Monitoring global vegetation

An attempt is made to identify the need for, and the current capability of, a technology which could aid in monitoring the Earth's vegetation resource on a global scale. Vegetation is one of our most critical natural resources, and accurate timely information on its current status and temporal dynamics is essential to understand many basic and applied environmental interrelationships which exist on the small but complex planet Earth

Dynamic Structure and Subsurface Oxygen Formation of a Working Copper Catalyst under Methanol Steam Reforming Conditions: An in Situ Time-Resolved Spectroscopic Study

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, 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/acscatal.8b05042."[EN] The dynamic behavior of a CuO/ZnO/Ga2O3 catalyst under methanol steam reforming (MSR) reaction conditions promoted by a high dispersion of the copper nanoparticles and defect sites of a nonstoichiometric ZnGa2O4 spinel phase has been observed, where structural changes taking place in the initial state of the reaction determine the final state of the catalyst in stationary reaction conditions. Mass spectrometry (MS) studies under transient conditions coupled to X-ray photoelectron spectroscopy (XPS) have shown copper oxidation to Cu+ in the initial state of the reaction (TOS = 4 min), followed by a fast reduction of the outer shell to Cu-0, while keeping dissolved oxygen species in the inner layers of the nanoparticle. The presence of this subsurface oxygen impairs a positive charge to the uppermost surface copper species, that is, Cu delta+, which undoubtedly plays an important role on the MSR catalytic activity. The detection of these features, unperceived by conventional spectroscopic and catalytic studies, has only been possible by combining synchrotron NAP-XPS studies with transient studies performed in a low volume catalytic reactor connected to MS and linked with Raman and laboratory scale XPS studies.The research leading to these results has received funding from the European Union's Seventh Framework Programme (FP/2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under Grant Agreement No. [303476]. Part of this work was financially supported by the following projects: (i) Project POCI-01-0145-FEDER-006939 (Laboratory for Process Engineering, Environment, Biotechnology and Energy UID/EQU/00511/2013) funded by the European Regional Development Fund (ERDF), through COMPETE2020 - Programa Operacional Competitividade e Internacionalizacao (POCI) and by national funds, through FCT - Fundacao para a Ciencia e a Tecnologia; (ii) NORTE-01-0145-FEDER-000005 - LEPABE-2-ECO-INNOVATION, supported by North Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (ERDF); and (iii) the Spanish Government-MINECO through "Severo Ochoa" Excellence Programme (SEV-2016-0683). D.R. thanks European Research Council project SYNCATMATCH (671093). J.C. thanks the Spanish Government (MINECO) for a "Severo Ochoa" grant (BES-2015-075748). The NAP-XPS experiments were performed at the NAPP branch of the CIRCE beamline at the ALBA Synchrotron with the collaboration of ALBA staff.Ruano-Sánchez, D.; Cored-Bandrés, J.; Azenha, C.; Pérez-Dieste, V.; Mendes, A.; Mateos-Pedrero, C.; Concepción Heydorn, P. (2019). Dynamic Structure and Subsurface Oxygen Formation of a Working Copper Catalyst under Methanol Steam Reforming Conditions: An in Situ Time-Resolved Spectroscopic Study. ACS Catalysis. 9(4):2922-2930. https://doi.org/10.1021/acscatal.8b05042S292229309

Tuning zirconia-supported metal catalysts for selective one-step hydrogenation of levoglucosenone

[EN] Levoglucosenone, directly produced from cellulose-containing residual biomass via pyrolysis treatments, is believed to be a promising bio-renewable platform for both fine and commodity chemicals. In this work, the possibilities given by tuneable catalysts based on Pd and Pt supported on metallic oxides to produce the desired product in the one-pot hydrogenation of levoglucosenone are evaluated. Particularly, the excellent catalytic performance of Pd/ZrO2 and Pt/ZrO2 type materials for the synthesis of dihydrolevoglucosenone (or Cyrene) and levoglucosanol, respectively, during the mild hydrogenation of levoglucosenone is demonstrated. In the Cyrene synthesis, the Pd/t-ZrO2 material showed the best catalytic activity compared to other Pd-supported on metallic oxides. This catalyst achieved nearly 95% yields of Cyrene by working under mild reaction conditions, with very low catalyst loadings (¿3 wt%) and using water as the solvent. On the other hand, the one-pot hydrogenation of levoglucosenone to levoglucosanol is reported for the first time with a Pt-based heterogeneous catalyst (Pt/ZrO2-mix, yield ¿90%), by working at low temperatures and mild H2 pressures with water as the solvent. Comparison of the results attained with other Pt-supported metallic oxides let us to conclude that the metal crystal facets (specifically the 100 facet) play an important role in the hydrogenation process to give levoglucosanol selectively. In addition, the stability and re-usability of both catalysts under operational conditions are also evaluated. Finally, catalytic tests including the use of crude bio-liquids obtained from cellulose-rich biomass pyrolysis and containing ¿66 wt% of levoglucosenone are also assayed, thus demonstrating the possibility of scaling-up the process over these metals supported on zirconia catalysts.Financial support by the Spanish Government (CTQ-201567592, SEV-2016-0683 and PGC2018-097277-B-100) is gratefully acknowledged. R.S. thanks the CONICET financial support (CONICET-CSIC, PVCE Program, RD 4183/15). J.M. thanks MICINN (CTQ2015-67592) for the PhD fellowship. Authors also thank the Electron Microscopy Service of Universitat Politecnica de Valencia for their support.Mazarío-Santa-Pau, J.; Parreño-Romero, M.; Concepción Heydorn, P.; Chávez-Sifontes, M.; Spanevello, RA.; Comba, MB.; Suárez, AG.... (2019). Tuning zirconia-supported metal catalysts for selective one-step hydrogenation of levoglucosenone. 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Green Chemistry, 13(11), 3306. doi:10.1039/c1gc15975eLu, Q., Ye, X., Zhang, Z., Dong, C., & Zhang, Y. (2014). Catalytic fast pyrolysis of cellulose and biomass to produce levoglucosenone using magnetic SO42−/TiO2–Fe3O4. Bioresource Technology, 171, 10-15. doi:10.1016/j.biortech.2014.08.075Wang, Z., Lu, Q., Zhu, X.-F., & Zhang, Y. (2010). Catalytic Fast Pyrolysis of Cellulose to Prepare Levoglucosenone Using Sulfated Zirconia. ChemSusChem, 4(1), 79-84. doi:10.1002/cssc.201000210Corne, V., Botta, M. C., Giordano, E. D. V., Giri, G. F., Llompart, D. F., Biava, H. D., … Spanevello, R. A. (2013). Cellulose recycling as a source of raw chirality. Pure and Applied Chemistry, 85(8), 1683-1692. doi:10.1351/pac-con-12-11-10Tsai, Y., Borini Etichetti, C. M., Di Benedetto, C., Girardini, J. E., Martins, F. T., Spanevello, R. A., … Sarotti, A. M. (2018). 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Self-Organization, Layered Structure, and Aggregation Enhance Persistence of a Synthetic Biofilm Consortium

Microbial consortia constitute a majority of the earth’s biomass, but little is known about how these cooperating communities persist despite competition among community members. Theory suggests that non-random spatial structures contribute to the persistence of mixed communities; when particular structures form, they may provide associated community members with a growth advantage over unassociated members. If true, this has implications for the rise and persistence of multi-cellular organisms. However, this theory is difficult to study because we rarely observe initial instances of non-random physical structure in natural populations. Using two engineered strains of Escherichia coli that constitute a synthetic symbiotic microbial consortium, we fortuitously observed such spatial self-organization. This consortium forms a biofilm and, after several days, adopts a defined layered structure that is associated with two unexpected, measurable growth advantages. First, the consortium cannot successfully colonize a new, downstream environment until it selforganizes in the initial environment; in other words, the structure enhances the ability of the consortium to survive environmental disruptions. Second, when the layered structure forms in downstream environments the consortium accumulates significantly more biomass than it did in the initial environment; in other words, the structure enhances the global productivity of the consortium. We also observed that the layered structure only assembles in downstream environments that are colonized by aggregates from a previous, structured community. These results demonstrate roles for self-organization and aggregation in persistence of multi-cellular communities, and also illustrate a role for the techniques of synthetic biology in elucidating fundamental biological principles

Biofilm Induced Tolerance towards Antimicrobial Peptides

Increased tolerance to antimicrobial agents is thought to be an important feature of microbes growing in biofilms. We address the question of how biofilm organization affects antibiotic susceptibility. We established Escherichia coli biofilms with differential structural organization due to the presence of IncF plasmids expressing altered forms of the transfer pili in two different biofilm model systems. The mature biofilms were subsequently treated with two antibiotics with different molecular targets, the peptide antibiotic colistin and the fluoroquinolone ciprofloxacin. The dynamics of microbial killing were monitored by viable count determination, and confocal laser microscopy. Strains forming structurally organized biofilms show an increased bacterial survival when challenged with colistin, compared to strains forming unstructured biofilms. The increased survival is due to genetically regulated tolerant subpopulation formation and not caused by a general biofilm property. No significant difference in survival was detected when the strains were challenged with ciprofloxacin. Our data show that biofilm formation confers increased colistin tolerance to cells within the biofilm structure, but the protection is conditional being dependent on the structural organization of the biofilm, and the induction of specific tolerance mechanisms

Influence of quorum sensing signal molecules on biofilm formation in Proteus mirabilis O18

The influence of basis of quorum sensing molecules on Proteus strains is much less known as compared to Pseudomonas or Escherichia. We have previously shown that a series of acylated homoserine lactones (acyl-HSL) does not influence the ureolytic, proteolytic, or hemolytic abilities, and that the swarming motility of Proteus mirabilis rods is strain specific. The aim of the presented study was to find out if the presence of a series of acyl-HSL influences biofilm formation of P. mirabilis laboratory strain belonging to O18 serogroup. This serogroup is characterized by the presence of a unique non-carbohydrate component, namely phosphocholine. Escherichia coli and P. mirabilis O18 strains used in this work contains cloned plasmids encoding fluorescent protein genes with constitutive gene expression. In mixed biofilms in stationary and continuous flow conditions, P. mirabilis O18 overgrow whole culture. P. mirabilis O18 strain has genetically proved a presence of AI–2 quorum sensing system. Differences in biofilm structure were observed depending on the biofilm type and culture methods. From tested acylated homoserine lactones (BHL, HHL, OHL, DHL, dDHL, tDHL), a significant influence had BHL on thickness, structure, and the amount of exopolysaccharides produced by biofilms formed by P. mirabilis O18 pDsRed2

Molecular characterization of the EhaG and UpaG trimeric autotransporter proteins from pathogenic Escherichia coli

Trimeric autotransporter proteins (TAAs) are important virulence factors of many Gram-negative bacterial pathogens. A common feature of most TAAs is the ability to mediate adherence to eukaryotic cells or extracellular matrix (ECM) proteins via a cell surface-exposed passenger domain. Here we describe the characterization of EhaG, a TAA identified from enterohemorrhagic Escherichia coli (EHEC) O157:H7. EhaG is a positional orthologue of the recently characterized UpaG TAA from uropathogenic E. coli (UPEC). Similarly to UpaG, EhaG localized at the bacterial cell surface and promoted cell aggregation, biofilm formation, and adherence to a range of ECM proteins. However, the two orthologues display differential cellular binding: EhaG mediates specific adhesion to colorectal epithelial cells while UpaG promotes specific binding to bladder epithelial cells. The EhaG and UpaG TAAs contain extensive sequence divergence in their respective passenger domains that could account for these differences. Indeed, sequence analyses of UpaG and EhaG homologues from several E. coli genomes revealed grouping of the proteins in clades almost exclusively represented by distinct E. coli pathotypes. The expression of EhaG (in EHEC) and UpaG (in UPEC) was also investigated and shown to be significantly enhanced in an hns isogenic mutant, suggesting that H-NS acts as a negative regulator of both TAAs. Thus, while the EhaG and UpaG TAAs contain some conserved binding and regulatory features, they also possess important differences that correlate with the distinct pathogenic lifestyles of EHEC and UPEC