Atypical Mo isotope signatures in eastern Mediterranean sediments

Suboxic sapropel S1 sediments of the eastern Mediterranean carry an untypically light δ98/95Mo signal, being even lighter than oxic Mn-enriched sediments and Mn-crusts/nodules, which were previously thought to carry the lightest Mo isotope values. The evaluation and comparison of oxic S1, diagenetically overprinted oxic S1, and suboxic S1 sediments indicates that this light isotope signal is primarily an oxic signal that has been overprinted by secondary diagenetic processes occurring after sediment burial. Such secondary processes bear the potential of additional Mo isotope fractionation in particular in non-steady state diagenetic environments that involve the discontinuous re-location of the redox boundary.

'Dime cómo hablas y te diré dónde vives'. Percepción lingüística y representaciones geosociales en la ciudad de Lima

Esta contribución se inscribe dentro de un proyecto de investigación en marcha desde enero de 2012 que tiene por objetivo analizar la percepción de las hablas limeñas y las actitudes frente a éstas que tienen los hablantes de la capital del Perú, en directa relación con las representaciones geosociales que manejan de su ciudad, para lo cual partimos del concepto de estilos de interacción. Al hablar de representaciones geosociales queremos hacer hincapié en el hecho de que nuestra investigación no gira en torno a datos efectivos, empíricamente comprobables mediante censos y estudios socioeconómicos sobre la composición sociodemográfica de Lima Metropolitana y sus distritos, sino que se centra en los mapas sociales que forman y perfilan sus habitantes como consecuencia de sus experiencias individuales y de percepciones colectivas sociohistórica y culturalmente motivadas. Subrayemos entonces que el enfoque teórico de este estudio es constructivista, a partir del cual se analizará cómo los hablantes de Lima, en tanto que actores sociales, moldean su espacio urbano mediante las percepciones de la lengua y en interacción dinámica con “el otro” . Dentro de este marco, en el presente estudio nos ocupamos específicamente de la manera como es percibida por jóvenes limeñas la forma de hablar de otras limeñas jóvenes cuyos padres proceden de la Sierra peruana: ¿qué rasgos actúan como indicadores socio-étnicos y dónde, sobre la base de dichas percepciones, son “localizadas” en los mapas mentales de las entrevistadas estas “nuevas” limeñas? Estas preguntas son relevantes en relación con las hablas limeñas porque dada la situación de la ciudad de Lima, cuya población ha crecido fuertemente debido a la emigración de habitantes originarios de otras regiones del país, un estudio sobre las percepciones, representaciones y actitudes que tienen las jóvenes limeñas puede dar luces acerca de la existencia de nuevas variedades fruto del contacto interdialectal en Lima, de su reconocimiento y de su aceptabilidad sociolingüística por parte de los hablantes.

High-Spin Molecules: Synthesis, X-ray Characterization, and Magnetic Behavior of Two New Cyano-Bridged Ni II 9 Mo V 6 and Ni II 9 W V 6 Clusters with a S = 12 Ground State

The preparations, X-ray structures, and magnetic characterizations are presented for two new pentadecanuclear cluster compounds:  [NiII{NiII(MeOH)3}8(μ-CN)30{MV(CN)3}6]·xMeOH·yH2O (MV = MoV (1) with x = 17, y = 1; MV = WV (2) with x = 15, y = 0). Both compounds crystallize in the monoclinic space group C2/c, with cell dimensions of a = 28.4957(18) Å, b = 19.2583(10) Å, c = 32.4279(17) Å, β = 113.155(6)°, and Z = 4 for 1 and a = 28.5278(16) Å, b = 19.2008(18) Å, c = 32.4072(17) Å, β = 113.727(6)°, and Z = 4 for 2. The structures of 1 and 2 consist of neutral cluster complexes comprising 15 metal ions, 9 NiII and 6 MV, all linked by μ-cyano ligands. Magnetic susceptibilities and magnetization measurements of compounds 1 and 2 in the crystalline and dissolved state indicate that these clusters have a S = 12 ground state, originating from intracluster ferromagnetic exchange interactions between the μ-cyano-bridged metal ions of the type NiII−NC−MV. Indeed, these data show clearly that the cluster molecules stay intact in solution. Ac magnetic susceptibility measurements reveal that the cluster compounds exhibit magnetic susceptibility relaxation phenomena at low temperatures since, with nonzero dc fields, χ‘ ‘M has a nonzero value that is frequency dependent. However, there appears no out-of-phase (χ‘ ‘M) signal in zero dc field down to 1.8 K, which excludes the expected signature for a single molecule magnet. This finding is confirmed with the small uniaxial magnetic anisotropy value for D of 0.015 cm-1, deduced from the high-field, high-frequency EPR measurement, which distinctly reveals a positive sign in D. Obviously, the overall magnetic anisotropy of the compounds is too low, and this may be a consequence of a small single ion magnetic anisotropy combined with the highly symmetric arrangement of the metal ions in the cluster molecule.

Decomposition studies of group 6 hexacarbonyl complexes. Part 1: Production and decomposition of Mo(CO)6 and W(CO)6

Chemical studies of superheavy elements require fast and efficient techniques, due to short half-lives and low production rates of the investigated nuclides. Here, we advocate for using a tubular flow reactor for assessing the thermal stability of the Sg carbonyl complex – Sg(CO)6. The experimental setup was tested with Mo and W carbonyl complexes, as their properties are established and supported by theoretical predictions. The suggested approach proved to be effective in discriminating between the thermal stabilities of Mo(CO)6 and W(CO)6. Therefore, an experimental verification of the predicted Sg–CO bond dissociation energy seems to be feasible by applying this technique. By investigating the effect of 104,105Mo beta-decay on the formation of 104,105Tc carbonyl complex, we estimated the lower reaction time limit for the metal carbonyl synthesis in the gas phase to be more than 100 ms. We examined further the influence of the wall material of the recoil chamber, the carrier gas composition, the gas flow rate, and the pressure on the production yield of 104Mo(CO)6, so that the future stability tests with Sg(CO)6 can be optimized accordingly.

Deletion of exon 8 from the EXT1 gene causes multiple osteochondromas (MO) in a family with three affected members.

Multiple osteochondromas (also called hereditary multiple exostoses) is an autosomal dominant disorder characterized by multiple cartilaginous tumors, which are caused by mutations in the genes for exostosin-1 (EXT1) and exostosin-2 (EXT2). The goal of this study was to elucidate the genetic alterations in a family with three affected members. Isolation of RNA from the patients' blood followed by reverse transcription and PCR amplification of selected fragments showed that the three patients lack a specific region of 90 bp from their EXT1 mRNA. This region corresponds to the sequence of exon 8 from the EXT1 gene. No splice site mutation was found around exon 8. However, long-range PCR amplification of the region from intron 7 to intron 8 indicated that the three patients contain a deletion of 4318 bp, which includes exon 8 and part of the flanking introns. There is evidence that the deletion was caused by non-homologous end joining because the breakpoints are not located within a repetitive element, but contain multiple copies of the deletion hotspot sequence TGRRKM. Exon 8 encodes part of the active site of the EXT1 enzyme, including the DXD signature of all UDP-sugar glycosyltransferases. It is conceivable that the mutant protein exerts a dominant negative effect on the activity of the EXT glycosyltransferase since it might interact with normal copies of the enzyme to form an inactive hetero-oligomeric complex. We suggest that sequencing of RNA might be superior to exome sequencing to detect short deletions of a single exon.