On the halogenation of N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid esters and the conformational preferences of their 5-halo-piperazic acid products. The importance of A1,3 rotameric-strain in determining N(2)-acyl piperazic acid ring conformation

In this Letter, an unambiguous synthetic strategy is reported for the preparation of enantiomerically purecis-5-halo-piperazic acid derivatives in single diastereoisomer form. Contrary to the recent report by Shin and co-workers (Chem. Lett. 2001, 1172), in which it is claimed that the Ph₃P and N-chlorosuccinimide (NCS)-mediated chlorination of (3R,5S)-trans-N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid derivative 1proceeds with retention of configuration at C(5) to give 2, we now show that this and related Ph₃P-mediated halogenations all occur with S_N2 inversion at the alcohol center, as is customary for such reactions. Specifically, we demonstrate that the (3R,5S)-trans-5-Cl-piperazic acid derivative 2 claimed by Shin and co-workers (Chem. Lett. 2001, 1172) is in actual fact the chlorinated (3S,5R)-enantiomer 6, which must have been prepared from the cis-(3S,5S)-alcohol 3, a molecule whose synthesis is not formally described in the Shin paper. We further show here that the cis-(3R,5R)-5-Cl-Piz 13 claimed by Shin and co-workers inChem. Lett. 2001, 1172, is also (3S,5R)-trans-5-Cl-Piz 6. Authentic 13 has now been synthesized by us, for the very first time, here. Since Lindsley and Kennedy have recently utilized the now invalid Shin and co-workers’ retentive Ph₃P/NCS chlorination procedure on 1 in their synthetic approach to piperazimycin A (Tetrahedron Lett. 2010, 51, 2493), it follows that their claimed 5-Cl-Piz-containing dipeptide 25 probably has the alternate structure 26, where the 5-Cl-Piz residue has a 3,5-cis-configuration. The aforementioned stereochemical misassignments appear to have come from a mix-up of starting materials by Shin and co-workers (Chem. Lett. 2001, 1172), and an under-appreciation of the various steric and conformational effects that operate in N(2)-acylated piperazic acid systems, most especially rotameric A^1,3-strain. The latter has now been unambiguously delineated and defined here under the banner of the A^1,3-rotamer effect.

Les fonctions de la dialectique chez Aristote selon Topiques I,2

Le but de ce mémoire est d’expliciter en détail et de voir la portée d'un passage bien précis du traité des Topiques, ouvrage où Aristote tente d'élaborer une méthode qui permettra de raisonner de manière dialectique. Dans le deuxième chapitre du premier livre (I, 2), il énonce de manière succincte trois utilités que le traité en question peut procurer à celui qui possède et maîtrise adéquatement cette méthode. En premier lieu, la dialectique servirait de gymnastique intellectuelle pour former l'esprit et lui donner plus de souplesse dans ses raisonnements. Dans un second temps, elle serait utile dans les rencontres de tous les jours avec autrui parce qu’elle permettrait de discuter et d'argumenter sur un sujet donné avec le premier venu. Enfin, il semble également que la dialectique soit utile pour les «connaissances de caractère philosophique», en ce sens qu'elle permettrait de développer les apories et ultimement, d'établir les principes ou les notions premières de chaque science. Dans ce travail, je me propose donc d’examiner chacune de ces prétendues utilités afin de voir comment, et dans quelle mesure, nous pouvons réellement affirmer que la dialectique s’avère profitable pour chacun des services énumérés en Topiques I, 2.

Energieberatungsbericht zum Universitätsgebäude Technik I/2, Kassel

Im Rahmen des vom Hessischen Ministerium der Finanzen geförderten Forschungsprojektes „Bausteine für die CO2-Neutralität im Liegenschaftsbestand hessischer Hochschulen“ wird die neu entwickelte Teilenergiekennwertmethode, kurz TEK - an dem Universitätsgebäude Technik III/2 in der Kurt-Wolters-Straße 3, 34127 Kassel, angewandt. Das Gebäude von 1983 wird als Institutsgebäude der Fachbereiche Maschinenbau und Bauingenieurwesen sowie als Sitz der amtlichen Materialprüfstelle genutzt und besitzt zusätzlich einen Hörsaal und mehrere Seminarräume. Charakteristisch für dieses Gebäude ist die 76 Meter lange und 10 Meter hohe Versuchshalle, die sich im Kern des Gebäudes befindet. Die aus den Analysen gewonnenen Gebäude- und Anlagendaten dienen als Datengrundlage für eine Querschnittsanalyse zum Nichtwohngebäudebestand. Der folgende Kurzbericht umfasst: • Eine kurze Beschreibung des Projektes und des Gebäudes, • die Bewertung des Ist-Zustands des Gebäudes, • die Angabe von Modernisierungsmaßnahmen unter Nennung der Energieeinsparung, der Grobkosten und der sich hieraus ergebenden Wirtschaftlichkeit, • einen Anhang mit ausführlichen Informationen zur Gebäudeanalyse. Der Primärenergiebedarf des Objektes wurde mit 227 kWh/(m²a) unter Berücksichtigung der vorhandenen Nutzung als „gering“ eingestuft. Es wird empfohlen bei zukünftigen Instandsetztungsmaßnahmen die RLT-Anlage komplett zu ersetzten. Bei der Sanierung der Dachkonstruktion sollte ein U-Wert von 0,15 W/(m²K) eingehalten werden. Zusätzlich kann eine Senkung des Stromverbrauchs durch den Einsatz moderner Beleuchtungstechnik mit Präsenzmeldern geschaffen werden.

A propòsit del silenci sobre l'informe PISA 2003 (i 2). 'A propósito del silencio sobre el informe PISA 2003 (y 2)'.

Se plantean propuestas prácticas a llevar a cabo por el profesorado con el fin de mejorar la calidad de la educación, a falta de cambios fundamentales en las reformas del sistema educativo.

Pràctica 1 i 2 de la llicenciatura de Psicopedagogia. Bienni 1997-1999. 'Práctica 1 y 2 de la licenciatura de Psicopedagogía. Bienio 1997-1999'.

Material recopilatorio de información de utilidad para el alumnado de psicopedagogía durante las prácticas de la licenciatura. El material recoge los objetivos y finalidades de esta asignatura, los órganos y personas que intervienen y sus funciones, los criterios de calificación y evaluación, los seminarios y talleres que se imparten y las fichas de seguimiento de la asignatura en los dos años en que se distribuye.

Pràctica 1 i 2 de la llicenciatura de Psicopedagogia. Bienni 1998-2000. 'Práctica 1 y 2 de la licenciatura de Psicopedagogía. Bienio 1998-2000'.

Material recopilatorio de información de utilidad para el alumnado de psicopedagogía durante las prácticas de la licenciatura. El material recoge los objetivos y finalidades de esta asignatura, los órganos y personas que intervienen y sus funciones, los criterios de calificación y evaluación, los seminarios y talleres que se imparten y las fichas de seguimiento de la asignatura en los dos años en que se distribuye.

Pràctica 1 i 2 de la llicenciatura de Psicopedagogia. Bienni 2000-2002. 'Práctica 1 y 2 de la licenciatura de Psicopedagogía. Bienio 2000-2002'.

Material recopilatorio de información de utilidad para el alumnado de psicopedagogía durante las prácticas de la licenciatura. El material recoge los objetivos y finalidades de esta asignatura, los órganos y personas que intervienen y sus funciones, los criterios de calificación y evaluación, los seminarios y talleres que se imparten y las fichas de seguimiento de la asignatura en los dos años en que se distribuye.

Pràctica 1 i 2 de la llicenciatura de Psicopedagogia. Bienni 2001-2003. 'Práctica 1 y 2 de la licenciatura de Psicopedagogía. Bienio 2001-2003'.

Material recopilatorio de información de utilidad para el alumnado de psicopedagogía durante las prácticas de la licenciatura. El material recoge los objetivos y finalidades de esta asignatura, los órganos y personas que intervienen y sus funciones, los criterios de calificación y evaluación, los seminarios y talleres que se imparten y las fichas de seguimiento de la asignatura en los dos años en que se distribuye.

Detecció de compostos volàtils, clorofenols, cloroanisoles i 2,4,6-tribromoanisole, relacionats amb el "gust del suro"

D'entre els defectes organolèptics associats al vi, en destaca l'anomenat "gust de suro" habitualment vinculat a la presència de cloroanisoles, els quals són productes de l'activitat microbiana formats a partir dels corresponents clorofenols. La present tesi doctoral recull, en primer lloc, metodologies analítiques adreçades principalment a la determinació dels compostos clorofenòlics (2,4,6-triclorofenol, 2,3,4,6-tetraclorofenol i pentaclorofenol) en el control de qualitat dels taps suro, emprant dissolucions hidroalcohòliques com a medi de maceració o d'extracció i utilitzant les tècniques d'extracció en fase sòlida (SPE) i microextracció en fase sòlida (SPME) acoblades a la cromatografia de gasos (GC). En segon lloc, per tal de dur a terme l'anàlisi de cloroanisoles juntament amb els seus precursors en matrius de suro s'ha avaluat un mètode basat en l'extracció amb dissolvent orgànic, el qual ha estat aplicat per a l'estudi de diferents sistemes d'eliminació d'aquests anàlits en la matriu citada. En darrer lloc, s'han proposat metodologies per l'anàlisi de mostres de vi, en les quals d'una banda s'han determinat els compostos clorofenòlics utilitzant la SPME i de l'altra el 2,4,6-tricloroanisole i el 2,4,6-tribromoanisole mitjançant l'acoblament de la SPE i la injecció de grans volums (LVI) en el sistema cromatogràfic.

Coordination and separation studies of the uranyl ion with iso-butyramide based ligands: Synthesis and structures of [UO2(NO3)(2)((C3H7CON)-C-i{(C4H9)-C-i}(2))(2)] and [UO2(C6H5COCHCOC6H5)(2)((C3H7CON)-C-i{(C3H7)-C-i}(2))]

The coordination chemistry of iso-butyramide based ligands such as: (C3H7CON)-C-i((C3H7)-C-i)(2), (C3H7CON)-C-i(C4H9)(2) and (C3H7CON)-C-i((C4H9)-C-i)(2) with [UO2(NO3)(2) center dot 6H(2)O], [UO2(OO)(2) center dot 2H(2)O] {where OO = C4H3SCOCHCCCF3 (TTA), C6H5COCHCOCF3 (BTA) and C6H5COCHCOC6H5 (DBM)), [Th(NO3)(4) center dot 6H(2)O] and [La(NO3)(3) center dot 6H(2)O] has been evaluated. Structures for the compounds [UO2(NO3)(2)CC3H7CON{(C4H9)-C-i}(2))(2)] and [UO2(C6H5COCHCOC6H5)(2)((C3H7CON)-C-i{(C3H7)-C-i)(2))] have been determined by single crystal X-ray diffraction methods. Preliminary separation studies from nitric acid medium using the amide (C3H7CON)-C-i((C4H9)-C-i)(2) with U(VI), Th(IV) and La(Ill) ions showed the selective precipitation of uranyl ion from the mixture. Thermal study of the compound [UO2(NO3)(2)((C3H7CON)-C-i((C4H9)-C-i)(2))(2)] in air revealed that the ligands can be destroyed completely on incineration. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis and characterization of carbamoyl methyl pyrazole(CMPz) compounds of palladium(II) chloride: the crystal and molecular structure of [PdCl2{(C3H3N2CH2CONBu2)-Bu-i}(2)]

Carbamoyl methyl pyrazole compound of palladium(II) chloride of the type [PdCl2L2] (where L = C5H7N2CH2CON(C4H9)(2), C5H7N2CH2CON((C4H9)-C-i)(2), C3H3N2CH2CON(C4H9)(2), or C3H3N2CH2CON((C4H9)-C-i)(2)) has been synthesized and characterized by IR and H-1 NMR spectroscopy. The structure of the compound [PdCl2{(C3H3N2CH2CONBu2}2)-Bu-i] has been determined by single crystal X-ray diffraction and shows that the ligands are bonded through the soft pyrazolyl nitrogen atom to the palladium(II) chloride in a trans disposition. (c) 2007 Elsevier B.V. All rights reserved.

Virulence determinants of infectious bursal disease virus

The very virulent (vv) pathotype of infectious bursal disease virus (IBDV) has spread rapidly throughout Europe, Asia, and the Middle East. Although Australia is currently unaffected, there remains the potential for incursion of an exotic isolate. The aim of this study was to identify putative virulence determinants of IBDV to facilitate the development of improved diagnostic assays for detection and characterisation of vvIBDV isolates. Sequencing of Indonesian vvIBDV Tasik94 revealed a unique substitution [ A�¨S222] in the hypervariable region (HVR) of viral protein (VP) VP2, which did not appear to impinge on virulence or antigenicity. Phylogenetic analyses indicated that Tasik94 was closely related to Asian and European vvIBDV strains. Extensive alignment of deduced protein sequences across the HVR of VP2 identified residuesI242 I256 and I294 as putative markers of the vv phcnotype. Comparison of the pathology induced by mildly-virulent Australian IBDV 002/73 and Indonesian vvIBDV Tasik94, revealed that histological lesions in the spleen, thymus and bone marrow were restricted to Tasik94-infected birds, suggesting the enhanced pathogenicity of vvIBDV might be attributed to replication in non-bursal lymphoid organs. The biological significance of the VP2 HVR in virulence was assessed using recombinant viruses generated by reverse genetics. Both genomic segments of Australian IBDV 002/73, and recombinant segment A constructs in which the HVR of 002/73 was replaced with the corresponding region of either tissue culture-adapted virus or vvIBDV (Tasik94), were cloned behind T7 RNA polymerase promoter sequences. In vitro transcription/translation of each construct resulted in expression of viral proteins. Co-transfection of synthetic RNA transcripts initiated replication of both tissue culture-adapted parental and recombinant viruses, however attempts to rescue non-adapted viruses in specific-pathogen-free (SPF) chickens were unsuccessful. Nucleotide sequence variation in the HVR of VP2 was exploited for the development of a new diagnostic assay to rapidly detect exotic IBDV isolates, including vvIBDV, using reverse transcription polymerase chain reaction (RT-PCR) amplification and Bmrl restriction enzyme digestion. The assay was capable of differentiating between endemic and exotic IBDV in 96% of 105 isolates sequenced to date.

Development and evaluation of an ELISA for the detection and 3D antibodies to foot and mouth disease virus

A group specific ELISA (enzyme-linked immunosorbent assay) was developed to detect virus infection associated antibodies in the serum of animals infected with any serotype of foot and mouth disease virus. The assay was developed from non-infectious sources, and is therefore suitable for use in countries where FMDV is exotic.

Drought-rainfall cycles as potential environmental drivers of fowl plague and Newcastle disease uutbreaks in Australian poultry

Climatic conditions in Australia are erratic and characterised by periods of intense rainfall followed by periods of intense drought. This has considerable impact on the population dynamics and ecology of many Australian species of waterfowl, which are thought to form the reservoir of avian influenza viruses (AIV) but may also be important carriers (and possibly reservoirs) of other diseases (e.g. bursal disease, Newcastle disease). During the wet, waterfowl numbers increase with many serologically naive juveniles entering the population. During the subsequent period of drought, bird densities increase in the few remaining wetlands. We hypothesise that it is during this period of increasing densities of naive birds that the population’s viral prevalence of some infectious diseases may increase dramatically. Indeed, there exists a remarkable and suggestive coincidence between outbreaks of fowl plaque and Newcastle disease in Australian poultry farms and the periods of drought following a very wet period. In other words, we suspect a link between increased risk for disease outbreaks in poultry farms and the hypothesised high in the prevalences of the viruses causing these diseases in waterfowl. Given that poultry farms may provide ideal conditions for development of high-pathogenic strains, there is also a reciprocal risk for wildlife involved during these periods.