Corrosion Mitigation in Molten Salt Environments.

The aim of this paper is to present methods for corrosion mitigation in molten salt environments. The corrosion of structural materials depends directly on the redox potential of the salt. When the redox potential of the salt is higher than the standard potentials of the elements constituting the structural materials, corrosion occurs. If the reverse is true, no corrosion is observed. Herein, a methodology for calculating the theoretical potential of a molten salt is provided and compared with experimental measurements. Three ways to mitigate corrosion by modifying the salt redox potential are proposed: (i) using a soluble/soluble redox system; (ii) using a potentiostatic method; and (iii) using an amphoteric compound such as UCl3, TiCl2, or TiCl3. Immersion tests were conducted under the above conditions to validate the methodology.

Citronellol biosynthesis in pelargonium is a multistep pathway involving progesterone 5ß-reductase and/or iridoid synthase-like enzymes.

Citronellol is a pleasant-smelling compound produced in rose (Rosa spp.) flowers and in the leaves of many aromatic plants, including pelargoniums (Pelargonium spp.). Although geraniol production has been well studied in several plants, citronellol biosynthesis has been documented only in crab-lipped spider orchid (Caladenia plicata) and its mechanism remains open to question in other species. We therefore profiled 10 pelargonium accessions using RNA sequencing and gas chromatography-MS analysis. Three enzymes from the progesterone 5ß-reductase and/or iridoid synthase-like enzymes (PRISE) family were characterized in vitroand subsequently identified as citral reductases (named PhCIRs). Transgenic RNAi lines supported a role for PhCIRs in the biosynthesis of citronellol as well as in the production of mint-scented terpenes. Despite their high amino acid sequence identity, the 3 enzymes showed contrasting stereoselectivity, either producing mainly (S)-citronellal or a racemate of both (R)- and (S)-citronellal. Using site-directed mutagenesis, we identified a single amino acid substitution as being primarily responsible for the enzyme's enantioselectivity. Phylogenetic analysis of pelargonium PRISEs revealed 3 clades and 7 groups of orthologs. PRISEs from different groups exhibited differential affinities toward substrates (citral and progesterone) and cofactors (NADH/NADPH), but most were able to reduce both substrates, prompting hypotheses regarding the evolutionary history of PhCIRs. Our results demonstrate that pelargoniums evolved citronellol biosynthesis independently through a 3-step pathway involving PRISE homologs and both citral and citronellal as intermediates. In addition, these enzymes control the enantiomeric ratio of citronellol thanks to small alterations of the catalytic site.

A DFT study of defects in paramagnetic Cr2O3.

Cr2O3 is not only a promising functional material, but also an essential barrier to protect chromia-forming alloys against high temperature corrosion. The Cr2O3 protecting layer grows slowly via defect-mediated diffusion. Several types of point defects could be responsible for the diffusion process depending on the oxidation environment, resulting in different semiconductor characters of chromia. According to the literature, the defect chemistry of Cr2O3 in the antiferromagnetic (AFM) state has been well studied using density functional theory (DFT) calculations but not in the paramagnetic (PM) state, which is the fundamental state of Cr2O3 above 318 K. PM Cr2O3 is simulated in this study using special quasi-random structures (SQS). The formation energies of intrinsic point defects in AFM and PM Cr2O3 are calculated to study the defect chemistry and the semiconductor properties in different oxidation environments (temperature and oxygen partial pressure PO2) using a thermodynamic model. It is found that O vacancies and insulating-type Cr2O3, in which commensurate electrons and holes are dominant before atomic defects are more favorable at high temperatures and at low PO2, while Cr vacancies and p-type Cr2O3 are more favorable at low temperatures and at high PO2, according to the calculations both in AFM and PM Cr2O3. However, the limits of dominant zones for defects and for semiconductor characters shift to higher temperatures or lower PO2 in PM state calculations.

Identification and Characterization of a New Type III Polyketide Synthase from a Marine Yeast, Naganishia uzbekistanensis.

A putative Type III Polyketide synthase (PKSIII) encoding gene was identified from a marine yeast, Naganishia uzbekistanensis strain Mo29 (UBOCC-A-208024) (formerly named as Cryptococcus sp.) isolated from deep-sea hydrothermal vents. This gene is part of a distinct phylogenetic branch compared to all known terrestrial fungal sequences. This new gene encodes a C-terminus extension of 74 amino acids compared to other known PKSIII proteins like Neurospora crassa. Full-length and reduced versions of this PKSIII were successfully cloned and overexpressed in a bacterial host, Escherichia coli BL21 (DE3). Both proteins showed the same activity, suggesting that additional amino acid residues at the C-terminus are probably not required for biochemical functions. We demonstrated by LC-ESI-MS/MS that these two recombinant PKSIII proteins could only produce tri- and tetraketide pyrones and alkylresorcinols using only long fatty acid chain from C8 to C16 acyl-CoAs as starter units, in presence of malonyl-CoA. In addition, we showed that some of these molecules exhibit cytotoxic activities against several cancer cell lines.

Functional Analysis of Four Terpene Synthases in Rose-Scented Pelargonium Cultivars (Pelargonium × hybridum) and Evolution of Scent in the Pelargonium Genus.

Pelargonium genus contains about 280 species among which at least 30 species are odorant. Aromas produced by scented species are remarkably diverse such as rose, mint, lemon, nutmeg, ginger and many others scents. Amongst odorant species, rose-scented pelargoniums, also named pelargonium rosat, are the most famous hybrids for their production of essential oil (EO), widely used by perfume and cosmetic industries. Although EO composition has been extensively studied, the underlying biosynthetic pathways and their regulation, most notably of terpenes, are largely unknown. To gain a better understanding of the terpene metabolic pathways in pelargonium rosat, we generated a transcriptome dataset of pelargonium leaf and used a candidate gene approach to functionally characterise four terpene synthases (TPSs), including a geraniol synthase, a key enzyme responsible for the biosynthesis of the main rose-scented terpenes. We also report for the first time the characterisation of a novel sesquiterpene synthase catalysing the biosynthesis of 10-epi-γ-eudesmol. We found a strong correlation between expression of the four genes encoding the respective TPSs and accumulation of the corresponding products in several pelargonium cultivars and species. Finally, using publically available RNA-Seq data and de novo transcriptome assemblies, we inferred a maximum likelihood phylogeny from 270 pelargonium TPSs, including the four newly discovered enzymes, providing clues about TPS evolution in the Pelargonium genus. Notably, we show that, by contrast to other TPSs, geraniol synthases from the TPS-g subfamily conserved their molecular function throughout evolution.

Ozone inactivation of resistant microorganisms: Laboratory analysis and evaluation of the efficiency of plants.

In this work, the ozone inactivation of resistant microorganisms is studied and a method to assess the efficiency of a drinking water plant to inactivate resistant microorganisms using ozone is proposed. This method aims at computing the fraction of resistant microorganisms that are not inactivated at the exit of an ozonation step by evaluating the duration of the lag phase of the ozone inactivation of these microorganisms and the contact time distribution of these microorganisms with the ozone in the step. To evaluate the duration of the lag phase of the ozone inactivation of resistant pathogenic microorganisms, an experimental procedure is proposed and applied to Bacillus subtilis spores. The procedure aims at characterizing the ozone inactivation kinetics of B. subtilis spores for different temperature and ozone concentration conditions. From experimental data, a model of the ozone inactivation of B. subtilis spores is built. One of the parameters of this model is called the lag time and it measures the duration of the lag phase of the ozone inactivation of B. subtilis spores. This lag time is identified for different temperature and ozone concentration conditions in order to establish a correlation between this lag time and the temperature and ozone concentration conditions. To evaluate the contact time distribution between microorganisms and the ozone in a disinfection step of a drinking water plant, a computational fluid dynamics tool is used. The proposed method is applied to the ozonation channel of an existing drinking water plant located in Belgium and operated by Vivaqua. Results show that lag times and contact times are both in the same order of magnitude of a few minutes. For a large range of temperatures and ozone concentrations in the Tailfer ozonation channel and for the highest hydraulic flow rate applied, a significant fraction of resistant microorganisms similar to B. subtilis spores is not inactivated.