Formamide adsorption at the amorphous silica surface : A combined experimental and computational approach

Mineral surfaces have been demonstrated to play a central role in prebiotic reactions, which are understood to be at the basis of the origin of life. Among the various molecules proposed as precursors for these reactions, one of the most interesting is formamide. Formamide has been shown to be a pluripotent molecule, generating a wide distribution of relevant prebiotic products. In particular, the outcomes of its reactivity are strongly related to the presence of mineral phases acting as catalysts toward specific reaction pathways. While the mineral-products relationship has been deeply studied for a large pool of materials, the fundamental description of formamide reactivity over mineral surfaces at a microscopic level is missing in the literature. In particular, a key step of formamide chemistry at surfaces is adsorption on available interaction sites. This report aims to investigate the adsorption of formamide over a well-defined amorphous silica, chosen as a model mineral surface. An experimental IR investigation of formamide adsorption was carried out and its outcomes were interpreted on the basis of first principles simulation of the process, adopting a realistic model of amorphous silica

Identification and characterization of Diaporthe spp. associated with twig cankers and shoot blight of almonds in Spain

[EN] Two hundred and twenty-fiveDiaportheisolates were collected from 2005 to 2019 in almond orchards showing twig cankers and shoot blight symptoms in five different regions across Spain. Multilocus DNA sequence analysis with five loci (ITS,tub,tef-1 alpha,calandhis), allowed the identification of four knownDiaporthespecies, namely:D. amygdali,D. eres,D. foeniculinaandD. phaseolorum. Moreover, a novel phylogenetic species,D. mediterranea, was described.Diaportheamygdaliwas the most prevalent species, due to the largest number of isolates (85.3%) obtained from all sampled regions. The second most frequent species wasD. foeniculina(10.2%), followed byD. mediterranea(3.6%),D.eresandD. phaseolorum, each with only one isolate. Pathogenicity tests were performed using one-year-old almond twigs cv. Vayro and representative isolates of the different species. Except forD. foeniculinaandD. phaseolorum, allDiaporthespecies were able to cause lesions significantly different from those developed on the uninoculated controls.Diaporthe mediterraneacaused the most severe symptoms. These results confirmD. amygdalias a key pathogen of almonds in Spain. Moreover, the new species,D. mediterranea, should also be considered as a potential important causal agent of twig cankers and shoot blight on this crop.Research funded by the Instituto Nacional de Investigacion y Tecnologia Agraria y Alimentaria (INIA), grants RTA2017-00009-C04-01, -02, -03 and -04 and with matching funds from the European Regional Development Fund (ERDF). G. Elena and C. Agusti-Brisach were supported by the Spanish post-doctoral grants "Juan de la Cierva-Formacion" and "Juan de la Cierva-Incorporacion", respectively. J. Luque and X. Miarnau were partially supported by the CERCA program, Generalitat de Catalunya. D. Gramaje was supported by the Ramon y Cajal program, Spanish Government (RYC-2017-23098).León Santana, M.; Berbegal Martinez, M.; Rodríguez-Reina, JM.; Elena, G.; Abad Campos, P.; Ramón-Albalat, A.; Olmo, D.... (2020). Identification and characterization of Diaporthe spp. associated with twig cankers and shoot blight of almonds in Spain. Agronomy. 10(8):1-23. https://doi.org/10.3390/agronomy10081062S123108Food and Agriculture Organization of the United Nationshttp://www.fao.org/faostat/es/#datDiogo, E. L. F., Santos, J. M., & Phillips, A. J. L. (2010). Phylogeny, morphology and pathogenicity of Diaporthe and Phomopsis species on almond in Portugal. Fungal Diversity, 44(1), 107-115. doi:10.1007/s13225-010-0057-xTuset, J. J., & Portilla, M. A. T. (1989). Taxonomic status of Fusicoccum amygdali and Phomopsis amygdalina. Canadian Journal of Botany, 67(5), 1275-1280. doi:10.1139/b89-168TUSET, J. J., HINAREJOS, C., & PORTILLA, M. T. (1997). 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Electron hole formation in acidic zeolite catalysts

The formation of an electron hole on an AlO4H center of the H-ZSM-5 zeolite has been studied by a hybrid quantum mechanics/shell-model ion-pair potential approach. The Becke-3-Lee-Yang-Parr (B3LYP) and Becke-Half&Half-Lee-Yang-Parr (BHLYP) hybrid density functionals yield electron holes of different nature, a delocalized hole for B3LYP and a hole localized on one oxygen atom for BHLYP. Comparison with coupled cluster calculations including single and double substitutions and with perturbative treatment of triple substitutions CCSD(T) and with experimental data for similar systems indicate that the localized description obtained with BHLYP is more accurate. Generation of the electron hole produces a substantial geometry relaxation, in particular an elongation of the Al-O distance to the oxygen atom with the unpaired electron. The zeolite framework stabilizes the positive charge by long-range effects. Our best estimates for the vertical and adiabatic ionization energies are 9.6–10.1 and 8.4–8.9 eV, respectively. Calculations for silicalite, the all-silica form of ZSM-5, also yield a localized electron hole, but the energy cost of the process is larger by 0.6–0.7 eV. The deprotonation energy of H-ZSM-5 is found to decrease from 12.86 to 11.40 eV upon electron hole formationPeer Reviewe