Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Circular economy emphasizes the idea of transforming products involving economic growth and improving the ecological system to reduce the negative consequences caused by the excessive use of raw materials. This can be achieved with the use of second-generation biomass that converts industrial and agricultural wastes into bulk chemicals. The use of catalytic processes is essential to achieve a viable upgrade of biofuels from the lignocellulosic biomass. We carried out density functional theory calculations to explore the relationship between 13 transition metals (TMs) properties, as catalysts, and their affinity for hydrogen and oxygen, as key species in the valourization of biomass. The relation of these parameters will define the trends of the hydrodeoxygenation (HDO) process on biomass-derived compounds. We found the hydrogen and oxygen adsorption energies in the most stable site have a linear relation with electronic properties of these metals that will rationalize the surface's ability to bind the biomass-derived compounds and break the C–O bonds. This will accelerate the catalyst innovation for low temperature and efficient HDO processes on biomass derivates, e.g. guaiacol and anisole, among others. Among the monometallic catalysts explored, the scaling relationship pointed out that Ni has a promising balance between hydrogen and oxygen affinities according to the d-band centre and d-band width models. The comparison of the calculated descriptors to the adsorption strength of guaiacol on the investigated surfaces indicates that the d-band properties alone are not best suited to describe the trend. Instead, we found that a linear combination of work function and d-band properties gives significantly better correlation

The influence of support materials on the structural and electronic properties of gold nanoparticles - a DFT study

Supported gold nanoparticles are used for a wide range of catalytic processes. In this work, we use dispersion corrected density functional theory (DFT-D) to study the effect of commonly used support materials (MgO, C, CeO2) on small gold particles with up to 19 atoms. Our results show that the preferred cluster shape and morphology is highly dependent on the support material due to different adsorption strength and structural mismatch between the cluster and the surface material. We developed an algorithm to measure the mismatch between the cluster interface and the support surface. Moreover, depending on the support material, the gold clusters exhibit a positive or negative polarisation, which ultimately has strong implications on the catalytic activity of such particles. This behaviour is rationalised by an analysis of the electronic structure of the metal particles and support materials

Limiting absorption principle for the dissipative Helmholtz equation

Adapting Mourre's commutator method to the dissipative setting, we prove a limiting absorption principle for a class of abstract dissipative operators. A consequence is the resolvent estimates for the high frequency Helmholtz equation when trapped trajectories meet the set where the imaginary part of the potential is non-zero. We also give the resolvent estimates in Besov spaces

SLC37A4-CDG : mislocalization of the glucose-6-phosphate transporter to the Golgi causes a new congenital disorder of glycosylation

Loss-of-function of the glucose-6-phosphate transporter is caused by biallelic mutations in SLC37A4 and leads to glycogen storage disease Ib. Here we describe a second disease caused by a single dominant mutation in the same gene. The mutation abolishes the ER retention signal of the transporter and generates a weak Golgi retention signal. Intracellular mislocalization of the transporter leads to a congenital disorder of glycosylation instead of glycogen storage disease

Density functional theory study of the partial oxidation of methane to methanol on Au and Pd surfaces

The partial oxidation of methane to methanol has been a goal of heterogeneous catalysis for many years. Recent experimental investigations have shown how AuPd nanoparticle catalysts can give good selectivity to methanol with only limited total oxidation of CH4 using hydrogen peroxide as an oxidant in aqueous media. Interestingly, the use of colloidal nanoparticles alone, without a support material, leads to efficient use of the oxidant and the possibility of introducing oxygen from O2(g) into the CH3O2H primary product. This observation indicates that a radical mechanism is being initiated by H2O2 but then the oxygen addition step, catalyzed by these nanoparticles, can incorporate O2(ads). In this contribution, we use density functional theory (DFT) to study the elementary steps in the partial oxidation of methane to methanol using H2O2 as a radical initiator and molecular oxygen as an oxidant over the low index surfaces of Pd and Au. We are able to show that pure Pd nanoparticles are prone to oxidation by O2(g), whereas the competitive adsorption of water on Au surfaces limits the availability of O2(ads). Calculations with Au added to Pd or vice versa show that both effects can be alleviated by using mixed metal surfaces. This provides a rationalization of the need to use alloy nanoparticles experimentally, and the insights from these results will aid future catalyst development

The hyperdominant tropical tree <i>Eschweilera coriacea</i> (Lecythidaceae) shows higher genetic heterogeneity than sympatric Eschweilera species in French Guiana

International audienceBackground and aims – The evolutionary history of Amazonia’s hyperabundant tropical tree species, also known as “hyperdominant” species, remains poorly investigated. We assessed whether the hyperdominant Eschweilera coriacea (DC.) S.A.Mori (Lecythidaceae) represents a single genetically cohesive species, and how its genetic constitution relates to other species from the same clade with which it occurs sympatrically in French Guiana.Methods – We sampled 152 individuals in nine forest sites in French Guiana, representing 11 species of the genus Eschweilera all belonging to the Parvifolia clade, with emphasis on E. coriacea. Samples were genotyped at four simple sequence repeat (SSR) markers. We delimited gene pools, i.e., genetically coherent putative taxa, using STRUCTURE software and principal component analysis. We compared the genetic assignment of individuals with their morphological species determination and estimated genetic diversity and differentiation for gene pools and species. We also estimated genome size using flow cytometry.Key results – SSR profiles commonly displayed up to four alleles per genotype, suggesting that the investigated Eschweilera species bear a paleopolyploid signature. Flow cytometry suggested that the studied species are diploid with haploid genome sizes of 871–1046 Mbp. We detected five gene pools and observed a good correspondence between morphological and genetic delimitation for Eschweilera sagotiana Miers and the undescribed morphospecies E. sp. 3 (which resembles E. grandiflora (Aubl.) Sandwith), and to a lesser extent for E. decolorans Sandwith and E. micrantha (O.Berg) Miers. Eschweilera coriacea was the most genetically diverse species and included individuals assigned to each gene pool.Conclusions – We found no conclusive evidence for cryptic species within E. coriacea in French Guiana. SSRs detected fewer gene pools than expected based on morphology in the Parvifolia clade but discriminated evolutionary relationships better than available plastid markers. A positive trend between demographic abundance of species and allelic richness illustrates that hyperdominants may have a high evolutionary potential. This hypothesis can be tested using more powerful genomic data in combination with tree phenotypic trait variation and characterization of niche breadth, to enhance our understanding of the causes of hyperdominance in Amazonian trees

Evolutionary patterns of volatile terpene emissions across 202 tropical tree species

International audiencePlant responses to natural enemies include formation of secondary metabolites acting as direct or indirect defenses. Volatile terpenes represent one of the most diverse groups of secondary metabolites. We aimed to explore evolutionary patterns of volatile terpene emission. We measured the composition of damage-induced volatile terpenes from 202 Amazonian tree species, spanning the angiosperm phylogeny. Volatile terpenes were extracted with solid-phase micro extraction and desorbed in a gas chromatography–mass spectrometry for compound identification. The chemical diversity of the terpene blend showed a strong phylogenetic signal as closely related species emitted a similar number of compounds. Closely related species also tended to have compositionally similar blends, although this relationship was weak. Meanwhile, the ability to emit a given compound showed no significant phylogenetic signal for 200 of 286 compounds, indicating a high rate of diversification in terpene synthesis and/or great variability in their expression. Three lineages (Magnoliales, Laurales, and Sapindales) showed exceptionally high rates of terpene diversification. Of the 70 compounds found in >10% of their species, 69 displayed significant correlated evolution with at least one other compound. These results provide insights into the complex evolutionary history of volatile terpenes in angiosperms, while highlighting the need for further research into this important class of compounds

A novel isoform of the Ly108 gene ameliorates murine lupus

Studies of human systemic lupus erythematosus patients and of murine congenic mouse strains associate genes in a DNA segment on chromosome 1 with a genetic predisposition for this disease. The systematic analysis of lupus-prone congenic mouse strains suggests a role for two isoforms of the Ly108 receptor in the pathogenesis of the disease. In this study, we demonstrate that Ly108 is involved in the pathogenesis of lupus-related autoimmunity in mice. More importantly, we identified a third protein isoform, Ly108-H1, which is absent in two lupus-prone congenic animals. Introduction of an Ly108-H1–expressing transgene markedly diminishes T cell–dependent autoimmunity in congenic B6.Sle1b mice. Thus, an immune response–suppressing isoform of Ly108 can regulate the pathogenesis of lupus.Peer Reviewe