Insertion of benzyne into the Pd–C bond. Synthesis of unnatural amino acid derivatives by sequential insertion of benzyne and CO: 2,2’-functionalized biaryls containing alkylamino and carboxymethyl substituents. Isolation of stable carbopalladated-benzyne intermediates

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemical Communications, copyright © Royal Society of Chemistry after peer review and technical editing by the publisher. This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/Reaction of ortho-palladated derivatives of phentermine and homoveratrylamine with benzyne allows the synthesis of enlarged eight-membered palladacycles resulting from the insertion of the aryne into the Pd–C bond, which subsequently react with CO, to render unnatural amino acid derivatives

Reactivity toward CO of Eight-Membered Palladacycles Derived from the Insertion of Alkenes into the Pd–C Bond of Cyclopalladated Primary Arylalkylamines of Pharmaceutical Interest. Synthesis of Tetrahydrobenzazocinones, Ortho-Functionalized Phenethylamines, Ureas, and an Isocyanate

This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical Society, after peer review and technical editing by the publisher.The ortho-metalated complex [Pd{C,N-C6H2CH2CH2NH2-2,(OMe)2-4,5}(μ-Br)]2 (1a) derived from homoveratrylamine reacts with ethyl acrylate, methyl vinyl ketone or 2-norbornene to give the dimeric complex arising from the insertion of the alkene into the Pd–C bond, [Pd{C,N-CH(R)CH2C6H2CH2CH2NH2-2,(OMe)2-4,5}(μ-Br)]2 (R = CO2Et (2a1), C(O)Me (2a2)) or [Pd{C,N-CH(C5H8)CHC6H2CH2CH2NH2-2,(OMe)2-4,5}(μ-Br)]2 (2a3). Complexes 2a and the phentermine homologues 2b react with CO to afford Pd(0) and (1) tetrahydrobenzazocinones, the heterocycles resulting from CO insertion into the Pd–C bond and C–N coupling, (2) unnatural aminoacid derivatives resulting from CO insertion and the reaction of the obtained acyl complex with the solvent (MeOH), or the product of protonolysis of the Pd–C bond, depending on the nature of the initial cyclopalladated compound or (3) ureas, alone or mixed with an isocyanate, in the presence of a base. Phentermine derivatives 2b react with HCl to give a dinuclear palladium complex [PdCl(μ- Cl)(L)], where L is the amine arising from the protonolysis of the Pd–C bond or the alkyl group resulting from Pd–N bond protonolysis, depending on the nature of the inserted alkene. The crystal structures of some palladium complexes and organic compounds have been determined by X-ray diffraction studies

A New Method for High Yield Cyclopalladation of Primary and Secondary Amines. Atom-Efficient Open-to-Air Inexpensive Synthesis of Buchwald-Type Precatalysts

This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/ This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/om200464sA new method for high yield cyclopalladation of primary and secondary amines involving the corresponding ammonium triflates, instead of the amines generally employed is reported. The method is applied for the synthesis of Buchwald-type precatalysts [Pd(C,N-C6H4CH2CH(R’)NHR- 2)X(phosphine)] that can be easily prepared by reaction of Pd(OAc)2, one equiv of the ammonium triflate [PhCH2CH(R’)NH2R]OTf and an excess of NaX, and then treating the resulting complexes [Pd2(C,N-C6H4CH2CH(R’)NHR-2)2(μ-X)2] with the appropriate phosphine. This new method has several advantages over Buchwald´s reported synthesis

Sur8, a determinant protein in colorectal cancer tumor progression

Resumen del trabajo presentado en el 43rd Annual Meeting of the SEBBM, celebrado en Barcelona (España) del 19 al 21 de julio de 2021.Colorectal cancer (CRC) has the highest incidence rate in the Spanish population. The most important challenge consists on the discovery of efficient disease treatments, due to high mortality rates in highly developed stages. Sur8 is a scaffold protein that positively modulates ERK signaling pathway, which has a major role in the progression and metastasis in colorectal cancer. The main goals of our research are to determine the role that Sur8 plays in the development and progression of CRC and to analyze its possible therapeutic potential. For this purpose, our group has developed an inducible conditional mouse model msur8f/fVillinCreERT2. In order to determine Sur8 action in the colonic tissue, we have developed organoids from the colon epithelium of healthy mice and have analyzed gene expression pattern by an RNAseq approach. Sur8 KO affects oncogenic CRC transcription factors expression, as well as the modulation of some Wnt pathway regulators. In regard to miRNA data, we have observed deregulation of miRNAs related to CRC in Sur8 KO organoids. To determine the role that Sur8 plays in the development and progression of CRC, we have subjected our inducible conditional mice to chemical carcinogenesis and we have observed that Sur8 KO males display less and smaller tumors and do not present any adenocarcinoma. In addition, we have carried out Sur8 silencing in human CRC cell lines by infection with constitutive shRNA lentiviruses. We have observed that Sur8 silencing produces decreases of cell tumor proliferation, and reduction of p-ERK levels. Finally, we are evaluating the effects of putative therapeutic agents against Sur8 in human CRC cell lines. Concretely, we are testing Celastrol, which has been described that binds and blocks the action of Sur8 in vitro. We have observed that Celastrol treatment diminishes the cell tumor proliferation in this model. Altogether, our results indicate that Sur8 may have a determinant role in CRC progression and that Sur8 could be a potential molecular target for the design of novel strategies against CRC

Els TFG de la Facultat de Biologia 10 anys després de Boloya. Adequant l'avaluació a la situació actual: La diversitat de TFG requereix diversitat de rúbriques

Codi del projecte: 2019PID-UB/035La experiència adquirida després de 10 anys de la implantació del model de Pràcticums i Treball Fi de Grau (TFG) a la Facultat de Biologia ha permès identificar diferents tipologies de projectes. L’actuació realitzada en aquest projecte contempla la incorporació en els TFGs d’un nou apartat que inclou la reflexió crítica dels estudiants sobre la contribució del seu projecte als Objectius del Desenvolupament Sostenible (ODS). Aquesta acció permet visualitzar els ODS i impulsar-los seguint les directrius de l’Agenda 2030 de la UB. Així, s’han generat dos productes que ja estat implementats i operatius des del curs 21-22. El primer producte consisteix en unes noves rúbriques que han adequat els ítems i continguts a la diversitat de tipologies de TFG que es realitzen a la Facultat de Biologia, incloent l’avaluació adaptada a la metodologies Aps. Aquestes rubriques també incorporen una nova dimensió avaluable sobre la contribució de cada treball de fi de grau als ODS a partir de la reflexió crítica realitzada per l’estudiantat en el seu TFG. El segon producte és la elaboració i difusió d’una guia de suport per a estudiants i tutors per a la incorporació dels ODS als treballs fi de grau. Aquesta guia ha estat incorporada al full de ruta de sostenibilitat de la UB per la seva distribució als diferents centres de la UB per tal d’incorporar aquesta activitat reflexiva a tots els treballs de fi de grau de la UB.Programa RIMD

The Black-Hole Mass in M87 from Gemini/NIFS Adaptive Optics Observations

We present the stellar kinematics in the central 2" of the luminous elliptical galaxy M87 (NGC 4486), using laser adaptive optics to feed the Gemini telescope integral-field spectrograph, NIFS. The velocity dispersion rises to 480 km/s at 0.2". We combine these data with extensive stellar kinematics out to large radii to derive a black-hole mass equal to (6.6+-0.4)x10^9 Msun, using orbit-based axisymmetric models and including only the NIFS data in the central region. Including previously-reported ground-based data in the central region drops the uncertainty to 0.25x10^9 Msun with no change in the best-fit mass; however, we rely on the values derived from the NIFS-only data in the central region in order to limit systematic differences. The best-fit model shows a significant increase in the tangential velocity anisotropy of stars orbiting in the central region with decreasing radius; similar to that seen in the centers of other core galaxies. The black-hole mass is insensitive to the inclusion of a dark halo in the models --- the high angular-resolution provided by the adaptive optics breaks the degeneracy between black-hole mass and stellar mass-to-light ratio. The present black-hole mass is in excellent agreement with the Gebhardt & Thomas value, implying that the dark halo must be included when the kinematic influence of the black hole is poorly resolved. This degeneracy implies that the black-hole masses of luminous core galaxies, where this effect is important, may need to be re-evaluated. The present value exceeds the prediction of the black hole-dispersion and black hole-luminosity relations, both of which predict about 1x10^9 Msun for M87, by close to twice the intrinsic scatter in the relations. The high-end of the black hole correlations may be poorly determined at present.Comment: 12 pages, accepted for publication in the Astrophysical Journa

Экологический риск и его страхование

Тез. докл. V Междунар. науч.-практ. конф., Гомель, 29–30 нояб. 2007 г

The spatial structure of lithic landscapes : the late holocene record of east-central Argentina as a case study

Fil: Barrientos, Gustavo. División Antropología. Facultad de Ciencias Naturales y Museo. Universidad Nacional de La Plata; ArgentinaFil: Catella, Luciana. División Arqueología. Facultad de Ciencias Naturales y Museo. Universidad Nacional de La Plata; ArgentinaFil: Oliva, Fernando. Centro Estudios Arqueológicos Regionales. Facultad de Humanidades y Artes. Universidad Nacional de Rosario; Argentin