Monocolor chemosensors for Ba2+ tagging experiments

Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.The BOLD experiment is focused on the observation of the neutrinoless double β decay of 136Xe to 136Ba2+ through the detection of the daughter cation. For this purpose, different molecular sensors can be developed. These chemosensors can be classified into monocolor (offon) or bicolor (on-on’), depending on the shifts (Δλ) and changes in the intensity (ΔI) observed in their emission spectra. In this context, different off-on radiometric chemosensors have been synthesized in order to understand their photophysics upon interaction with Ba2+ ions in vacuo and in solution. These sensors incorporate two components: a fluorophore and a metal-binding group. The fluorophores are kept as simple as possible, using structures with well-known photophysical properties. On the other hand, N-aza-crown ether derivatives have been used as metal-binding groups. Finally, the effects of disconnecting the abovementioned elements by splitting of components Ar1 and Ar2 (Figure 1: Description of the off-on chemosensors synthesized in this work), will be discussed.Financial support from the Basque Government (IT-1346-19 and IT-1180-19), the Spanish MICINN (PID2019-104772-GB-I00, PID2019-111281-GB-I00, RED2018-102387-T, and RED2018-102471-T), and by the European Commission (ERC-2020-SyG-951281) is gratefully acknowledged.Peer reviewe

New generation of fluorescent bicolour sensors for barium tagging experiments

Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.One of the most important questions in particle physics and cosmology consists of demonstrating that the neutrino is a Majorana fermion. Observation of the neutrinoless double β decay of 136Xe to generate the daughter cation 136Ba2+ is the most promising practical way to demonstrate this hypothesis. Within this context, our research group has designed and synthesized the first generation of fluorescent bicolour sensors (FBI-G1), whose emission spectra change upon binding to Ba2+ ions by formation of supramolecular complexes in dry media involving solid-gas interphases. In this presentation, the synthesis of a second generation (G2) of bicolour sensors is reported. These sensors have two essential components, a metal-binding group, and a fluorophore. The latest structure is based on a benzo[a]imidazo[2,1,5-cd]indolizine derivative (Figure 1: Description of generation 1 (left) and generation 2 (right) chemosensors). Finally, preliminary research involving the linkage of our sensors to surfaces such as indium tin oxide glass (ITO), will be discussed.Financial support from the Basque Government (IT-1346-19 and IT-1180-19), the Spanish MICINN (PID2019-104772-GB-I00, PID2019-111281-GB-I00, RED2018-102387-T, and RED2018-102471-T), and by the European Commission (ERC-2020-SyG-951281) is gratefully acknowledged.Peer reviewe

Iridium-based sensor for cations

Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.Traditionally, techniques such as inductively coupled plasma mass spectroscopy or gas chromatography have been used for cation detection. However, these methods need long analysis times and sophisticated instrumentation. Simpler and faster methods have been developed these days, such us optical methods (colorimetric and/or fluorescent), which can entail easy visualization, high sensitivity and cheaper instrumentation. Among these, ratiometric (bicolour) fluorescent sensors stand out due to the lower limit of detection. In this area, both organic molecules and metal complexes are being developed as luminescent probes. Indeed, some iridium complexes demonstrated to be selective luminescent sensors for different cations. Different strategies are used to trap or interact with the cation, which permits a rational tuning of the iridium’s emission. In our group, we have been working with iridium complexes for a variety of objectives. In this contribution, an iridium-based sensor for cations will be described including its response to cations in solution and on solid supports.Financial support from the Basque Government (PRE_2020_2_0230, IT-1346-19 and IT-1180-19), the Spanish MICINN (PID2019-104772-GB-I00, PID2019-111281-GB-I00, RED2018-102387-T, and RED2018-102471-T), and by the European Commission (ERC-2020-SyG-951281) is gratefully acknowledged.Peer reviewe

Boosting background suppression in the NEXT experiment through Richardson-Lucy deconvolution

Next-generation neutrinoless double beta decay experiments aim for half-life sensitivities of similar to 10(27) yr, requiring suppressing backgrounds to < 1 count/tonne/yr. For this, any extra background rejection handle, beyond excellent energy resolution and the use of extremely radiopure materials, is of utmost importance. The NEXT experiment exploits differences in the spatial ionization patterns of double beta decay and single-electron events to discriminate signal from background. While the former display two Bragg peak dense ionization regions at the opposite ends of the track, the latter typically have only one such feature. Thus, comparing the energies at the track extremes provides an additional rejection tool. The unique combination of the topology-based background discrimination and excellent energy resolution (1% FWHM at the Q-value of the decay) is the distinguishing feature of NEXT. Previous studies demonstrated a topological background rejection factor of 5 when reconstructing electron-positron pairs in the Tl-208 1.6 MeV double escape peak (with Compton events as background), recorded in the NEXT-White demonstrator at the Laboratorio Subterraneo de Canfranc, with 72% signal efficiency. This was recently improved through the use of a deep convolutional neural network to yield a background rejection factor of similar to 10 with 65% signal efficiency. Here, we present a new reconstruction method, based on the Richardson-Lucy deconvolution algorithm, which allows reversing the blurring induced by electron diffusion and electroluminescence light production in the NEXT TPC. The new method yields highly refined 3D images of reconstructed events, and, as a result, significantly improves the topological background discrimination. When applied to real-data 1.6 MeV e(-)e(+) pairs, it leads to a background rejection factor of 27 at 57% signal efficiency.The NEXT Collaboration acknowledges support from the following agencies and institutions: the European Research Council (ERC) under the Advanced Grant 339787-NEXT; the European Union's Framework Programme for Research and Innovation Horizon 2020 (2014-2020) under the Grant Agreements No. 674896, 690575 and 740055; the Ministerio de Economia y Competitividad and the Ministerio de Ciencia, Innovacion y Universidades of Spain under grants FIS2014-53371-C04, RTI2018-095979, the Severo Ochoa Program grants SEV-2014-0398 and CEX2018-000867-S, and the Maria de Maeztu Program MDM-2016-0692; the Generalitat Valenciana under grants PROMETEO/2016/120 and SEJI/2017/011; the Portuguese FCT under project PTDC/FIS-NUC/2525/2014 and under projects UID/04559/2020 to fund the activities of LIBPhys-UC; the U.S. Department of Energy under contracts No. DE-AC02-06CH11357 (Argonne National Laboratory), DE-AC02-07CH11359 (Fermi National Accelerator Laboratory), DE-FG02-13ER42020 (Texas A&M) and DE-SC0019223/DE-SC0019054 (University of Texas at Arlington); the University of Texas at Arlington (U.S.A.); and the Pazy Foundation (Israel) under grants 877040 and 877041. DGD acknowledges Ramon y Cajal program (Spain) under contract number RYC-2015-18820. JM-A acknowledges support from Fundacion Bancaria "la Caixa" (ID 100010434), grant code LCF/BQ/PI19/11690012. AS acknowledges support from the Kreitman School of Advanced Graduate Studies at Ben-Gurion University. Documen

Proteinak eta DNA Funtzio Katalitiko Zein Biologikoen Sustatzaile Gisa: Huisgenasetatik Kimioterapiara

El capítulo 3, anexos y otros pequeños fragamentos sujetos a confidencialidad pentiente patente 360 p. (eng), 122 p. (eus)La presente Tesis Doctoral se ha divido en dos apartados principales. En el segundo capítulo se presenta el empleo de las proteínas CTPR como enzimas que catalizan la reacción de Huisgen entre iminas y nitroestirenos, describiendo una de las primeras actividades catalíticas Huisgenasas inequívocas. Posteriormente, se desarrollan varias mutaciones en estas proteínas para entender el mecanismo de reacción presente en esta catálisis. Basándonos en una hipótesis inicial y mediante el uso de cálculos QM/MM se proponen dos mecanismos diferentes basados en la actividad catalítica de diadas o monadas presentes en las proteínas CTPR. Finalmente, se llevó a cabo un estudio por RMN para analizar la interacción entre el substrato y las mencionadas proteínas. Por otro lado, en el tercer capítulo se presenta el diseño, síntesis y evaluación biológica de una nueva familia de derivados de platino(II) que potencialmente pueden superar los mecanismos de resistencia desarrollados por las células tumorales frente a cisplatino. Se diseño una serie de 20 compuestos nuevos que posteriormente fueron testado en la línea celular de cáncer de ovario resistente a cisplatino A2780cis empleando ensayos de viabilidad celular WST-1 y de citometría de flujo para analizar la muerte celular. Se obtuvieron resultados muy prometedores en los que se observa que esta nueva familia de compuestos es capaz de superar la resitencia, finalmente, se estudio la unión de varios compuestos al DNA mediante TEM y AFM

Proteinak eta DNA Funtzio Katalitiko Zein Biologikoen Sustatzaile Gisa: Huisgenasetatik Kimioterapiara

El capítulo 3, anexos y otros pequeños fragamentos sujetos a confidencialidad pentiente patente 360 p. (eng), 122 p. (eus)La presente Tesis Doctoral se ha divido en dos apartados principales. En el segundo capítulo se presenta el empleo de las proteínas CTPR como enzimas que catalizan la reacción de Huisgen entre iminas y nitroestirenos, describiendo una de las primeras actividades catalíticas Huisgenasas inequívocas. Posteriormente, se desarrollan varias mutaciones en estas proteínas para entender el mecanismo de reacción presente en esta catálisis. Basándonos en una hipótesis inicial y mediante el uso de cálculos QM/MM se proponen dos mecanismos diferentes basados en la actividad catalítica de diadas o monadas presentes en las proteínas CTPR. Finalmente, se llevó a cabo un estudio por RMN para analizar la interacción entre el substrato y las mencionadas proteínas. Por otro lado, en el tercer capítulo se presenta el diseño, síntesis y evaluación biológica de una nueva familia de derivados de platino(II) que potencialmente pueden superar los mecanismos de resistencia desarrollados por las células tumorales frente a cisplatino. Se diseño una serie de 20 compuestos nuevos que posteriormente fueron testado en la línea celular de cáncer de ovario resistente a cisplatino A2780cis empleando ensayos de viabilidad celular WST-1 y de citometría de flujo para analizar la muerte celular. Se obtuvieron resultados muy prometedores en los que se observa que esta nueva familia de compuestos es capaz de superar la resitencia, finalmente, se estudio la unión de varios compuestos al DNA mediante TEM y AFM

The microwave-assisted organocatalyzed rearrangement of Propargyl vinyl ethers to salicylaldehydes derivatives

Trabajo presentado en el 19th European Symposium of Organic Chemistry, celebrado en Lisboa del 12 al 16 de julio de 2015.Propargyl vinyl ethers constitute a privileged group of small size, densely functionalized and readily accessible linear scaffolds. The main key to the chemical reactivity encoded in these structures is the [3,3]-sigmatropic rearrangement (propargyl Claisen rearrangement) shown in Scheme 1A, which takes place irreversibly and under thermodynamic control to generate the allene 2 which isomerizes to dienal. We have developed a microwave-assisted, catalytic (imidazole 10 mol-%) and scalable methodologyto transform these allenes into salicylaldehyde motives supported on a broad range of topologies, which spanned from simple aromatic monocycles to complex fused polycyclic systems. The reaction manifold is depicted in Scheme 1B. We have performed a theoretical study of this reaction which is in full agreement with the observed experimental results. The reaction scope and the proposed mechanism will be commented in our presentation.This research was supported by the Spanish Ministerio de Economía y Competitividad (MINECO), and the European FEDER and Regional Development Fund (CTQ2011-28417-C01-02). L. Cotos and D.M. thank MICINN and CSIC for a FPI and a JAE-PRE grant respectively.Peer Reviewe

The microwave-assisted organocatalyzed rearrangement of Propargyl vinyl ethers to salicylaldehydes derivatives

Trabajo presentado en la reunión XXXV Bienal de la Real Sociedad Española de Química, celebrada en A Coruña del 19 al 23 de julio de 2015.Propargyl vinyl ethers constitute a privileged group of small size, densely functionalized and readily accessible linear scaffolds. The main key to the chemical reactivity encoded in these structures is the [3,3]-sigmatropic rearrangement (propargyl Claisen rearrangement) shown in Scheme 1A, which takes place irreversibly and under thermodynamic control to generate the allene 2 which isomerizes to dienal. We have developed a microwave-assisted, catalytic (imidazole 10 mol-%) and scalable methodologyto transform these allenes into salicylaldehyde motives supported on a broad range of topologies, which spanned from simple aromatic monocycles to complex fused polycyclic systems. The reaction manifold is depicted in Scheme 1B. We have performed a theoretical study of this reaction which is in full agreement with the observed experimental results. The reaction scope and the proposed mechanism will be commented in our presentation.This research was supported by the Spanish Ministerio de Economía y Competitividad (MINECO), and the European FEDER and Regional Development Fund (CTQ2011-28417- C01-02). L. Cotos and D.M. thank MICINN and CSIC for a FPI and a JAE-PRE grant respectively.Peer Reviewe