Dichloro(methyl) silyl-substituted cyclopentadienyl titanium complexes

The synthesis of (C5H4)(SiMeCl2)(SiMe3) is described. The reaction of a dichloromethane solution of this compound with one equivalent of titanium tetrachloride leads to the monocyclopentadienyl complex [TiCl3{η5-C5H4(SiMeCl2)}]. Treatment of this complex with the lithium amides LiN(SiMe3)2 and LiNHtBu affords [TiCl2{N(SiMe3)2}{η5-C5H4(SiMeCl2)}] and [TiCl2{η5-C5H4[SiMeCl(η-NtBu)]}], respectively. Alkylation of the trichlorotitanium derivative with 1.5 equivalents of Mg(CH2C6H5)2(THF)2 leads to the tribenzyl derivative [Ti(CH2C6H5)3{η5-C5H4(SiMeCl2)}]. Hydrolysis of the trichloro- and tribenzyl-complexes leads to the μ-oxo dititanium compounds [TiX2μ-{η5-C5H4(η-OSiMeCl)}]2 (X=Cl, CH2Ph). All of the new complexes were characterized by elemental analysis and NMR spectroscopy.We are grateful to the DGICYT (Project PB-92-0178-C) and CAM (I + D 0034/94) for financial support.\ud B.R. acknowledges Universidad de Alcalá de Henares for support provided (Project 042/95

Dicyclopentadienyl zirconium and hafnium complexes with the bridged (dimethylsilanodiyl)dicyclopentadienyl [(SiMe2)(η5-C5H4)2]2 ligand. X-ray molecular structure of [Zr{(SiMe2)(η5-C5H4)2}(CH2Ph)]2(μ-O)

Reaction of the bridged (dimethylsilanediyl)dicyclopentadienyl dilithium salt [(SiMe2)(C5H4)2Li2] with MCl4, in toluene, gave the zirconium and hafnium complexes [M{(SiMe2)(η5-C5H4)2}Cl2] [M=Zr (1), Hf (2)]. Addition of two equivalents of M′R (M′=MgCl, R=CH3; M′=Li, R=CH2CMe2Ph; M′=MgBz, R=CH2Ph) to toluene or diethyl ether solutions of [M{(SiMe2)(η5-C5H4)2}Cl2] afforded the dialkyl derivatives [M{(SiMe2)(η5-C5H4)2}R2] [R=CH3, M=Zr (3), Hf (4); R=CH2CMe2Ph, M=Zr (5), Hf (6); R=CH2Ph, M=Zr (7)]. Compound 1 reacted with LiMe and Mg(CH2Ph)2(THF)2 in the presence of a stoichiometric amount of water to give the μ-oxo derivatives [Zr{(SiMe2)(η5-C5H4)2}R]2(μ-O) [R=CH3 (8), CH2Ph (9)]. The X-ray molecular structure of [Zr{(SiMe2)(η5-C5H4)2}(CH2Ph)]2(μ-O) (9) has been determined by diffraction methods. Its most remarkable feature is the planarity of the BzZrOZrBz and the linearity of the ZrOZr systems.We acknowledge the Dirección General de Investigación Científica y Técnica (Spain) for financial support of this research (Project PB97-0776)

Nitric oxide induces the alternative oxidase pathway in Arabidopsis seedlings deprived of inorganic phosphate

Phosphate starvation compromises electron fow through the cytochrome pathway of the mitochondrial electron transport chain, and plants commonly respond to phosphate deprivation by increasing fow through the alternative oxidase (AOX). To test whether this response is linked to the increase in nitric oxide (NO) production that also increases under phosphate starvation, Arabidopsis thaliana seedlings were grown for 15 d on media containing either 0 or 1 mM inorganic phosphate. The effects of the phosphate supply on growth, the production of NO, respiration, the AOX level and the production of superoxide were compared for wild-type (WT) seedlings and the nitrate reductase double mutant nia. Phosphate deprivation increased NO production in WT roots, and the AOX level and the capacity of the alternative pathway to consume electrons in WT seedlings; whereas the same treatment failed to stimulate NO production and AOX expression in the nia mutant, and the plants had an altered growth phenotype. The NO donor S-nitrosoglutathione rescued the growth phenotype of the nia mutants under phosphate deprivation to some extent, and it also increased the respiratory capacity of AOX. It is concluded that NO is required for the induction of the AOX pathway when seedlings are grown under phosphate-limiting conditions.This work was supported by research grants (AGL2010-16167; AGL2014-52396-P) from the Spanish Ministry of Economy and Competitiveness (MINECO) to JFM, an FPI fellowship from MINECO (BR), and a Marie Curie Intra-European Fellowship for Career Development within the 7th European Community Framework Programme (KJG and RGR).Peer Reviewe

La violencia de género en el cine de Icíar Bollaín. El caso de Te doy mis ojos.

La violencia de género es una lacra que afecta al conjunto de la sociedad desde hace décadas. A través de este trabajo, realizaré un breve recorrido sobre el tratamiento del asunto en el arte cinematográfico, comenzando por una panorámica general de películas que tratan sobre este tema. A continuación, me centraré en la figura de la directora madrileña Icíar Bollaín, repasando su filmografía y los aspectos estéticos y narrativos de su cine. Del mismo modo y para concluir, analizaré la película Te doy mis ojos y como la realizadora ha sabido reflejar de una forma veraz y realista los malos tratos.<br /

Divulgación de información financiera en Internet en las principales ciudades españolas

Debido a la gran corrupción que ha aparecido en nuestro país y a otros factores de diversa índole, la transparencia está tomando un rol cada vez más importante en la gestión de los ayuntamientos, que cada vez hacen un esfuerzo mayor para satisfacer a los ciudadanos, y supone un principio básico de la gestión pública actual. Con la realización de este trabajo lo que se persigue es realizar un análisis sobre la divulgación de información financiera por parte de los ayuntamientos de las cincuenta ciudades más grandes de España y analizar los principales factores que pueden explicar las diferencias de los resultados obtenidos. Para llevar a cabo dicho análisis se ha realizado una selección de veinte ítems de información económica, y se ha realizado un análisis univariante, llegando a la conclusión de que el tamaño del municipio explica el grado de divulgación de información y que la información que más se divulga es la información presupuestaria y, la que menos la de tipo financiero (en concreto, los informes de auditoría). Más del 80% de las ciudades analizadas obtienen una puntuación en transparencia superior al 50%, por lo que destaca el gran esfuerzo que ya han hecho las ciudades para adaptarse al nuevo marco normativo, aunque les queda mucho por mejorar

Click-Derived Triazoles and Triazolylidenes of Manganese for Electrocatalytic Reduction of CO2

022162, CEECIND/00509/2017, PTDC/QUI-QIN/28151/2017, RECI/BBB-BEP/0124/2012, SFRH/BD/131955/2017, UIDB/00100/2020, UIDB/04378/2020, UIDB/04612/2020, UIDP/00100/2020, UIDP/04046/2020, UIDP/04378/2020, UIDP/50006/2020, UIPD/04612/2020 Funding Information: This research was funded by FUNDA??O DE CI?NCIA E TECNOLOGIA, FCT, grant numbers: PTDC/QUI-QIN/28151/2017, SFRH/BD/131955/2017, CEECIND/00509/2017. The MOSTMICRO-ITQB was funded by UIDB/04612/2020 and UIPD/04612/2020. The NMR spectrome-ters at CERMAX were funded by 022162. LAQV and UCIBIO were funded by UIDB/50006/2020, UIDP/50006/2020, UIDB/04378/2020, and UIDP/04378/2020. The X-ray infrastructure was funded by RECI/BBB-BEP/0124/2012. The BioISI was funded by UIDB/04046/2020, UIDP/04046/2020, UIDB/00100/2020, and UIDP/00100/2020. We thank C. Almeida for elemental analysis at ITQB laboratories. Funding Information: Funding: This research was funded by FUNDAÇÃO DE CIÊNCIA E TECNOLOGIA, FCT, grant numbers: PTDC/QUI-QIN/28151/2017, SFRH/BD/131955/2017, CEECIND/00509/2017. The MOSTMICRO-ITQB was funded by UIDB/04612/2020 and UIPD/04612/2020. The NMR spectrometers at CERMAX were funded by 022162. LAQV and UCIBIO were funded by UIDB/50006/2020, UIDP/50006/2020, UIDB/04378/2020, and UIDP/04378/2020. The X-ray infrastructure was funded by RECI/BBB-BEP/0124/2012. The BioISI was funded by UIDB/04046/2020, UIDP/04046/2020, UIDB/00100/2020, and UIDP/00100/2020. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.A series of new fac-[Mn(L)(CO)3 Br] complexes where L is a bidentate chelating ligand containing mixed mesoionic triazolylidene-pyridine (MICˆpy, 1), triazolylidene-triazole (MICˆtrz, 2), and triazole-pyridine (trzˆpy, 3) ligands have been prepared and fully characterized, including the single crystal X-ray diffraction studies of 1 and 2. The abilities of 1–3 and complex fac-[Mn(MICˆMIC)(CO)3 Br] (4) to catalyze the electroreduction of CO2 has been assessed for the first time. It was found that all complexes displayed a current increase under CO2 atmosphere, being 3 and 4 the most active complexes. Complex 3, bearing a NˆN-based ligand exhibited a good efficiency and an excellent selectivity for reducing CO2 to CO in the presence of 1.0 M of water, at low overpotential. Interestingly, complex 4 containing the strongly electron donating di-imidazolylidene ligand exhibited comparable activity to 3, when the experiments were performed in neat acetonitrile at slightly higher overpotential (−1.86 vs. −2.14 V).publishersversionpublishe

3D Cell Cultures as Prospective Models to Study Extracellular Vesicles in Cancer

The improvement of culturing techniques to model the environment and physiological conditions surrounding tumors has also been applied to the study of extracellular vesicles (EVs) in cancer research. EVs role is not only limited to cell-to-cell communication in tumor physiology, they are also a promising source of biomarkers, and a tool to deliver drugs and induce antitumoral activity. In the present review, we have addressed the improvements achieved by using 3D culture models to evaluate the role of EVs in tumor progression and the potential applications of EVs in diagnostics and therapeutics. The most employed assays are gel-based spheroids, often utilized to examine the cell invasion rate and angiogenesis markers upon EVs treatment. To study EVs as drug carriers, a more complex multicellular cultures and organoids from cancer stem cell populations have been developed. Such strategies provide a closer response to in vivo physiology observed responses. They are also the best models to understand the complex interactions between different populations of cells and the extracellular matrix, in which tumor-derived EVs modify epithelial or mesenchymal cells to become protumor agents. Finally, the growth of cells in 3D bioreactor-like systems is appointed as the best approach to industrial EVs production, a necessary step toward clinical translation of EVs-based therapy.The review is supported by Spanish Ministry of Science and Innovation, within the national Plan RTI2018-094969-B-I00, and Excellence Severo Ochoa grant Innovative Research Grant (SEV-2016- 0644), and by the European Union’s Horizon 2020 research and innovation program, grant number 860303