25 research outputs found
Ba+2 ion trapping using organic submonolayer for ultra-low background neutrinoless double beta detector
If neutrinos are their own antiparticles the otherwise-forbidden nuclear reaction known as neutrinoless double beta decay can occur. The very long lifetime expected for these exceptional events makes its detection a daunting task. In order to conduct an almost background-free experiment, the NEXT collaboration is investigating novel synthetic molecular sensors that may capture the Ba dication produced in the decay of certain Xe isotopes in a high-pressure gas experiment. The use of such molecular detectors immobilized on surfaces must be explored in the ultra-dry environment of a xenon gas chamber. Here, using a combination of highly sensitive surface science techniques in ultra-high vacuum, we demonstrate the possibility of employing the so-called Fluorescent Bicolor Indicator as the molecular component of the sensor. We unravel the ion capture process for these molecular indicators immobilized on a surface and explain the origin of the emission fluorescence shift associated to the ion trapping.This material is based upon work supported by the following agencies and institutions: the European Research Council (ERC) under ERC-2020-SyG 951281; the MCIN/AEI/10.13039/501100011033 of Spain and ERDF A way of making Europe under grants PID2020-114252GB-I00, PID2019-107338RB-C63, PID2019-104772GB-I00, PID2019-111281GB-I00, and RTI2018-095979, the Severo Ochoa Program grant CEX2018-000867-S; the Basque Government (GV/EJ) under grants IT-1553-22, IT-1591-22. The NEXT Collaboration acknowledges support from the following agencies and institutions: the European Union’s Framework Programme for Research and Innovation Horizon 2020 (2014-2020) under Grant Agreement No. 957202-HIDDEN; the MCIN/AEI of Spain and ERDF A way of making Europe under grants RTI2018-095979 and PID2021-125475NB, the Severo Ochoa Program grant CEX2018-000867-S and the Ramón y Cajal program grant RYC-2015-18820; the Generalitat Valenciana of Spain under grants PROMETEO/2021/087 and CIDEGENT/2019/049; the Department of Education of the Basque Government of Spain under the predoctoral training program non-doctoral research personnel; the Portuguese FCT under project UID/FIS/04559/2020 to fund the activities of LIBPhys-UC; the Pazy Foundation (Israel) under grants 877040 and 877041; the US Department of Energy under contracts number DE-AC02-06CH11357 (Argonne National Laboratory), DE-AC02-07CH11359 (Fermi National Accelerator Laboratory), DE-FG02-13ER42020 (Texas A&M), DE-SC0019054 (Texas Arlington) and DE-SC0019223 (Texas Arlington); the US National Science Foundation under award number NSF CHE 2004111; the Robert A Welch Foundation under award number Y-2031-20200401. Finally, we are grateful to the Laboratorio Subterráneo de Canfranc for hosting and supporting the NEXT experiment
Efficient Homogeneous Hydridoirida-β-Diketone-Catalyzed Methanolysis of Ammonia-Borane for Hydrogen Release in Air. Mechanistic Insights
The hydridoirida-beta-diketone [(IrH{(PPh2(o-C6H4CO))(2)H})(2)(mu-Cl)][BF4] (2) has been used as a homogeneous catalyst for the methanolysis of ammonia-borane to release up to 3 equivalents of hydrogen in the presence of air. With catalyst loadings as low as 0.2 mol%, ammonia-borane undergoes methanolysis within 6 min at 30 degrees C, with TOF50% of 320 mol(H2) .mol(Ir)(-1).min(-1), or within 80 s at 60 degrees C, with an excellent TOF50% of 1991 mol(H2).mol(Ir)(-1).min(-1), and maintains its catalytic activity in consecutive runs. Triethylamine-borane fails to undergo methanolysis. Kinetic studies indicate first-order dependence on substrate and on catalyst concentration and suggest cleavage of the solvent O-H bond being involved in the rate determining step of the reaction. In methanol solution 2 forms cationic [IrH(MeOH){(PPh2(o-C6H4CO))(2)H}](+) (3) and reacts with Me3N-BH3 to afford a hydridoirida-beta-diketone [IrH(Me3NBH3){(PPh2(o-C6H4CO))(2)H}](+) (4), with the borane adduct eta(1)-coordinated to iridium. Compound [4][BAr4F] shows dynamic behaviour in solution due to exchange of bridging and terminal B-H bonds. A multinuclear NMR study of the catalyzed reaction shows the formation of two ammonia-methoxyborane adduct intermediates, H3N-BH2(OCH3) and H3N-BH(OCH3)(2), and an iridium species proposed of the hydridodiacyl type [IrH(H3NBH3-x(OCH3)(x))(PPh2(o-C6H4CO))(2)] with a coordinated borane adduct. On account of experimental evidence, a simplified catalytic cycle is suggested for the methanolysis of AB to release hydrogen.Partial financial support by Ministerio de Economia y Competitividad MINECO/FEDER (CTQ2015-65268-C2-1-P and PID2019-111281GB-I00), Gobierno Vasco (GIC 18/143 and IT1180-19) Universidad del Pais Vasco (UPV/EHU) and Diputacion Foral de Gipuzkoa are gratefully acknowledged. I. B. acknowledges support by UPV/EHU
Bicolour fluorescent molecular sensor for cations: design and experimental validation
Molecular entities whose fluorescence spectra are different when they bind metal cations are termed
bicolour fluorescent molecular sensors. The basic design criteria of this kind of compound are presented
and the different fluorescent responses are discussed in terms of their chemical behaviour and electronic
features. These latter elements include intramolecular charge transfer (ICT), formation of intramolecular
and intermolecular excimer/exciplex complexes and Fo ̈rster resonance energy transfer (FRET). Changes in
the electronic properties of the fluorophore based on the decoupling between its constitutive units upon
metal binding are also discussed. The possibility of generating fluorescent bicolour indicators that can
capture metal cations in the gas phase and at solid–gas interfaces is also discussedThis work was supported by the Basque Government (Grants IT-1346-19 and IT1180-19), by the Spanish Ministry of Science and Innovation (MICINN-FEDER, Grants PID2019-104772GB-I00, PID2019-111281GB-I00, RED2018-102387-T, and RED2018-102471-T), and by the European Research Council (ERC) under the European's Union Horizon 2020 research and innovation programme (Grant agreement ERC-2020-SyG 951281)
Hydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silanes
[EN] An unprecedented quantum tunneling effect has been observed in catalytic Si-H bond activations at room temperature. The cationic hydrido-silyl-iridium(III) complex, {Ir[SiMe(o-C6H4SMe)(2)](H)(PPh3)(THF)}[BAr4F], has proven to be a highly efficient catalyst for the hydrolysis and the alcoholysis of organosilanes. When triethylsilane was used as a substrate, the system revealed the largest kinetic isotopic effect (KIESi-H/Si-D=346 +/- 4) ever reported for this type of reaction. This unexpectedly high KIE, measured at room temperature, together with the calculated Arrhenius preexponential factor ratio (A(H)/A(D)=0.0004) and difference in the observed activation energy [(EaD -EaH )=34.07 kJ mol(-1)] are consistent with the participation of quantum tunneling in the catalytic process. DFT calculations have been used to unravel the reaction pathway and identify the rate-determining step. Aditionally, isotopic effects were considered by different methods, and tunneling effects have been calculated to be crucial in the process.This research was supported by the Universidad del Pais Vasco (UPV/EHU) (GIU13/06), Ministerio de Economia y Competitividad (PID2019-111281GB-00), Gobierno Vasco (IT1880-19 and IT1254-19). Technical and human support provided by IZO-SGI, SGIKER (UPV/EHU, MICINN, GV/EJERDF and ESF), is gratefully acknowledged for assistance and generous allocation of computational resources. N.A. is grateful to Diputacion Foral de Gipuzkoa (OF215/2016), and M.A.H. and Z.F. to IKERBASQUE for funding. We would like to thank Dr. Eugene E. Kwan for his support and fruitful discussion using PyQuiver program
Monocolor chemosensors for Ba2+ tagging experiments
Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de QuÃmica, 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 QuÃmica, 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 QuÃmica, 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
Ba+2 ion trapping using organic submonolayer for ultra-low background neutrinoless double beta detector
If neutrinos are their own antiparticles the otherwise-forbidden nuclear reaction known as neutrinoless double beta decay can occur. The very long lifetime expected for these exceptional events makes its detection a daunting task. In order to conduct an almost background-free experiment, the NEXT collaboration is investigating novel synthetic molecular sensors that may capture the Ba dication produced in the decay of certain Xe isotopes in a high-pressure gas experiment. The use of such molecular detectors immobilized on surfaces must be explored in the ultra-dry environment of a xenon gas chamber. Here, using a combination of highly sensitive surface science techniques in ultra-high vacuum, we demonstrate the possibility of employing the so-called Fluorescent Bicolor Indicator as the molecular component of the sensor. We unravel the ion capture process for these molecular indicators immobilized on a surface and explain the origin of the emission fluorescence shift associated to the ion trapping.This material is based upon work supported by the following agencies and institutions: the European Research Council (ERC) under ERC-2020-SyG 951281; the MCIN/AEI/10.13039/501100011033 of Spain and ERDF A way of making Europe under grants PID2020-114252GB-I00, PID2019-107338RB-C63, PID2019-104772GB-I00, PID2019-111281GB-I00, and RTI2018-095979, the Severo Ochoa Program grant CEX2018-000867-S; the Basque Government (GV/EJ) under grants IT-1553-22, IT-1591-22. The NEXT Collaboration acknowledges support from the following agencies and institutions: the European Union’s Framework Programme for Research and Innovation Horizon 2020 (2014-2020) under Grant Agreement No. 957202-HIDDEN; the MCIN/AEI of Spain and ERDF A way of making Europe under grants RTI2018-095979 and PID2021-125475NB, the Severo Ochoa Program grant CEX2018-000867-S and the Ramón y Cajal program grant RYC-2015-18820; the Generalitat Valenciana of Spain under grants PROMETEO/2021/087 and CIDEGENT/2019/049; the Department of Education of the Basque Government of Spain under the predoctoral training program non-doctoral research personnel; the Portuguese FCT under project UID/FIS/04559/2020 to fund the activities of LIBPhys-UC; the Pazy Foundation (Israel) under grants 877040 and 877041; the US Department of Energy under contracts number DE-AC02-06CH11357 (Argonne National Laboratory), DE-AC02-07CH11359 (Fermi National Accelerator Laboratory), DE-FG02-13ER42020 (Texas A&M), DE-SC0019054 (Texas Arlington) and DE-SC0019223 (Texas Arlington); the US National Science Foundation under award number NSF CHE 2004111; the Robert A Welch Foundation under award number Y-2031-20200401. Finally, we are grateful to the Laboratorio Subterráneo de Canfranc for hosting and supporting the NEXT experiment.Peer reviewe
Chiral calix[4]arene-based diphosphites as ligands in the asymmetric hydrogenation of prochiral olefins
Chiral calixarene-based diphosphite ligands 3a-d have been obtained via lower-rim functionalisation of the p-tert-butylcalix[4]arene core. High enantiomeric excesses (up to 94 %) and good activities were obtained in the rhodium-catalyzed asymmetric hydrogenation of prochiral olefins with TADDOL-containing diphosphites 3c,d. This is the first example of chiral calix[4]arene-modified ligands that induce high enantioselectivity in metal-catalysed asymmetric reactions.</p