D)2BF2+ relatives (D =monod~ntate t-amines or pyridines). The chelated haloboron cations (DD)BFCI+, and (DD)BFBr+ were generated from D.BFX2 adducts for all ligands that form BF2+ cations above. In addition, the (DD)BCI2+ and (DD)BBr2+ cations were formed from D.BX3 adducts by the chelating aromatic ligands, except for the aromatic ligand 1,8-bis(dimethylamino)naphthalene, which formed only the (DD)BF2+ cation, apparently due to its extreme steric hindrance. Chelation by a donor is a two-step reaction. For polydentate tertiary-amine ligands, the two rates appear to be very dependent on the two possible leaving groups on the central boron atom. The order of increasing ease of displacement for the donors was: pyr < Cl < Br < ISOX. The rate of chelation by polydentate aromatic ligands appears to be dependent on the displacement of the first ligand from the boron. The order of increasing ease of displacement for the donors was: pyr < CI < ISOX ~ Br < Et20.

Zerreißproben

Die vorliegende Arbeit beschäftigt sich mit dem Werk des französischen Philosophen Gilles Deleuze (1925-1995), indem sie dessen vielfältig-pluralistisches, in mancher Hinsicht sogar heterogenes Denken in einen Zusammenhang mit vitalistischen Philosophien der ersten Hälfte des 20. Jahrhunderts stellt (an erster Stelle Henri Bergson, aber auch Hans Driesch und Jakob von Uexküll), um auf diese Weise – durch Vergleiche und Gegenüberstellungen - zu verdeutlichen, dass und inwiefern der Vitalismus in der Version von Deleuze unter dem Eindruck der Entwicklung der Biologie seit Darwin (für die hier besonders die wissenschaftsphilosophischen Überlegungen der französischen Molekularbiologen François Jacob und Jacques Monod herangezogen werden) nicht mehr in erster Linie naturphilosophisch verstanden werden kann, sondern experimentell. Das, womit hier gedanklich experimentiert wird, sind Intensitäten. Und Intensität – so wird dargelegt – ist der Schlüsselbegriff zum Verständnis von Deleuzes’ erstem philosophischen Hauptwerk „Differenz und Wiederholung“. Im Zeichen eines Denkens der Intensitäten versucht Deleuze etablierte Dualismen wie die von Natur (physis) und Kunst (techné), Mensch und Tier, Individualität und Allgemeinheit zu unterlaufen. Weil dieser Versuch sich selbst als ein – wie es in dem von Deleuze gemeinsam mit dem Psychiater Félix Guattari verfassten Buch „Tausend Plateaus“ heißt - Vorstoß in "eine Welt aus formlosen, gegenstandslosen und gesichtslosen Schnelligkeiten und Langsamkeiten" versteht, stellt sich mit der Frage nach den lebenspraktischen Aspekten dieses grenzüberschreitenden und Freiräume eröffnenden Vorhabens auch die nach den damit verbundenen Risiken und Nebenwirkungen. Zur Konkretisierung werden Beispiele aus der modernen Literatur (die Verzeitlichung des Denkens bei Marcel Proust, aber auch die existentielle Sprachskepsis Antonin Artauds), der bildenden Kunst (die Deformationskunst in der Malerei Francis Bacons) und der Moral- bzw. moralkritischen Philosophie (der Stoizismus als eine Art Kunst der Selbstverteidigung, Nietzsches Umwertung aller Werte als eine Kunst der Selbstüberbietung) erörtert. Was in diesen Praktiken stattfindet und zum Ausdruck gebracht wird, sind Zerreißproben, d. h. radikale Belastungen oder Erprobungen von Vermögen wie Sinnlichkeit, Einbildungskraft, Denken, weshalb diese Versuche mit Deleuze, der sich hier von den stilpsychologischen Untersuchungen des Kunsthistorikers Wilhelm Worringer hat inspirieren lassen, als Spielarten eines nichtorganischen Lebens zu verstehen sind. Sich darauf in einem ständigen Wechsel von Annäherung und Distanzierung einzulassen, macht das ausgeprägte Pathos der Philosophie aus, auf das man im Denken von Gilles Deleuze trifft.

Reflexiones en torno al concepto de vida

Esto texto examina cuatro conceptos de vida que se consideran notables en el siglo XX, los contrasta y propone algunos aspectos que pueden enriquecer el concepto.

La m??sica en el Quijote

No creemos que Cervantes tuviese una frecuente relaci??n con los m??sicos de su tiempo, aunque no ser??a extra??o. Lo cierto es que, ha sabido extraer de sus propias experiencias f??rmulas cr??ticas de finura extraordinaria, frente a la m??sica, sus detalles y circunstancias que pudieran dar la impresi??n de ser una persona cultivada en este tema.. Es evidente, que Cervantes sinti?? un gran amor por la m??sica en su obra, distingu??a perfectamente entre monod??a, tr??o, coro, polifon??a. Adem??s, no da preferencia a ning??n instrumento.

Hacia una fundamentación biológica de la moral.

Se presentan una serie de autores que siguen la línea de pensamiento de la fundamentación biológica de la moral o de la capacidad ética. Entre ellos están: Herbert Spencer, Honrad Lorenz, Jacques Monod, y F. J. Ayala. Por último, se establecen una serie de conclusiones donde se tienen en cuenta las afirmaciones de estos autores.

Pippi Longstocking, juvenile delinquent? Hachette, self-censorship and the moral reconstruction of postwar France

This paper looks at the blockages to the publication of children’s literature caused by the intellectual climate of the postwar era, through a case study of the editorial policy of Hachette, the largest publisher for children at this time. This period witnessed heightened tensions surrounding the social and humanitarian responsibilities of literature. Writers were blamed for having created a culture of defeatism, and collaborationist authors were punished harshly in the purges. In the case of children’s literature, the discourse on responsibility was made more urgent by the assumption that children were easily influenced by their reading material, and by the centrality of the young to the discourse on the moral reconstruction of France. As the politician and education reformer Gustave Monod put it: “penser l’avenir, c’est penser le sort des enfants et de la jeunesse.” These concerns led to the expansion of associations and publications dedicated to protecting children and promoting “good” reading matter for them, and, famously, to the 1949 law regulating publications for children, which banned the depiction of crime, debauchery and violence that might demoralise young readers. Using the testimonials of former employees, along with readers’ reports and editorial correspondence preserved in the Hachette archives, this paper will examine how individual editorial decisions and self-censorship strategies were shaped by the 1949 law with its attendant discourse of moral panic on children’s reading, and how national concerns for future citizens were balanced with commercial imperatives.

Clavulanic acid production processes in a tower bioreactor with immobilised cells

The feasibility of using Streptomyces clavuligerus ATCC 27064 bioparticles supported on alginate gel containing alumina to produce clavulanic acid (CA) was investigated. To this end, effectiveness factors for spherical bioparticles, relating respiration rates of immobilised and free cells, were experimentally determined for various dissolved oxygen (DO) levels and bioparticle radii. Monod kinetics was assumed as representative of the oxygen consuming reaction, while internal oxygen diffusion was considered the limiting step. A comparison was made of the results from a tower bioreactor operating under batch, repeated-batch and continuous conditions with immobilised bioparticles. The theoretical curve of the effectiveness factor for the zero-order reaction model, considering an inert nucleus - the dead core model - was very well fitted to the experimental data. The results of the bioprocess indicated that the batch operation was the most efficient and productive, requiring a do concentration in the reactor above 60% of the saturation value. (C) 2007 Elsevier B.V. All rights reserved.

Modeling and simulation of cephalosporin C production in a fed-batch tower-type bioreactor

Immobilized cell utilization in tower-type bioreactor is one of the main alternatives being studied to improve the industrial bioprocess. Other alternatives for the production of beta -lactam antibiotics, such as a cephalosporin C fed-batch p recess in an aerated stirred-tank bioreactor with free cells of Cepha-losporium acremonium or a tower-type bioreactor with immobilized cells of this fungus, have proven to be more efficient than the batch profess. In the fed-batch process, it is possible to minimize the catabolite repression exerted by the rapidly utilization of carbon sources (such as glucose) in the synthesis of antibiotics by utilizing a suitable flow rate of supplementary medium. In this study, several runs for cephalosporin C production, each lasting 200 h, were conducted in a fed-batch tower-type bioreactor using different hydrolyzed sucrose concentrations, For this study's model, modifications were introduced to take into account the influence of supplementary medium flow rate. The balance equations considered the effect of oxygen limitation inside the bioparticles. In the Monod-type rate equations, eel concentrations, substrate concentrations, and dissolved oxygen were included as reactants affecting the bioreaction rate. The set of differential equations was solved by the numerical method, and the values of the parameters were estimated by the classic nonlinear regression method following Marquardt's procedure with a 95% confidence interval. The simulation results showed that the proposed model fit well with the experimental data,and based on the experimental data and the mathematical model an optimal mass flow rate to maximize the bioprocess productivity could be proposed.

Studies on the respiration rate of free and immobilized cells of Cephalosporium acremonium in cephalosporin C production

Bioprocesses using filamentous fungi immobilized in inert supports present many advantages when compared to conventional free cell processes. However, assessment of the real advantages of the unconventional process demands a rigorous study of the limitations to diffusional mass transfer of the reagents, especially concerning oxygen. In this work, a comparative study was carried out on the cephalosporin C production process in defined medium containing glucose and sucrose as main carbon and energy sources, by free and immobilized cells of Cephalosporium acremonium ATCC 48272 in calcium alginate gel beads containing alumina. The effective diffusivity of oxygen through the gel beads and the effectiveness factors related to the respiration rate of the microorganism were determined experimentally. By applying Monod kinetics, the respiration kinetics parameters were experimentally determined in independent experiments in a complete production medium. The effectiveness factor experimental values presented good agreement with the theoretical values of the approximated zero-order effectiveness factor, considering the dead core model. Furthermore, experimental results obtained with immobilized cells in a 1.7-L tower bioreactor were compared with those obtained in 5-L conventional fermenter with free cells. It could be concluded that it is possible to attain rather high production rates working with relatively large diameter gel beads (ca. 2.5 mm) and sucrose consumption-based productivity was remarkably higher with immobilized cells, i.e., 0.33 gCPC/kg sucrose/h against 0.24 gCPC/kg sucrose/h in the aerated stirred tank bioreactor process. (C) 1999 John Wiley & Sons, Inc.

O efeito da duração de pausa no exercício intermitente: um estudo pelo modelo da potência crítica

Pós-graduação em Ciências da Motricidade - IBRC

Força crítica, análise de parâmetros aeróbios e anaeróbios em exercício resistido - supino reto

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Protocolos invasivos e não invasivos para avaliação aeróbia e anaeróbia de ratos wistar

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Comparative Genome Analysis of Trichophyton rubrum and Related Dermatophytes Reveals Candidate Genes Involved in Infection

The major cause of athlete's foot is Trichophyton rubrum, a dermatophyte or fungal pathogen of human skin. To facilitate molecular analyses of the dermatophytes, we sequenced T. rubrum and four related species, Trichophyton tonsurans, Trichophyton equinum, Microsporum canis, and Microsporum gypseum. These species differ in host range, mating, and disease progression. The dermatophyte genomes are highly colinear yet contain gene family expansions not found in other human-associated fungi. Dermatophyte genomes are enriched for gene families containing the LysM domain, which binds chitin and potentially related carbohydrates. These LysM domains differ in sequence from those in other species in regions of the peptide that could affect substrate binding. The dermatophytes also encode novel sets of fungus-specific kinases with unknown specificity, including nonfunctional pseudokinases, which may inhibit phosphorylation by competing for kinase sites within substrates, acting as allosteric effectors, or acting as scaffolds for signaling. The dermatophytes are also enriched for a large number of enzymes that synthesize secondary metabolites, including dermatophyte-specific genes that could synthesize novel compounds. Finally, dermatophytes are enriched in several classes of proteases that are necessary for fungal growth and nutrient acquisition on keratinized tissues. Despite differences in mating ability, genes involved in mating and meiosis are conserved across species, suggesting the possibility of cryptic mating in species where it has not been previously detected. These genome analyses identify gene families that are important to our understanding of how dermatophytes cause chronic infections, how they interact with epithelial cells, and how they respond to the host immune response. IMPORTANCE Athlete's foot, jock itch, ringworm, and nail infections are common fungal infections, all caused by fungi known as dermatophytes (fungi that infect skin). This report presents the genome sequences of Trichophyton rubrum, the most frequent cause of athlete's foot, as well as four other common dermatophytes. Dermatophyte genomes are enriched for four gene classes that may contribute to the ability of these fungi to cause disease. These include (i) proteases secreted to degrade skin; (ii) kinases, including pseudokinases, that are involved in signaling necessary for adapting to skin; (iii) secondary metabolites, compounds that act as toxins or signals in the interactions between fungus and host; and (iv) a class of proteins (LysM) that appear to bind and mask cell wall components and carbohydrates, thus avoiding the host's immune response to the fungi. These genome sequences provide a strong foundation for future work in understanding how dermatophytes cause disease.