Osmium impregnated on magnetite as a heterogeneous catalyst for the syn-dihydroxylation of alkenes

A new catalyst derived from osmium has been prepared, fully characterized and tested in the dihydroxylation of alkenes. The catalyst was prepared by wet impregnation methodology of OsCl3·3H2O on a commercial micro-magnetite surface. The catalyst allowed the reaction with one of the lowest osmium loadings for a heterogeneous catalyst and was selective for the monodihydroxylation of 1,5-dienes. Moreover, the catalyst was easily removed from the reaction medium by the simple use of a magnet. The selectivity of catalyst is very high with conversions up to 99%. Preliminary kinetics studies showed a first-order reaction rate with respect to the catalyst.

Selective hydrosilylation of 1,3-diynes catalyzed by titania-supported platinum

Titania-supported platinum (mainly as Pt(II)) has been found to effectively catalyze the hydrosilylation of 1,3-diynes at 70 °C with low catalyst loading (0.25 mol %) under solvent-free conditions. Monohydrosilylation was achieved for diaryl-substituted diynes, whereas dialkyl-substituted diynes were transformed into the corresponding dihydrosilylated products in good yields. In every case, the process was proven to be highly stereoselective, with syn addition of the silicon–hydrogen bond, and regioselective, with the silicon moiety exclusively bonded to the most internal carbon atom of the 1,3-diyne (β-E product), as confirmed by X-ray crystallography.

La sección de San Miguel de Salinas (Cuenca del Bajo Segura): significado paleoambiental de las asociaciones de foraminíferos en relación con la Crisis de Salinidad del Messiniense

In the composite section of San Miguel de Salinas the following synthems are represented: MI (preevaporitic Messinan), MII (syn-evaporitic Messinian) and P (post-evaporitic Pliocene). The foraminiferal assemblages of these synthems have been studied in order to reveal the palaeoenvironmental changes related to the Mediterranean Salinity Crisis. The change between MI and MII synthems is characterized by the reduction of the foraminiferal biodiversity. Synthem MII records palaeoenvironmental stress related to the evaporitic deposition during the Salinity Crisis. Synthem P marks an abrupt increase of the foraminiferal biodiversity in coincidence with the Pliocene reflooding of the Mediterranean Sea.

La Galite Archipelago (Tunisia, North Africa): stratigraphic and petrographic revision and insights for geodynamic evolution of the Maghrebian Chain

The location of the La Galite Archipelago on the Internal/External Zones of the Maghrebian Chain holds strong interest for the reconstruction of the geodynamic evolution of the Mesomediterranean Microplate-Africa Plate Boundary Zone. New stratigraphic and petrographic data on sedimentary successions intruded upon by plutonic rocks enabled a better definition of the palaeogeographic and palaeotectonic evolutionary model of the area during the early-middle Miocene. The lower Miocene sedimentary units (La Galite Flysch and Numidian-like Flysch) belong to the Mauritanian (internal) and Massylian (external) sub-Domains of the Maghrebian Chain, respectively. These deposits are related to a typical syn-orogenic deposition in the Maghrebian Flysch Basin Domain, successively backthrusted above the internal units. The backthrusting age is post-Burdigalian (probably Langhian-Serravallian) and the compressional phase represents the last stage in the building of the accretionary wedge of the Maghrebian orogen. These flysch units may be co-relatable to the similar well-known formations along the Maghrebian and Betic Chains. The emplacement of potassic peraluminous magmatism, caused local metamorphism in the Late Serravallian-Early Tortonian (14–10 Ma), after the last compressional phase (backthrusting), during an extensional tectonic event. This extensional phase is probably due to the opening of a slab break-off in the deep subduction system. La Galite Archipelago represents a portion of the Maghrebian Flysch Basin tectonically emplaced above the southern margin of the “Mesomediterranean Microplate” which separated the Piemontese-Ligurian Ocean from a southern oceanic branch of the Tethys (i.e. the Maghrebian Flysch Basin). The possible presence of an imbricate thrust system between La Galite Archipelago and northern Tunisia may be useful to exclude the petroleum exploration from the deformed sectors of the offshore area considered.

Synthesis of α,β-diamino acid derivatives via asymmetric Mannich reactions of glycine imino esters catalyzed by a chiral phosphoramidite·silver complex

AgOTf·phosphoramidite complexes efficiently catalyze the enantioselective Mannich-type reaction between benzophenone-imine glycine methyl ester and N-tosyl aldimines in the absence of a base. The corresponding syn-adducts, which are the direct precursors of α,β-diamino acids, are obtained with moderate to good syn-diastereoselectivities (up to 9:1) and high enantioselectivities (up to 99% ee).

Glyoxylic Acid versus Ethyl Glyoxylate for the Aqueous Enantio­selective Synthesis of α-Hydroxy-γ-Keto Acids and Esters by the N-Tosyl-(S a)-binam-l-prolinamide-Organocatalyzed Aldol Reaction

N-Tosyl-(S a)-binam-l-prolinamide is an efficient catalyst for the aqueous aldol reaction between ketones and glyoxylic acid, as the monohydrate or as an aqueous solution, or a 50% toluene solution of ethyl glyoxylate. These reactions led to the formation of chiral α-hydroxy-γ-keto carboxylic acids and esters in high levels of diastereo- and enantioselectivities (up to 97% ee), providing mainly anti aldol products. Only cyclopentanone and cyclohexane-1,4-dione afforded an almost 1:1 mixture of the syn/anti-diastereoisomers; however, the reaction between 4-phenylcyclohexanone and ethyl glyoxylate gave the corresponding syn,syn-product as the major diastereoisomer.

Phosphorylated α-synuclein-immunoreactive retinal neuronal elements in Parkinson's disease subjects

Visual symptoms are relatively common in Parkinson's disease (PD) and optical coherence tomography has indicated possible retinal thinning. Accumulation of aggregated α-synuclein is thought to be a central pathogenic event in the PD brain but there have not as yet been reports of retinal synucleinopathy. Retinal wholemounts were prepared from subjects with a primary clinicopathological diagnosis of PD (N = 9), dementia with Lewy bodies (DLB; N = 3), Alzheimer's disease (N = 3), progressive supranuclear palsy (N = 2) as well as elderly normal control subjects (N = 4). These were immunohistochemically stained with an antibody against α-synuclein phosphorylated at serine 129, which is a specific molecular marker of synucleinopathy. Phosphorylated α-synuclein-immunoreactive (p-syn IR) nerve fibers were present in 7/9 PD subjects and in 1/3 DLB subjects; these were sparsely distributed and superficially located near or at the inner retinal surface. The fibers were either long and straight or branching, often with multiple en-passant varicosities along their length. The straight fibers most often had an orientation that was radial with respect to the optic disk. Together, these features are suggestive of either retinopetal/centrifugal fibers or of ganglion cell axons. In one PD subject there were sparse p-syn IR neuronal cell bodies with dendritic morphology suggestive of G19 retinal ganglion cells or intrinsically photosensitive ganglion cells. There were no stained nerve fibers or other specific staining in any of the non-PD or non-DLB subjects. It is possible that at least some of the observed visual function impairments in PD subjects might be due to α-synucleinopathy.

Paleogene evolution of the External Betic Zone and geodynamic implications

Interdisciplinary studies combining field data (geological and tectonic mapping, lithostratigraphic reconstructions, lithofacies characterization, correlations and sampling) and laboratory analyses (biostratigraphy, chronostratigraphy, clay mineralogy and sandstone petrography) of eight Senonian-Paleogene successions from the Sierra de La Pila and Sierra de El Carche areas (Murcia province, SE Spain) belonging to the External Betic Zone are presented. Field evidence of tectonic activity (slumps, olistostromes, syn-genetic folds, lateral variability, changes in thicknesses, para- and unconformity boundaries, stratigraphic gaps, shallowing upward trends to emersion, etc.) was found in several Paleogene intervals. The results enable a better reconstruction of the stratigraphic architecture and chronostratigraphy of the Paleogene record, highlighting in particular: facies evolution, discontinuities, depositional sequences (Middle-Upper Maastrichtian, Upper Paleocene-Middle Eocene, Oligocene-Lower Aquitanian), environmental evolution (homogeneous conditions during the Late Cretaceous and successive realm diversification from platform to slope to basin) and correlations, along the Prebetic to Subbetic transition, which is a key sector to understand the northeastward variations of the South Iberian margin. A conclusive paleogeographic and geodynamic evolutionary model for the study area is proposed, hypothesizing that Paleogene compressive tectonics affected the eastern External Betic Zone. In addition, correlations with successions from the western External Betic Zone evidenced asynchronous deformation from east to west along the internalmost External Betic Zone. Moreover, a comparison with the external Tunisian Tell enables the recognition of similar sedimentarytectonic events, imposing new constraints in the Paleogene geodynamic reconstruction throughout the western Tethys.

Paleogene-Aquitanian Tectonic Breakup in the Eastern External Betic Zone (Alicante, SE Spain)

Six Paleogene-Aquitanian successions have been reconstructed in the Alicante area (eastern External Betic Zone). The lithofacies association evidences “catastrophic” syn-sedimentary tectonic processes consisting of slumps, mega-olisthostromes, “pillow-beds” and turbiditic deposits. This kind of sedimentation is related to unconformity surfaces delimiting sequence and para-sequence cycles in the stratigraphic record. The data compiled have enabled the reconstruction of the Paleogene-Aquitanian paleogeographic and geodynamic evolution of this sector of the External Betics. During the Eocene the sedimentary basin is interpreted as a narrow trough affected by (growth) folding related to blind thrust faulting with a source area from the north-western margin, while the southeastern margin remained inactive. During the Oligocene-Aquitanian, the sourcing margin becames the southeastern margin of the basin affected by a catastrophic tectonic. The activity of the margins is identified from specific sediment source areas for the platform-slope-trough system and from tectofacies analysis. The southeastern South Iberian Margin is thought to be closer to the Internal Betic Zone, which was tectonically pushing towards the South Iberian Margin. This pushing could generate a lateral progressive elimination of subbetic paleogeographic domains in the eastern Betics. This geodynamic frame could explain the development of such “catastrophic” tectono-sedimentary processes during the Late Oligocene-Early Miocene.

The Early Miocene “Bisciaro volcaniclastic event” (northern Apennines, Italy): a key study for the geodynamic evolution of the central-western Mediterranean

The Early Miocene Bisciaro Fm., a marly limestone succession cropping out widely in the Umbria–Romagna–Marche Apennines, is characterized by a high amount of volcaniclastic content, characterizing this unit as a peculiar event of the Adria Plate margin. Because of this volcaniclastic event, also recognizable in different sectors of the central-western Mediterranean chains, this formation is proposed as a “marker” for the geodynamic evolution of the area. In the Bisciaro Fm., the volcaniclastic supply starts with the “Raffaello” bed (Earliest Aquitanian) that marks the base of the formation and ends in the lower portion of the Schlier Fm. (Late Burdigalian–Langhian p.p.). Forty-one studied successions allowed the recognition of three main petrofacies: (1) Pyroclastic Deposits (volcanic materials more than 90 %) including the sub-petrofacies 1A, Vitroclastic/crystallo-vitroclastic tuffs; 1B, Bentonitic deposits; and 1C, Ocraceous and blackish layers; (2) Resedimented Syn-Eruptive Volcanogenic Deposits (volcanic material 30–90 %) including the sub-petrofacies 2A, High-density volcanogenic turbidites; 2B, Low-density volcanogenic turbidites; 2C, Crystal-rich volcanogenic deposits; and 2D, Glauconitic-rich volcaniclastites; (3) Mixing of Volcaniclastic Sediments with Marine Deposits (volcanic material 5–30 %, mixed with marine sediments: marls, calcareous marls, and marly limestones). Coeval volcaniclastic deposits recognizable in different tectonic units of the Apennines, Maghrebian, and Betic Chains show petrofacies and chemical–geochemical features related to a similar calc-alkaline magmatism. The characterization of this event led to the hypothesis of a co-genetic relationship between volcanic activity centres (primary volcanic systems) and depositional basins (depositional processes) in the Early Miocene palaeogeographic and palaeotectonic evolution of the central-western Mediterranean region. The results support the proposal of a geodynamic model of this area that considers previously proposed interpretations.

Compositional signatures of the Cenozoic sedimentary succesions of the Malaguide Complex (Betic Cordillera, Spain)

The studied Cenozoic sedimentary successions consist of deposits from continental/shallow-water to deep-marine environments of the Malaguide Complex (Betic Cordillera) outcropping in the Sierra Espuña area (SE Spain). The aim of this study is to characterize the composition, source area(s) provenance and weathering processes of these sedimentary successions from the pre-orogenic (Paleocene-Early Oligocene) to the syn-orogenic (Late Oligocene-Early Miocene) stage using petrological and geochemical methodologies. The studied sandstones are mainly quartzolithic with abundant metamorphic and sedimentary lithic fragments. In particular, the composition of samples from the pre-orogenic cycle is mainly carbonate with important siliciclastic components that occur within the medium to fine grained arenites. The composition of samples from the syn-orogenic cycle is characterized by a sharp change from carbonate to siliciclastic terms. Thus, the composition of the overall sandstone samples is very heterogeneous and suggests a source area mainly characterized by the Malaguide basement and lower units of the Internal Betic Zone, that partially compose the Mesomediterranean Microplate. The geochemical proxies suggest a provenance mainly from felsic source area with a minor supply from mafic rocks in some samples of the syn-orogenic stage. Furthermore, palaeoweathering indices indicate low to moderate weathering conditions for the sources. The Cenozoic sedimentary successions of the Malaguide Complex played an important role in the geodynamic evolution of the Betic Cordillera that represents the key tectonic element of the western domains of the Mesomediterranean Microplate.