Facile ketene-ketene and ketene-ketenimine rearrangements: A study of the 1,3-migration of alpha-substituents interconverting alpha-imidoylketenes and alpha-oxoketenimines, a pseudopericyclic reaction

Theoretical calculations (B3LYP/6-311+G(3df,2p)//B3LYP/6-31G*) of the 1,3 migration of NR2 transforming alpha-oxoketenimines 1 to alpha-imidoylketenes 3 and vice versa indicate that this process is a pseudo-pericyclic reaction with a low activation energy (NH2 97 kJ mol(-1), N(CH3)(2) 62 kJ mol(-1)). The oxoketenimines were found to be more stable (by 18-35 kJ mol(-1)) which is in line with experimental observations. The hindered amine rotation in the amide and amidine moieties adjacent to the cumulenes are important in the migration of the NR2 group, as one of the rotation transition states is close to the 1,3 migration pathway. This gives an interesting potential energy surface with a valley-ridge inflection (VRI) between the orthogonal hindered amine rotation and 1,3 migration transition states. The imidoylketene may also undergo ring closure to an azetinone 5; however, this is metastable, and under the conditions that allow the 1,3-migration, the oxoketenimine 1 will be favored. The imine NH E/Z-interconversion of the ketenimine group takes place by inversion and has a low activation barrier (similar to40 kJ mol(-1)). In all the amidines examined the E/Z-interconversion of the imine function was predicted to be by rotation with a high barrier (>80 kJ mol(-1)), in contrast to all other reported imine E/Z-interconversions which are by inversion.

Mesoionic 1,3-oxazinium olates. Rearrangement to acylketenes and 3-azabicyclo[3.1.1]heptanetriones

Metastable but isolable mesoionic 1,3-oxazinium 4-olates 9d-f undergo ring opening to acylketenes 10 at or near room temperature. The ketenes undergo intramolecular criss-cross [2 + 2] cycloaddition to afford 3-azabicyclo[3.1.1]heptanetriones 12. The structure of 12d was established by X-ray crystallography.

A METÁFORA DO CORPO NA I CARTA DE CLEMENTE DE ROMA AOS CORÍNTIOS (37.5-38.1): Uma análise dialógica

A I Carta de Clemente de Roma aos Coríntios faz parte de uma coleção de escritos cristãos antigos intitulados Pais Apostólicos. Esse texto é uma autêntica correspondência enviada da comunidade cristã de Roma para a comunidade cristã de Corinto, escrita pelo seu secretário Clemente. Esta pesquisa, em contraposição às desenvolvidas pela disciplina teológica chamada patrologia , analisa a carta a partir das teorias de Mikhail M. Bakhtin e seu círculo e da micro-história assumidamente relacionada com as teorias do mesmo autor delimitando o trecho 37.5-38.1, onde se encontra a metáfora do corpo.

Cleavage of caspases-1, -3, -6, -8 and -9 substrates by proteases in skeletal muscles from mice undergoing cancer cachexia

A prominent feature of several type of cancer is cachexia. This syndrome causes a marked loss of lean body mass and muscle wasting, and appears to be mediated by cytokines and tumour products. There are several proteases and proteolytic pathways that could be responsible for the protein breakdown. In the present study, we investigated whether caspases are involved in the proteolytic process of skeletal muscle catabolism observed in a murine model of cancer cachexia (MAC16), in comparison with a related tumour (MAC13), which does not induce cachexia. Using specific peptide substrates, there was an increase of 54% in the proteolytic activity of caspase-1, 84% of caspase-8, 98% of caspase-3 151% to caspase-6 and 177% of caspase-9, in the gastrocnemius muscle of animals bearing the MAC16 tumour (up to 25% weight loss), in relation to muscle from animals bearing the MAC13 tumour (1-5% weight loss). The dual pattern of 89 kDa and 25 kDa fragmentation of poly (ADP-ribose) polymerase (PARP) occurred in the muscle samples from animals bearing the MAC16 tumour and with a high amount of caspase-like activity. Cytochrome c was present in the cytosolic fractions of gastrocnemius muscles from both groups of animals, suggesting that cytochrome c release from mitochondria may be involved in caspase activation. There was no evidence for DNA fragmentation into a nucleosomal ladder typical of apoptosis in the muscles of either group of mice. This data supports a role for caspases in the catabolic events in muscle involved in the cancer cachexia syndrome. © 2001 Cancer Research Campaign.

Reversible addition–fragmentation chain transfer polymerization of 2-chloro-1,3-butadiene

Controlled polymerization of 2-chloro-1,3-butadiene using reversible addition–fragmentation chain transfer (RAFT) polymerization has been demonstrated for the first time. 2-Chloro-1,3-butadiene, more commonly known as chloroprene, has significant industrial relevance as a crosslinked rubber, with uses ranging from adhesives to integral automotive components. However, problems surrounding the inherent toxicity of the lifecycle of the thiourea-vulcanized rubber have led to the need for control over the synthesis of poly(2-chloro-1,3-butadiene). To this end, four chain transfer agents in two different solvents have been trialed and the kinetics are discussed. 2-Cyano-2-propylbenzodithioate (CPD) is shown to polymerize 2-chloro-1,3-butadiene in THF, using AIBN as an initiator, with complete control over the target molecular weight, producing polymers with low polydispersities (Mw/Mn < 1.25 in all cases).

Structure and physical properties of [µ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘')iron(II)] Bis(hexafluorophosphate), a new Fe(II) spin-crossover compound with a three-dimensional threefold interlocked crystal lattice

[μ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘)iron(II)] bis(hexafluorophosphate), [Fe(btzb)3](PF6)2, crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T1/2 = 174 K and a hysteresis of about 4 K between T1/2 and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, 57Fe-Mössbauer spectroscopy, and variable temperature far and midrange FTIR spectroscopy. The title compound crystallizes in the trigonal space group P30¯(No. 147) with a unit cell content of one formula unit plus a small amount of disordered solvent. The lattice parameters were determined by X-ray diffraction at several temperatures between 100 and 300 K. Complete crystal structures were resolved for 9 of these temperatures between 100 (only low spin, LS) and 300 K (only high spin, HS), Z = 1 [Fe(btzb)3](PF  6)2:  300 K (HS), a = 11.258(6) Å, c = 8.948(6) Å, V = 982.2(10) Å3; 100 K (LS), a = 10.989(3) Å, c = 8.702(2) Å, V = 910.1(4) Å3. The molecular structure consists of octahedral coordinated iron(II) centers bridged by six N4,N4‘ coordinating bis(tetrazole) ligands to form three 3-dimensional networks. Each of these three networks is symmetry related and interpenetrates each other within a unit cell to form the interlocked structure. The Fe−N bond lengths change between 1.993(1) Å at 100 K in the LS state and 2.193(2) Å at 300 K in the HS state. The nearest Fe separation is along the c-axis and identical with the lattice parameter c.

Fragm. lat. V 97 - Summa casuum (Zu den Dekretalen Gregors IX.: 2.27 - 28; 3.1 - 3, 8, 10)

Trägerband: Inc. qu. 960; Vorbesitzer: Zacharias Konrad von Uffenbach

(Tables 1-3) Water chemistry of cloud forest streams at baseflow conditions, Rio San Francisco, Ecuador

We investigated controls on the water chemistry of a South Ecuadorian cloud forest catchment which is partly pristine, and partly converted to extensive pasture. From April 2007 to May 2008 water samples were taken weekly to biweekly at nine different subcatchments, and were screened for differences in electric conductivity, pH, anion, as well as element composition. A principal component analysis was conducted to reduce dimensionality of the data set and define major factors explaining variation in the data. Three main factors were isolated by a subset of 10 elements (Ca2+, Ce, Gd, K+, Mg2+, Na+, Nd, Rb, Sr, Y), explaining around 90% of the data variation. Land-use was the major factor controlling and changing water chemistry of the subcatchments. A second factor was associated with the concentration of rare earth elements in water, presumably highlighting other anthropogenic influences such as gravel excavation or road construction. Around 12% of the variation was explained by the third component, which was defined by the occurrence of Rb and K and represents the influence of vegetation dynamics on element accumulation and wash-out. Comparison of base- and fast flow concentrations led to the assumption that a significant portion of soil water from around 30 cm depth contributes to storm flow, as revealed by increased rare earth element concentrations in fast flow samples. Our findings demonstrate the utility of multi-tracer principal component analysis to study tropical headwater streams, and emphasize the need for effective land management in cloud forest catchments.

(Table 6) Number of specimens of Polymastiidae and Suberitidae spp. found in ANDEEP I and II stations, POLARSTERN cruises ANT-XIX/4 and ANT-XXII/3

The Antarctic deep-water fauna of Polymastiidae and Suberitidae is revised using recently collected material from the Weddell Sea. The former family appeared to be more abundant and diverse than the latter family in the studied area. Seven species within five polymastiid genera and three species within three suberitid genera are described. Relatively high sponge abundance at two stations deeper than 4700 m was mainly constituted by a polymastiid species Radiella ant- arctica sp. nov. Previously, representatives of Radiella have never been found in the Antarctic. An eurybathic species, Polymastia invaginata , well known from the Antarctic and subantarctic, appeared to be especially abundant at less than 1000 m depth. Another eurybathic polymastiid species, Tentorium cf. semisuberites , known for its bipolar distribution, was the third abundant species at the depths between 1000-2600 m, with the highest density found at the deeper stations. Tentorium papillatum , endemic of the Southern Hemisphere, was registered only at a depth of about 1000 m. Other spe- cies studied were less abundant. Astrotylus astrotylus , the representative of the endemic Antarctic genus, was found exclusively deeper than 4500 m, often together with R. antarctica . Acanthopolymastia acanthoxa , the endemic deep- water Antarctic species, was registered at 3000 m. The discovery of suberitid Aaptos robustus sp. nov. at about 2300 m is the first signalization of Aaptos in the Antarctic and at such a considerable depth. The finding of Suberites topsenti deeper than 4700 m is also remarkable. In general the results achieved confirm the high degree of geographical ende- mism of the Antarctic deep-water sponge fauna and the eurybathic distribution of many Antarctic sponge species.

Aplicação informática para verificação de perfis enformados a frio segundo a EN1993-1-3

Os perfis enformados a frio estão em crescente uso na indústria da construção, utilizados como estruturas secundárias e primárias, por apresentar resistência em relação ao baixo peso, facilidade de utilização em obra e sustentabilidade. A norma europeia EN1993-1-3, também adotada em Portugal, que apresenta as especificações normativas sobre o uso estrutural de perfis enformados a frio é de difícil aplicação para os projetistas devido à quantidade e complexidade de cálculos para que sejam efetuadas as verificações de segurança necessárias, pelas limitações dos programas informáticos e complexidade de compreensão dos fenómenos da instabilidade local e distorcional que condicionam o comportamento deste tipo de secções, classificadas como de classe 4. O presente trabalho procura explicar os procedimentos do eurocódigo e os seus aspetos mais controversos, como, por exemplo, o processo de cálculo da distribuição de tensões numa secção arbitrária constituída por segmentos retos, o cálculo de larguras efetivas e espessuras reduzidas e as verificações de segurança em termos de resistência e estabilidade global requeridos pela norma. O principal objetivo deste trabalho é o desenvolvimento um programa de cálculo para verificar barras com secções de classe 4 que tenha a abrangência das especificações do Eurocódigo (EC3-1-3), que possa auxiliar engenheiros no processo de projeto, dimensionamento e verificação regulamentar de estruturas metálicas que utilizem este tipo de secções. Para isso foi criada uma aplicação informática, em ambiente Windows®, que está ligada ao programa Autodesk® Robot Structural Analisys® para obtenção de dados de cálculo e executar os cálculos de secções efetivas e verificações de segurança de acordo com a norma europeia. São apresentados diagramas de blocos com a sequência do procedimento de cálculo das várias fases de cálculo de secções efetivas e de verificação de barras, com vista a mostrar a lógica de funcionamento interno da aplicação criada no âmbito deste trabalho. Por fim desenvolve-se um manual de utilização da aplicação e um exemplo comparativo, de cálculo das propriedades efetivas de uma secção, entre os resultados do programa e documentos de referência com cálculos manuais

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

(Table 1) Water column silicic acid concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Silicon isotopic signatures (d30Si) of water column silicic acid (Si(OH)4) were measured in the Southern Ocean, along a meridional transect from South Africa (Subtropical Zone) down to 57° S (northern Weddell Gyre). This provides the first reported data of a summer transect across the whole Antarctic Circumpolar Current (ACC). d30Si variations are large in the upper 1000 m, reflecting the effect of the silica pump superimposed upon meridional water transfer across the ACC: the transport of Antarctic surface waters northward by a net Ekman drift and their convergence and mixing with warmer upper-ocean Si-depleted waters to the north. Using Si isotopic signatures, we determine different mixing interfaces: the Antarctic Surface Water (AASW), the Antarctic Intermediate Water (AAIW), and thermoclines in the low latitude areas. The residual silicic acid concentrations of end-members control the d30Si alteration of the mixing products and with the exception of AASW, all mixing interfaces have a highly Si-depleted mixed layer end-member. These processes deplete the silicic acid AASW concentration northward, across the different interfaces, without significantly changing the AASW d30Si composition. By comparing our new results with a previous study in the Australian sector we show that during the circumpolar transport of the ACC eastward, the d30Si composition of the silicic acid pools is getting slightly, but significantly lighter from the Atlantic to the Australian sectors. This results either from the dissolution of biogenic silica in the deeper layers and/or from an isopycnal mixing with the deep water masses in the different oceanic basins: North Atlantic Deep Water in the Atlantic, and Indian Ocean deep water in the Indo-Australian sector. This isotopic trend is further transmitted to the subsurface waters, representing mixing interfaces between the surface and deeper layers. Through the use of d30Si constraints, net biogenic silica production (representative of annual export), at the Greenwich Meridian is estimated to be 5.2 ± 1.3 and 1.1 ± 0.3 mol Si/m**2 for the Antarctic Zone and Polar Front Zone, respectively. This is in good agreement with previous estimations. Furthermore, summertime Si-supply into the mixed layer of both zones, via vertical mixing, is estimated to be 1.6 ± 0.4 and 0.1 ± 0.5 mol Si/m**2, respectively.

Annotated record of the detailed examination of Mn deposits from DSDP Site 40, Leg 5 (Cores 5-40-1, 5-40-11)

Site 40 was located by the JOIDES Pacific Advisory Panel in the region between the Molokai and Clarion Fracture Zones with the objective of recovering a continuous sediment core for the paleontologic and biostratigraphic study of the variation in sediment components at the transition between the North Pacific gyral and the Equatorial Current System.

Annotated record of the detailed examination of Mn deposits from DSDP Site 39, Leg 5 (Cores 5-39-1, 5-39-2)

Site 39 was located in the region between the Pioneer and Murray Fracture Zones, with the objective of recovering a continuous sediment core for paleontologic and stratigraphic study of the longitudinal variations in sediment components in the eastern Pacific. This site was selected, together with the adjacent ones in the north-south line along 140°W, to provide information on the geologic history of the North Pacific gyral, insofar as this might be recorded in the sediments.

Annotated record of the detailed examination of Mn deposits from DSDP Site 37, Leg 5 (Cores 5-37-1, 5-37-2)

The JOIDES Pacific Advisory Panel proposed Site 37 to meet two principal objectives: to determine the significance of the magnetic anomaly pattern, and the longitudinal profile of the sediment sequence in the eastern Pacific. Site 37 was to be located on the same magnetic anomaly as was Site 33 (#10, 32 million years age), for comparison across the intervening Mendocino Fracture Zone. As basement had not been reached at Site 33, this objective could not be met specifically. However, sediment comparison across the fracture zone was possible.