gem-selective cross-dimerization and cross-trimerization of alkynes with silylacetylenes promoted by a Rhodium-Pyridine-N-heterocyclic carbene catalyst

The gem-selective cross-dimerization and -trimerization of silylacetylenes with alkynes through C[BOND]H activation using a rhodium(I)–pyridine–N-heterocyclic carbene catalyst have been developed. This reaction is applied to various aliphatic or aromatic terminal alkynes, internal alkynes, and gem-1,3-disubsituted enynes to afford the corresponding enynes and dienynes with high regio- and stereoselectivities and in good isolated yields (up to 91 %).Financial support from the Spanish Ministerio de Economía y Competitividad (MEC/FEDER) of Spain Project (CTQ2010-15221), the Diputación General de Aragón (E07), the KFUPMUNIZAR agreement, and CONSOLIDER INGENIO-2010, under the Project MULTICAT (CSD2009-00050) are gratefully acknowledged. L. R.-P. thanks CONACyT (Mexico, 186898 and 204033) for a postdoctoral fellowship.Peer Reviewe

Short-Term Response of Cytosolic N O 3 - to Inorganic Carbon Increase in Posidonia oceanica Leaf Cells.

The concentration of CO2 in the atmosphere has increased over the past 200 years and is expected to continue rising in the next 50 years at a rate of 3 ppm·year-1. This increase has led to a decrease in seawater pH that has changed inorganic carbon chemical speciation, increasing the dissolved HC O 3 - . Posidonia oceanica is a marine angiosperm that uses HC O 3 - as an inorganic carbon source for photosynthesis. An important side effect of the direct uptake of HC O 3 - is the diminution of cytosolic Cl- (Cl-c) in mesophyll leaf cells due to the efflux through anion channels and, probably, to intracellular compartmentalization. Since anion channels are also permeable to N O 3 - we hypothesize that high HC O 3 - , or even CO2, would also promote a decrease of cytosolic N O 3 - ( N O 3 - c ). In this work we have used N O 3 - - and Cl--selective microelectrodes for the continuous monitoring of the cytosolic concentration of both anions in P. oceanica leaf cells. Under light conditions, mesophyll leaf cells showed a N O 3 - c of 5.7 ± 0.2 mM, which rose up to 7.2 ± 0.6 mM after 30 min in the dark. The enrichment of natural seawater (NSW) with 3 mM NaHCO3 caused both a N O 3 - c decrease of 1 ± 0.04 mM and a Cl c - decrease of 3.5 ± 0.1 mM. The saturation of NSW with 1000 ppm CO2 also produced a diminution of the N O 3 - c , but lower (0.4 ± 0.07 mM). These results indicate that the rise of dissolved inorganic carbon ( HC O 3 - or CO2) in NSW would have an effect on the cytosolic anion homeostasis mechanisms in P. oceanica leaf cells. In the presence of 0.1 mM ethoxyzolamide, the plasma membrane-permeable carbonic anhydrase inhibitor, the CO2-induced cytosolic N O 3 - diminution was much lower (0.1 ± 0.08 mM), pointing to HC O 3 - as the inorganic carbon species that causes the cytosolic N O 3 - leak. The incubation of P. oceanica leaf pieces in 3 mM HC O 3 - -enriched NSW triggered a short-term external N O 3 - net concentration increase consistent with the N O 3 - c leak. As a consequence, the cytosolic N O 3 - diminution induced in high inorganic carbon could result in both the decrease of metabolic N flux and the concomitant biomass N impoverishment in P. oceanica and, probably, in other aquatic plants

Local adsorption structure and bonding of porphine on Cu(111) before and after self-metalation

We have experimentally determined the lateral registry and geometric structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P) adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction (PhD), and compared the experimental results to density functional theory (DFT) calculations that included van der Waals corrections within the Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center above a surface bridge site. Consistency is obtained between the experimental and DFT-predicted structural models, with a characteristic change in the corrugation of the four N atoms of the molecule's macrocycle following metalation. Interestingly, comparison with previously published data for cobalt porphine adsorbed on the same surface evidences a distinct increase in the average height of the N atoms above the surface through the series 2H-P, Cu-P, cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted adsorption strength, with 2H-P having the smallest adsorption height despite the weakest calculated adsorption energy. In addition, our findings suggest that for these macrocyclic compounds, substrate-to-molecule charge transfer and adsorption strength may not be univocally correlated

Efficient Rhodium-catalyzed multicomponent reaction for the synthesis of novel propargylamines

[{Rh(μ-Cl)(H)2(IPr)}2] (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazole-2-ylidene) was found to be an efficient catalyst for the synthesis of novel propargylamines by a one-pot three-component reaction between primary arylamines, aliphatic aldehydes, and triisopropylsilylacetylene. This methodology offers an efficient synthetic pathway for the preparation of secondary propargylamines derived from aliphatic aldehydes. The reactivity of [{Rh(μ-Cl)(H)2(IPr)}2] with amines and aldehydes was studied, leading to the identification of complexes [RhCl(CO)IPr(MesNH2)] (MesNH2 = 2,4,6-trimethylaniline) and [RhCl(CO)2IPr]. The latter shows a very low catalytic activity while the former brought about reaction rates similar to those obtained with [{Rh(μ-Cl)(H)2(IPr)}2]. Besides, complex [RhCl(CO)IPr(MesNH2)] reacts with an excess of amine and aldehyde to give [RhCl(CO)IPr{MesN[DOUBLE BOND]CHCH2CH(CH3)2}], which was postulated as the active species. A mechanism that clarifies the scarcely studied catalytic cycle of A3-coupling reactions is proposed based on reactivity studies and DFT calculations.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) (CONSOLIDER INGENIO CSD2009-0050, CTQ2011-27593, CTQ2012-35665 and CTQ2013-42532-P projects) and the DGA/FSE-E07. The support from KFUPM-University of Zaragoza research agreement and the Centre of Research Excellence in Petroleum Refining & KFUPM is gratefully acknowledged. V. P. thankfully acknowledges the resources from the supercomputer >Memento>, technical expertise and assistance provided by BIFI-ZCAM (Universidad de Zaragoza). L.R.-P thanks to CONACyT for a postdoctoral fellowship (204033).Peer Reviewe

Distribution of polymorphic variants of CYP2A6 and their involvement in nicotine addiction

Tobacco consumption has become a major public health issue, which has motivated studies to identify and understand the biological processes involved in the smoking behavior for prevention and smoking cessation treatments. CYP2A6 has been identified as the main gene that codifies the enzyme that metabolizes nicotine. Many alleles have been identified after the discovery of CYP2A6, suggesting a wide interethnic variability and a diverse smoking behavior of the allele carrying individuals. The main purpose of this review is to update and highlight the effects of the CYP2A6 gene variability related to tobacco consumption reported from diverse human populations. The review further aims to consider CYP2A6 in future studies as a possible genetic marker for the prevention and treatment of nicotine addiction. Therefore, we analyzed several population studies and their importance at addressing and characterizing a population using specific parameters. Our efforts may contribute to a personalized system for detecting, preventing and treating populations at a higher risk of smoking to avoid diseases related to tobacco consumption

miRNA/phasiRNA mediated regulation of plant defense response against P. syringae

Gene silencing is a mechanism of regulation of gene expression where the small RNAs (sRNAs) are key components for giving specificity to the system. In plants, two main types of noncoding small RNA molecules have been found: microRNAs (miRNAs) and small interfering RNAs (siRNAs). DCL proteins acting on large RNA precursors produce the mature forms of sRNAs (20-24nt) that can act as negative regulators of gene expression. In recent years, the role of miRNAs in regulation of gene expression in plant responses against bacterial pathogens is becoming clearer. Comparisons carried out in our lab between expression profiles of different Arabidopsis thaliana mutants affected in gene silencing, and plants challenged with Pseudomonas syringae pathovar tomato DC3000, led us to identify a set of uncharacterized R genes, belonging to the TIR-NBS-LRR gene family, as differentially expressed in these conditions. Through the use of bioinformatics tools, we found a miRNA* of 22 nt putatively responsible for down-regulating expression of these R genes. We have validated this regulation, and have also established that the corresponding pri-miRNA is down-regulated upon PAMPs or bacteria perception. Using GUS reporters, we have characterized the expression pattern of both pri-miRNA and its best target R genes. We demonstrate that plants with altered levels of miRNA* (knockdown or overexpression lines) exhibit altered PTI-associated phenotypes, supporting a role for this miRNA* in the defence response against this bacterial pathogen. Finally, we identify phasiRNAs that arise from the transcript of one of the R target genes in a miRNA*-RDR6-DCL4-dependent manner.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech