Non-covalent interactions in molecular clusters : competition between ?- and H-bonding

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Crystallographic Visualization of a Double Water Molecule Addition on a Pt-1-MOF during the Low-temperature Water-Gas Shift Reaction

This is the peer reviewed version of the following article: C. Bilanin, E. Tiburcio, J. Ferrando-Soria, D. Armentano, A. Leyva-Pérez, E. Pardo, ChemCatChem 2021, 13, 1195, which has been published in final form at https://doi.org/10.1002/cctc.202001492. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] The low-temperature water-gas shift reaction (WGSR, CO+H2O H-2+CO2) is considered a very promising reaction -candidate for fuel cells- despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt-1) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H2O molecule to CO, with generation of CO2 and H-2. Here we show, experimentally, that not one but two H2O molecules are added to CO on the Pt-1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measurements, and finally by in-operando single crystal X-ray diffraction on a Pt-1-MOF, to visualize the formation of the hemiacetal intermediate on the solid catalytic site. These results confirm our previous DFT predictions and provide a paradigmatic shift in the assumed mechanism of the WGSR, which may open the debate if two H2O molecules are recurrently added during the WGSR, not only for Pt-1 catalysts but also for other metal catalysts.This work was supported by the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) and the Ministerio de Ciencia e Innovacion (Spain) (Projects PID2019-104778GB-I00 and CTQ2017-86735-P and the excellence units "Severo Ochoa" SEV-2016-0683 and "Maria de Maeztu" CEX2019-000919-M). C. B. and E. T. thank ITQ and MINECO for the concession of fellowships. Thanks are extended to the "2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011" (J. F.-S.). D.A. acknowledges the financial support of the Fondazione CARIPLO / "Economia Circolare: ricerca per un futuro sostenibile" 2019, Grant number: 2019-2090, MOCA. We thank to Dr. R. Adam, Dr. J. Oliver-Meseguer and J. C. Arango for their help. E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme / ERC Grant Agreement No 814804, MOF-reactors. We acknowledge Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities with dosing gas cell and thank Dr Mark Warren for his assistance at I19 beamline (Proposal number MT18768-2).Bilanin-Artigado, C.; Tiburcio, E.; Ferrando-Soria, J.; Armentano, D.; Leyva Perez, A.; Pardo, E. (2021). Crystallographic Visualization of a Double Water Molecule Addition on a Pt-1-MOF during the Low-temperature Water-Gas Shift Reaction. ChemCatChem. 13(4):1195-1200. https://doi.org/10.1002/cctc.202001492S1195120013

Mass analyzed threshold ionization spectra of phenol⋯Ar2: ionization energy and cation intermolecular vibrational frequencies

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.The phenol+⋯Ar2 complex has been characterized in a supersonic jet by mass analyzed threshold ionization (MATI) spectroscopyvia different intermediate intermolecular vibrational states of the first electronically excited state (S1). From the spectra recorded via the S100 origin and the S1βx intermolecular vibrational state, the ionization energy (IE) has been determined as 68 288 ± 5 cm−1, displaying a red shift of 340 cm−1 from the IE of the phenol+ monomer. Well-resolved, nearly harmonic vibrational progressions with a fundamental frequency of 10 cm−1 have been observed in the ion ground state (D0) and assigned to the symmetric van der Waals (vdW) bending mode, βx, along the x axis containing the C–O bond. MATI spectra recorded via the S1 state involving other higher-lying intermolecular vibrational states (σ1s, β3x, σ1sβ1x, σ1sβ2x) are characterized by unresolved broad structures

Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope

[EN] Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type zeolites (Y and X) or a metal organic framework (MOF), to give a reusable heterogeneous catalyst which provides an industrially viable process well below the flammability limit of alcohols and amines.This work was supported by the MINECO (Spain) (Projects CTQ2017-86735-P, CTQ2016-75671-P, CTQ2014-56312-P, CTQ2014-55178-R, and MAT2013-40823-R and Excellence Units "Severo Ochoa" SEV2016-0683 and "Maria de Maeztu" and MDM-2015-0538) and the European Union through ERC-AdG-2014-671093 (SynCatMatch) and the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) (FFABR 2017). M.M. thanks the MINECO for a predoctoral contract. RA. thanks UPV for a postdoctoral contract. J.F.-S. acknowledges financial support from the Subprograma Atraccio de Talent - Contractes Postdoctorals de la Universitat de Valencia. We also acknowledge SOLEIL for provision of the synchrotron radiation facility and thank Pierre Fertey for his assistance.Mon, M.; Adam-Ortiz, R.; Ferrando-Soria, J.; Corma Canós, A.; Pardo, E.; Armentano, D.; Leyva Perez, A. (2018). Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope. ACS Catalysis. 8(11):10401-10406. https://doi.org/10.1021/acscatal.8b03228S104011040681

Resistenza all'uso degli ipoglicemizzanti orali nel trattamento del diabete tipo 2: uno studio multicentrico

Type 2 diabetes is an important social and health care system variable due to its large diffusion, frequency of clinical complications and its health care costs. The studied population is relative to 4 italian centers distributed all over the country (Brescia, Roma, Rossano Calabro and Avola). This work has the aim to describe the Italian type 2 population according to treatment choice ruled by diabetes stage, glycemia control and HbA1c concentration. The analysis present a description of the therapeutic changes during the year of observation too, giving a complete picture of patients distribution and their treatment path through diabetes evolution in Italy

Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

[EN] The preparation of novel efficient catalyststhat could be applicable in industrially important chemical processeshas attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag-2(0) subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal-organic framework, with the formula [Ag-2(0)]@(Ag2Na2I)-Na-I{Ni-4(II)[Cu-2(II)(Me(3)mpba)(2)](3)}middot48H(2)O [Me(3)mpba(4-) = N,N '-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalystfully characterized with the help of single-crystal X-ray diffractionexhibits high catalytic activity for the catalytic Buchner ring expansion reaction.This work was supported by the Ministero dell'Universita e della Ricerca (Italy), the MICIIN (Spain) (projects PID2020- 115100GB-I00, PID2019-104778GB-I00 and Excellence Unit "Maria de Maeztu" CEX2019-000919-M) , and the Generalitat Valenciana (project PROMETEO/2021/054). Thanks are also extended to the Ramon y Cajal Program (RYC2019-027940-I) (J. F.-S.) and the Diamond Light Source for the awarded beamtime and provision of synchrotron radiation facilities (proposal no. CY22411-1). We particularly acknowledge Dr David Allan and Sarah Barnett for their assistance at the I19 beamline. E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme/ERC grant agreement no 814804, MOF-reactors. M.M. thanks MICIIN from a contract under the Juan de la Cierva program (FJC2019-040523-I). Y.Z. thanks the China Scholarship Council (CSC no: 202009350009) for a Ph.D. fellowship.Tiburcio, E.; Zheng, Y.; Mon-Conejero, M.; Martín, N.; Ferrando-Soria, J.; Armentano, D.; Leyva Perez, A.... (2022). Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction. Inorganic Chemistry. 61:11796-11802. https://doi.org/10.1021/acs.inorgchem.2c0150811796118026

Tissue transglutaminase is involved in the inflammatory processes of active chronic gastritis

Since tissue transglutaminase-2 (TG2) can represent a marker of inflammation for some gastrointestinal (GI) diseases, we aimed to evaluate TG2 and inflammatory markers? mucosal content in gastric antrum biopsies to shed light on the histological and biochemical background of chronic gastritis inflammation. Fifty-one of 78 patients who underwent upper GI endoscopy (UGIE) for dyspeptic symptoms, had a gastric biopsy. The symptom profile was assessed by a GI symptom rating scale (GSRS) score. Thirty-five patients (69%) showed chronic gastritis. TG2, interleukin-6 (IL)-6, IL-8, IL-10, tumor necrosis factor (TNF)-?, lipopolysaccharides (LPS) and toll-like receptor (TLR)-4 were evaluated in serum and the culture medium of gastric biopsies. TG2, IL-8, IL-10, TLR-4 and TNF-? were significantly higher in active chronic gastritis than in the inactive one and were linked to macrophage concentration. IL-6 was significantly lower in the active form of chronic gastritis than in the inactive one and negatively correlated with TG2. Lastly, IL-10 significantly correlated with the macrophage score. TG2 can exert an active role in chronic gastritis pathogenesis by cooperating with different markers of inflammation. It seems that TG2 can represent a possible therapeutic target for modulating inflammation and disease progression

Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions

[EN] The search for simple, earth-abundant, cheap, and nontoxic metal catalysts able to perform industrial hydrogenations is a topic of interest, transversal to many catalytic processes. Here, we show that isolated FeIII¿O sites on solids are able to dissociate and chemoselectively transfer H2 to acetylene in an industrial process. For that, a novel, robust, and highly crystalline metal¿organic framework (MOF), embedding FeIII¿OH2 single sites within its pores, was prepared in multigram scale and used as an efficient catalyst for the hydrogenation of 1% acetylene in ethylene streams under front-end conditions. Cutting-edge X-ray crystallography allowed the resolution of the crystal structure and snapshotted the single-atom nature of the catalytic FeIII¿O site. Translation of the active site concept to even more robust and inexpensive titania and zirconia supports enabled the industrially relevant hydrogenation of acetylene with similar activity to the Pd-catalyzed process.This work was supported by the MINECO (Spain) (Projects CTQ2016-75671-P, CTQ2014-56312-P, CTQ2014-55178-R, and Excellence Units "Severo Ochoa" and "Maria de Maeztu" SEV-2016-0683 and MDM-2015-0538) and the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) (FFABR 2017). M.M. thanks the mineco for a predoctoral contract. Thanks are also extended to the Ramon y Cajal Program (E.P.) and the "Suprograma atraccio de talent-contractes postdoctorals de la Universitat de Valencia" (J.F.-S.). A.L.-P. and J.F.S. also thank fBBVA for the concession of a young investigator grants.Tejeda-Serrano, M.; Mon, M.; Ross, B.; Gonell-Gómez, F.; Ferrando-Soria, J.; Corma Canós, A.; Leyva Perez, A.... (2018). Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions. Journal of the American Chemical Society. 140(28):8827-8832. https://doi.org/10.1021/jacs.8b04669S882788321402