Atom-Economical Synthesis of the Versatile Ruthenium Precursor [TpRuCl(COD)] (Tp = Hydrotris(pyrazol-1-yl)borate) Discloses a Diamine Ligand Dealkylation Process

An atom-economical, more environmentally friendly alternative method of synthesis of the versatile complex [TpRuCl(COD)] (1) (Tp = hydrotris(pyrazol-1-yl)borate; COD = 1,5-cyclooctadiene) has been developed. Instead of starting from [RuHCl(COD)(NH2NMe2)3]+, 1 can be conveniently prepared by reaction of the derivative trans-[RuCl2(COD)(Me2NCH2- CH2NHMe)] (2) with KTp in acetone at 55 °C. Compound 2, which has been structurally characterized by X-ray crystallography, results from an unexpected diamine dealkylation process which takes place in the course of the reaction of [{RuCl2(COD)}n] with tmeda (tmeda = Me2NCH2CH2NMe2) in toluene at 80 °C. This process had been overlooked in the literature, as compound 2 had been misidentified as cis-[RuCl2(COD)(tmeda)], and suggests that amine dealkylation might occur more commonly than previously anticipated

Activation of Propargyl Alcohols by TpRu Complexes Bearing a Bidentate NHC Ligand

The complex [TpRuCl(COD)] reacts with L·Ag2Cl2 (L = bis(3- methylimidazol-2-ylidene)) in dichloroethane at 120 °C for a period of 20 h, furnishing the bis(carbene) derivative [TpRuCl(L)] (1). This compound reacts with NaBAr′4 in FPh under dinitrogen to yield the cationic dinitrogen complexes [TpRu(N2)(L)][BAr′4] (2′) and [{TpRu(L)}(μ-N2)][BAr′4]2 (2). The terminal dinitrogen complex 2′ is labile and spontaneously converts into 2, which was structurally characterized. The reaction of 2 with CO is slow and affords [TpRu(CO)(L)][BAr′4] (3). The kinetics of the substitution of coordinated dinitrogen in 2 by CD3CN has been studied. The value of 25 ± 4 kcal mol−1 determined for ΔG⧧ 298 for the substitution reaction is consistent with the observation that the dinitrogen ligand is strongly bound to ruthenium in 2. Complex 1 reacts with propargyl alcohols HC≡CC(OH)RR′ (RR′ = Me2 , (CH2)5, MePh, HPh) and NaBPh4 in MeOH at 50−60 °C, yielding the corresponding γ-methoxyvinylidene complexes [TpRu=C=CHC(OMe)RR′(L)][BPh4] (RR′ = Me2 (4a), (CH2)5 (4b), MePh (4c), HPh (4d)). The reaction of 1 with HC≡CCH2OH under the same conditions led to the γ-hydroxyvinylidene derivative [TpRu=C=CHCH2OH(L)][BPh4] (5), whereas the reaction with HC≡CC(OH)Ph2 resulted in the formation of the deep purple allenylidene complex [TpRu=C=C=CPh2(L)][BPh4] (6). A series of N- and S-donor molecules such as pyrazole, piperidine, 2-pyridinethiol, and 1,3-benzenedithiol add to the Cα atom of the allenylidene ligand in 6 to yield the corresponding diphenylvinylcarbene species [TpRu=C(X)CH=CPh2(L)][BPh4] (X = C3H3N2 (7), N(CH2)4CH2 (8), SC5H4N (9), SC6H4SH (10)), of which compound 7 was structurally characterized. The reaction of 6 with KOBut in acetone produced the neutral σ-alkynyl derivative [TpRuC≡CC(CH2COCH3)Ph2(L)] (11), resulting from the addition of acetone enolate to the Cγ of the allenylidene ligand

Using oceanography to control and forecast nuclear accidents and other passive particles problems

This article is the last improved version of a previously published model (Toscano-Jimenez and Garcia-Tenorio, 2004) for the transport of the nuclear contamination and other passive particles in the ocean. Two interesting advances have been developed during last two years for the author's PhD thesis to be finished in the next months: (a) a suspended particulate matter (SPM) submodel, including erosion, transport and sedimentation. (b) A new advection-diffusion approach with numerical and computational improvements: finite elements (FE), finite differences (FD) and Monte Carlo (MC) methods have been compared and calibrated. The Baltic Sea has been elected as the validation scenario of the model and the radioisotope 137 Cs is the radiotracer to be analysed. This scenario was the most contaminated ecosystem out of the Soviet Union due to the Chernobyl accident which occurred at the end of April 1986, and the elected radiotracer 137 Cs was the main long-lived radioisotope emitted to the environment. However, an important aim of this model is its potential usefulness in other oceanic scenarios affected by a nuclear disaster in the future. It could be an interesting tool to predict and minimize the ecological and economical impacts of future accidents. This model can also be extended easily to non-nuclear contamination problems such as: oil accidents, nutrients dynamics and other biological problems

Conotoxin Diversity in the Venom Gland Transcriptome of the Magician’s Cone, Pionoconus magus

The transcriptomes of the venom glands of two individuals of the magician’s cone, Pionoconus magus, from Okinawa (Japan) were sequenced, assembled, and annotated. In addition, RNA-seq raw reads available at the SRA database from one additional specimen of P. magus from the Philippines were also assembled and annotated. The total numbers of identified conotoxin precursors and hormones per specimen were 118, 112, and 93. The three individuals shared only five identical sequences whereas the two specimens from Okinawa had 30 sequences in common. The total number of distinct conotoxin precursors and hormones for P. magus was 275, and were assigned to 53 conotoxin precursor and hormone superfamilies, two of which were new based on their divergent signal region. The superfamilies that had the highest number of precursors were M (42), O1 (34), T (27), A (18), O2 (17), and F (13), accounting for 55% of the total diversity. The D superfamily, previously thought to be exclusive of vermivorous cones was found in P. magus and contained a highly divergent mature region. Similarly, the A superfamily alpha 4/3 was found in P. magus despite the fact that it was previously postulated to be almost exclusive of the genus Rhombiconus. Di erential expression analyses of P. magus compared to Chelyconus ermineus, the only fish-hunting cone from the Atlantic Ocean revealed that M and A2 superfamilies appear

Chromosome-level genome of the venomous snail Kalloconus canariensis: a valuable model for venomics and comparative genomics

BACKGROUND: Genomes are powerful resources to understand the evolutionary mechanisms underpinning the origin and diversification of the venoms of cone snails (Conidae: Caenogastropoda) and could aid in the development of novel drugs. FINDINGS: Here, we used PacBio continuous long reads and Omni-C data to assemble the chromosome-level genome of Kalloconus canariensis, a vermivorous cone endemic to the Canary Islands. The final genome size was 2.87 Gb, with a N50 of 79.75 Mb and 91% of the reads located into the 35 largest scaffolds. Up to 55.80% of the genome was annotated as repetitive regions, being class I of transposable elements (16.65%) predominant. The annotation estimated 34,287 gene models. Comparative analysis of this genome with the 2 cone snail genomes released to date (Dendroconus betulinus and Lautoconus ventricosus) revealed similar genome sizes and organization, although chromosome sizes tended to be shorter in K. canariensis. Phylogenetic relationships within subclass Caenogastropoda were recovered with strong statistical support. The family Conidae was recovered as a clade, with K. canariensis plus L. ventricosus sister to D. betulinus. CONCLUSIONS: Despite the great diversity of cone snails (>900 species) and their venoms (hundreds of peptides per species), only 2 recently reported genomes are available for the group. The high-quality chromosome-level assembly of K. canariensis will be a valuable reference for studying the origin and evolution of conotoxin genes as well as whole-genome duplication events during gastropod evolution

Estudo etnográfico sobre dramatização da alegria por classes sociais e do estigma dos idosos do Albergue Santo Antônio (Colômbia)

Objetivo: Analizar las interacciones sociales de los internos del asilo San Antonio (Barranquilla) desde la perspectiva dramática, con el fin de entender los mecanismos por medio de los cuales asumen sus estigmas para acomodarse al sistema. Metodología: Etnografía interaccionista de corte analítico. Se recogió la información por medio de observación participante, notas de campo, registro fotográfico y 22 entrevistas en profundidad a informantes clave. La información, previamente organizada en unidades de registro, contexto y categorías, se sometió a un análisis crítico del discurso para hallar patrones de relevancia que sirvieron para desarrollar, analíticamente, los resultados en cinco ejes. Resultados: se identificaron cinco estrategias dramáticas por medio de las cuales los internos del asilo incorporan los estigmas en aras de complacer tácticamente al sistema: la presencia de los propios investigadores como agentes estigmatizadores, la obediencia atribuida, la excesiva trasparencia identitaria como enfermo, la autoimposición del estigma y el edadismo estratégico. Conclusiones: Los internos del Asilo San Antonio terminan por participar de su propio sometimiento, incorporando los estigmas que le son atribuidos por el sistema. Abogamos por desarrollar una visión cultural humanista de los cuidados que restituya, al espacio de atención a personas sensibles, su valor antropológico, para que prevalezca sobre los procedimientos institucionales.Objective: Analyze the social interactions of the San Antonio asylum inmates (Barranquilla) from the dramatic perspective, in order to understand the mechanisms by which they assume their stigmas to accommodate the system. Method: Interactionist ethnography of an analytical nature. The information was collected through participant observation, field notes, photographic record and 22 in-depth interviews with key informants. The information, previously organized in units of registration, context and categories, underwent a critical discourse analysis to find patterns of relevance that served to develop, analytically, the results in five axes. Results: Five dramatic strategies were identified through which the inmates of the asylum incorporate the stigmas in order to tactfully please the system: the presence of the researchers themselves as stigmatizing agents, the attributed obedience, the excessive identity transparency as a patient, the self-imposed stigma and strategic ageism. Conclusion: The San Antonio asylum inmates end up participating in their own subjection, incorporating the stigmas attributed to them by the system. We advocate to develop a humanistic cultural vision of the care that restores, to the space of attention to sensitive people, its anthropological value, so that it prevails over institutional procedures.Objetivo: analisar as interações sociais dos internos do Asilo Santo Antônio (Barranquilla) desde a perspectiva dramática, com a finalidade de entender os mecanismos através dos quais assumem seus estigmas para adequar-se ao sistema. Metodologia: Etnografía Interacionista de corte analítico. Apanhou-se a informação mediante o uso da observação participante, anotações de campo, registro fotográfico e 22 entrevistas em profundidade em informantes clave. A informação previamente organizada em unidades de registro, contexto e categorias, foi submetida a uma análise crítica do discurso para encontrar padrões de relevância que serviram para desenvolver, analiticamente, os resultados em cinco eixos. Resultados: foram identificadas cinco estrategias dramáticas através das quais os interno do asilo incorporam os estigmas em áreas de complacer taticamente ao sistema: a presença dos mesmos pesquisadores como agentes estigmatizadores, a obediência atribuída, a excesiva transparência identitária como doente, a auto-imposição do estigma e o edadismo estratégico. Conclusões: os internos do Asilo Santo Antônio findam participando de seu próprio submetimento, incorporando os estigmas que lhes são atribuídos pelo sistema. Advogamos pelo desenvolvimento de uma visão humanista dos cidadãos que restitua, ao espaço de atenção a pessoas sensíveis, seu valor antropológico, para que prevaleça sobre os procedimentos institucionais

Searching for indicators of age, sex and population in European mouflon mandibles

Mandibles from separate populations of free-living mouflons (Ovis aries musimon) from Southern Spain, submitted to different ecological conditions, were studied. Searching for ontogenetic shape variations we used geometric morphometrics tools and we explored the use of several mathematical models for describing growth rate variations between populations and sexes. A strong allometry was detected with variations in shape mainly matching with molar and premolar eruption. Mandible shape did not vary significantly with sex nor was sexual size dimorphism detected in adults, whatever the population. By modeling growth we detected differences between populations in all parameters such as the maturity rate describing precocity, and the time it took to reach asymptotic size (varying from 9 up to 18 months). A longer period of growth did not result in a larger asymptotic size, but it led to smaller mandibles. Mouflons with relatively late teeth replacement, lower maturation rate and smaller adult size were those of the population submitted to extreme environmental conditions, like epizootic disease, droughts and ungulate overpopulations. We discuss how a delay in reaching mature size has probably an important subsequent impact on reproductive and life-history traits in this species. Being able to record the effects of density-dependent and density-independent factors, mandibles become a target of interest for ecological and management studies also on mouflons

First examples of neutral and cationic indenyl nickel(II) complexes bearing arsine or stibine ligands: highly active catalysts for the oligomerisation of styrene

New indenyl nickel(II) complexes bearing arsine or stibine ligands synthesised by a new methodology exhibit very high catalytic activities for the oligomerisation of styrene

Counteranion-Dependent Reaction Pathways in the Protonation of Cationic Ruthenium−Vinylidene Complexes

The tetraphenylborate salts of the cationic vinylidene complexes [Cp*Ru=C=CHR(iPr2PNHPy)]+ (R = p-C6H4CF3 (1a-BPh4), Ph (1b-BPh4), p-C6H4CH3 (1c- BPh4), p-C6H4Br (1d-BPh4), tBu (1e-BPh4), H (1f-BPh4)) have been protonated using an excess of HBF4·OEt2 in CD2Cl2, furnishing the dicationic carbyne complexes [Cp*Ru≡CCH2R(iPr2PNHPy)]2+ (R = p-C6H4CF3 (2a), Ph (2b), p-C6H4CH3 (2c), p-C6H4Br (2d), tBu (2e), H (2f)), which were characterized in solution at low temperature by NMR spectroscopy. The corresponding reaction of the chloride salts 1a-Cl, 1b-Cl, 1c-Cl, and 1d-Cl followed a different pathway, instead affording the novel alkene complexes [Cp*RuCl(κ1(N),η2(C,C)-C5H4N-NHPiPr2CH=CHR)][BF4] (3a−d). In these species, the entering proton is located at the α- carbon atom of the former vinylidene ligand, which also forms a P−C bond with the phosphorus atom of the iPr2PNHPy ligand. To shed light on the reaction mechanism, DFT calculations have been performed by considering several protonation sites. The computational results suggest metal protonation followed by insertion. The coordination of chloride to ruthenium leads to alkenyl species which can undergo a P−C coupling to yield the corresponding alkene complexes. The noncoordinating nature of [BPh4]− does not allow the stabilization of the unsaturated species coming from the insertion step, thus preventing this alternative pathway

Unraveling the effect of silent, intronic and missense mutations on VWF splicing: contribution of next generation sequencing in the study of mRNA

Large studies in von Willebrand disease patients, including Spanish and Portuguese registries, led to the identification of >250 different mutations. It is a challenge to determine the pathogenic effect of potential splice site mutations on VWF mRNA. This study aimed to elucidate the true effects of 18 mutations on VWF mRNA processing, investigate the contribution of next-generation sequencing to in vivo mRNA study in von Willebrand disease, and compare the findings with in silico prediction. RNA extracted from patient platelets and leukocytes was amplified by RT-PCR and sequenced using Sanger and next generation sequencing techniques. Eight mutations affected VWF splicing: c.1533+1G>A, c.5664+2T>C and c.546G>A (p.=) prompted exon skipping; c.3223-7_3236dup and c.7082-2A>G resulted in activation of cryptic sites; c.3379+1G>A and c.7437G>A) demonstrated both molecular pathogenic mechanisms simultaneously; and the p.Cys370Tyr missense mutation generated two aberrant transcripts. Of note, the complete effect of three mutations was provided by next generation sequencing alone because of low expression of the aberrant transcripts. In the remaining 10 mutations, no effect was elucidated in the experiments. However, the differential findings obtained in platelets and leukocytes provided substantial evidence that four of these would have an effect on VWF levels. In this first report using next generation sequencing technology to unravel the effects of VWF mutations on splicing, the technique yielded valuable information. Our data bring to light the importance of studying the effect of synonymous and missense mutations on VWF splicing to improve the current knowledge of the molecular mechanisms behind von Willebrand disease. clinicaltrials.gov identifier:02869074