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In the present work, the novel Al0.15CoCrFeNiW0.15 High-Entropy Alloy (HEA) has been designed by CALPHAD (CALculation of PHAse Diagrams) computations with the in-house built Genova High-Entropy Alloys (GHEA) database, aiming to a mostly monophasic face-centered cubic (FCC) alloy strengthened by the precipitation of secondary μ phase. To explore different preparation routes, alloy samples have been synthesized by both arc melting (AM) and spark plasma sintering (SPS). Samples were characterized by low optical microscopy (LOM), scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD), and microhardness measurements. Long-term annealing at 1100 °C has been performed, followed by quenching or furnace cooling. AM as-cast sample showed a monophasic FCC microstructure, characterized by large grains. Precipitation of μ phase was observed in the equilibrated and quenched sample, in good agreement with the thermodynamic calculations. On the other hand, SPS samples resulted in a finer microstructure, characterized by the presence of small particles of Al2O3 and μ phase, already present before annealing. Contrary to the thermodynamic predictions, after equilibration and quenching, the dissolution of the μ phase was observed due to the Gibbs-Thomson effect, which enhanced W solubility in the FCC solid solution. Annealing of the SPSed alloy followed by furnace cooling, however, allowed the precipitation of μ, thanks to the slower cooling rate. Overall, this study highlighted CALPHAD's utility for composition selection in complex multicomponent systems and demonstrated how AM and SPS lead to significantly different microstructures and properties, with grain size playing a key role in determining the alloy performances.

New lead-vanadate based sorbents were synthesized with the aim to entrap and confine gaseous iodine in off-gas streams coming from reprocessing facilities of spent nuclear fuel. Their synthesis relies on the shaping of a lead-vanadate, lead sulfide and alginic acid mix as millimetric beads. These beads were calcined between 220°C and 500°C to remove organic alginic compounds template. However, according to the calcination temperature, lead sulfide could be partially oxidized, limiting iodine loading capacity. A compromise temperature between 290°C and 350°C was found to remove most of the alginic acid template and avoiding lead sulfide oxidation. These sorbents were tested for iodine trapping in static conditions at 60°C. They performed well with a sorption capacity up to 155 mg.g−1 by forming PbI2. Furthermore, these iodine-loaded sorbents could be easily converted into an iodine-containing lead-vanadate apatite matrix by spark plasma sintering. A dense sample was produced for a sintering temperature of 500°C under 70 MPa. Such a material could be suitable for radioactive iodine conditioning in deep geological disposal. Finally, lead-vanadate sorbents could provide an easy way to entrap and confine radioactive iodine from off-gas streams into a durable material within a few steps.

Carrageenans are major gel forming polysaccharides in the extracellular matrix of the red macroalga Chondrus crispus. These galactans are made of linear chains of repetitive disaccharide motifs based on d-galactose residues alternately linked by β-1,4 and α-1,3 glycosidic bonds. A definite number of disaccharide motifs are known, based on their regular sulfations and the presence of a 3,6-anhydro bridge. While these motifs are variable as a function of species, life cycle phases, or seasons, our understanding of the in vivo regulation of carrageenan fine structures is still limited. Characterized hydrolytic enzymes (κ-, ι- and λ-carrageenases) are powerful tools for identifying glycan structures in extracted ECMs. Their use, combined to chromatography and high-resolution mass spectrometry, allowed us to refine our understanding of carrageenan variability in the phases of C. crispus. We provide the first demonstration that κ/ι carrabiose motifs are not limited to gametophytes, but are also present in tetrasporophytes, together with over- and under-sulfated λ-motifs. Our findings highlight a more complex carrageenan composition than previously described in this model system. These results are further discussed in the light of recent transcriptomic data and suggest that the historical hypotheses on the biosynthetic pathway of carrageenans in red algae may need revision. HYPOTHESIS: Combined characterized hydrolytic enzymes to chromatography and high-resolution mass spectrometry can refine our understanding of carrageenan variability in the phases of C. crispus., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Water absorption in wheat flour is a crucial parameter for optimizing bread-making processes. The determinants of wheat flour water absorption were investigated through the analysis of 28 compositional and technological properties of 150 wheats grown in France. A multiple linear regression approach was used to predict the water absorption, selecting the best model through successive examination of Bayesian Information Criterion, Variance Inflation Factor and minimizing the total number of variables. A model with protein content, soluble starch, damaged starch and specific viscosity from water extractable arabinoxylans was identified as the best trade-off between the number of variables and the predictive performances among all possible models. Soluble Starch, varying between 1.11 and 6.21 g/100 g flour a new criterion measured alongside water-extractable arabinoxylans content, varying between 0.26 and 0.86 g/100 g flour, shows significant potential to predict water absorption compared to damaged starch., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Assembling and remodelling the cell wall is essential for plant development. Cell wall dynamics is controlled by cell wall proteins, polysaccharide biosynthesis, and a variety of sensor and receptor systems. LecRK-I.9, an Arabidopsis thaliana plasma membrane-localised lectin receptor kinase, was previously shown to be involved in cell wall-plasma membrane contacts and to play roles in plant-pathogen interactions, but so far, its role in development was unknown. LecRK-I.9 is transcribed at a high level in root tissues including the pericycle. Comparative transcript profiling of a loss-of-function mutant vs wild type identifies LecRK-I.9 as a regulator of cell wall metabolism. Consistently, lecrk-I.9 mutants display an increased pectin methylesterification level correlated with decreased pectin methylesterase and increased polygalacturonase activities. Also, LecRK-I.9 negatively impacts lateral root development through the direct or indirect regulation of genes encoding (i) cell wall remodelling proteins during early events of lateral root initiation, and (ii) cell wall signalling peptides (CLE2, CLE4) repressing lateral root emergence and growth. Besides, low nitrate reduces LecRK-I.9 expression in roots, particularly in the lateral root emergence zone: even in these conditions, the control of CLE2 and CLE4 expression is maintained. Altogether, the results show that LecRK-I.9 is a key player in negatively regulating both pre-branch site formation and lateral root emergence., (© The Author(s) 2024. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For commercial re-use, please contact reprints@oup.com for reprints and translation rights for reprints. All other permissions can be obtained through our RightsLink service via the Permissions link on the article page on our site—for further information please contact journals.permissions@oup.com.)

Breast milk composition is influenced by maternal diet. This study aimed to evaluate if supplementation of maternal diet with a prebiotic fibre, through its potential effect on milk composition, can be a leverage to orientate the gut microbiota of infants in a way that would be beneficial for their health. Twelve sows received a diet supplemented with short chain fructo-oligosaccharides or maltodextrins during the last month of gestation and the lactation. Oligosaccharidic and lipidomic profiles of colostrum and mature milk (21 days), as well as faecal microbiota composition and metabolomic profile of 21 day-old piglets were evaluated. The total porcine milk oligosaccharide concentration tended to be lower in scFOS-supplemented sows, mainly due to the significant reduction of the neutral core oligosaccharides (in particular that of a tetrahexose). Maternal scFOS supplementation affected the concentration of 31 lipids (mainly long-chain triglycerides) in mature milk. Faecal short-chain fatty acid content and that of 16 bacterial metabolites were modified by scFOS supplementation. Interestingly, the integrative data analysis gave a novel insight into the relationships between (i) maternal milk lipids and PMOs and (ii) offspring faecal bacteria and metabolites. In conclusion, scFOS-enriched maternal diet affected the composition of mature milk, and this was associated with a change in the colonisation of the offspring intestinal microbiota., (© 2024. The Author(s).)

Lytic polysaccharide monooxygenases (LPMOs) can perform oxidative cleavage of glycosidic bonds in carbohydrate polymers (e.g., cellulose, chitin), making them more accessible to hydrolytic enzymes. While most studies have so far mainly explored the role of LPMOs in a (plant) biomass conversion context, alternative roles and paradigms begin to emerge. The AA10 LPMOs are active on chitin and/or cellulose and mostly found in bacteria and in some viruses and archaea. Interestingly, AA10-encoding genes are also encountered in some pathogenic fungi of the Ustilaginomycetes class, such as Ustilago maydis , responsible for corn smut disease. Transcriptomic studies have shown the overexpression of the AA10 gene during the infectious cycle of U. maydis . In fact, U. maydis has a unique AA10 gene that codes for a catalytic domain appended with a C-terminal disordered region. To date, there is no public report on fungal AA10 LPMOs. In this study, we successfully produced the catalytic domain of this LPMO ( Um AA10_cd) in Pichia pastoris and carried out its biochemical characterization. Our results show that Um AA10_cd oxidatively cleaves α- and β-chitin with C1 regioselectivity and boosts chitin hydrolysis by a GH18 chitinase from U. maydis ( Um GH18A). Using a biologically relevant substrate, we show that Um AA10_cd exhibits enzymatic activity on U. maydis fungal cell wall chitin and promotes its hydrolysis by Um GH18A. These results represent an important step toward the understanding of the role of LPMOs in the fungal cell wall remodeling process during the fungal life cycle.IMPORTANCELytic polysaccharide monooxygenases (LPMOs) have been mainly studied in a biotechnological context for the efficient degradation of recalcitrant polysaccharides. Only recently, alternative roles and paradigms begin to emerge. In this study, we provide evidence that the AA10 LPMO from the phytopathogen Ustilago maydis is active against fungal cell wall chitin. Given that chitin-active LPMOs are commonly found in microbes, it is important to consider fungal cell wall as a potential target for this enigmatic class of enzymes., Competing Interests: The authors declare no conflict of interest.

Filamentous fungi are keystone microorganisms in the regulation of many processes occurring on Earth, such as plant biomass decay and pathogenesis as well as symbiotic associations. In many of these processes, fungi secrete carbohydrate-active enzymes (CAZymes) to modify and/or degrade carbohydrates. Ten years ago, while evaluating the potential of a secretome from the maize pathogen Ustilago maydis to supplement lignocellulolytic cocktails, we noticed it contained many unknown or poorly characterized CAZymes. Here, and after reannotation of this data set and detailed phylogenetic analyses, we observed that several CAZymes (including glycoside hydrolases and carbohydrate oxidases) are predicted to act on the fungal cell wall (FCW), notably on β-1,3-glucans. We heterologously produced and biochemically characterized two new CAZymes, called Um GH16_1-A and Um AA3_2-A. We show that Um GH16_1-A displays β-1,3-glucanase activity, with a preference for β-1,3-glucans with short β-1,6 substitutions, and Um AA3_2-A is a dehydrogenase catalyzing the oxidation of β-1,3- and β-1,6-gluco-oligosaccharides into the corresponding aldonic acids. Working on model β-1,3-glucans, we show that the linear oligosaccharide products released by Um GH16_1-A are further oxidized by Um AA3_2-A, bringing to light a putative biocatalytic cascade. Interestingly, analysis of available transcriptomics data indicates that both Um GH16_1-A and Um AA3_2-A are coexpressed, only during early stages of U. maydis infection cycle. Altogether, our results suggest that both enzymes are connected and that additional accessory activities still need to be uncovered to fully understand the biocatalytic cascade at play and its physiological role. IMPORTANCE Filamentous fungi play a central regulatory role on Earth, notably in the global carbon cycle. Regardless of their lifestyle, filamentous fungi need to remodel their own cell wall (mostly composed of polysaccharides) to grow and proliferate. To do so, they must secrete a large arsenal of enzymes, most notably carbohydrate-active enzymes (CAZymes). However, research on fungal CAZymes over past decades has mainly focused on finding efficient plant biomass conversion processes while CAZymes directed at the fungus itself have remained little explored. In the present study, using the maize pathogen Ustilago maydis as model, we set off to evaluate the prevalence of CAZymes directed toward the fungal cell wall during growth of the fungus on plant biomass and characterized two new CAZymes active on fungal cell wall components. Our results suggest the existence of a biocatalytic cascade that remains to be fully understood.

Fibre bundles are groups of elementary fibres glued together thanks to the middle lamella, and are the main fraction in plant fibre composites. In this study, relationship between the mechanical properties of flax fibre bundles, chemical composition and cellulose structure were investigated. To do so, a sequential biopolymer extraction was implemented. Fibre bundles were first depectinated by oxalate extraction, and then the hemicelluloses were extracted by LiCl/dimethyl sulfoxide (DMSO) and KOH. The oxalate extract consisted of homogalacturonans and type I rhamnogalacturonans, while the LiCl extract was composed mainly of glucomannans and the KOH extract of xyloglucans. The KOH stage resulted in the appearance of cellulose II in flax bundles. The extraction of pectin and hemicelluloses led to the disappearance of the middle lamella concomitant with a decrease in the tensile Young's modulus and maximum strength. Finally, the fibre bundle composition, ultrastructure and mechanical properties are discussed together in view of the thin middle lamella., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

During this global pandemic of the COVID-19 disease, a lot of information has arisen in the media and online without scientific validation, and among these is the possibility that this disease could be aggravated by a secondary bacterial infection such as Prevotella, as well as the interest or not in using azithromycin, a potentially active antimicrobial agent. The aim of this study was to carry out a systematic literature review, to prove or disprove these allegations by scientific arguments. The search included Medline, PubMed, and Pubtator Central databases for English-language articles published 1999-2021. After removing duplicates, a total of final eligible studies ( n =149) were selected. There were more articles showing an increase of Prevotella abundance in the presence of viral infection like that related to Human Immunodeficiency Virus (HIV), Papillomavirus (HPV), Herpesviridae and respiratory virus, highlighting differences according to methodologies and patient groups. The arguments for or against the use of azithromycin are stated in light of the results of the literature, showing the role of intercurrent factors, such as age, drug consumption, the presence of cancer or periodontal diseases. However, clinical trials are lacking to prove the direct link between the presence of Prevotella spp. and a worsening of COVID-19, mainly those using azithromycin alone in this indication.

Sulfated fucans from brown algae are a heterogeneous group of biologically active molecules. To learn more on their structure and to analyze and exploit their biological activities, there is a growing need to develop reliable and cost effective protocols for their preparation. In the present study, a brown alga Pelvetia canaliculata (Linnaeus) was used as a rich source of sulfated fucans. Sulfated fucan preparation methods included neutral and acidic extractions followed by purification with activated charcoal (AC), polyvinylpolypyrrolidone (PVPP), or cetylpyridinium chloride (CPC). Final products were compared in terms of yield, purity, monosaccharide composition and molecular weight. Acidic extractions provided higher yields compared to neutral ones, whereas the AC purification provided sulfated fucan products with the highest purity. Mass spectrometry analyses were done on oligosaccharides produced by the fucanase MfFcnA from the marine bacterium Mariniflexille fucanivorans. This has provided unique insight into enzyme specificity and the structural characteristics of sulfated fucans., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Heteroxylans (HX) from vitreous and floury parts of maize endosperm were isolated. Structural analysis showed a xylan backbone with few unsubstituted xylose residues (<9%) demonstrating the high content in side chains in both fractions. HX from floury endosperm contained more arabinose and galactose than vitreous HX. The mono-substitution rate was 15% higher in the vitreous endosperm HX. Similar amounts of uronic acids were present in both fractions (~7% DM). Galactose in the floury endosperm HX was present exclusively in terminal position. A xylanase preparation solubilized more material from floury (40.5%) than from vitreous endosperm cell walls (15%). This could be a consequence of the structural differences between the two fractions and/or of the impact of structure on the interaction abilities of these fractions with other cell wall polysaccharides. Our study advances the understanding of cell wall polysaccharides in maize endosperm and their role in enzymatic susceptibility of maize grain., (Copyright © 2021. Published by Elsevier Ltd.)

Cell wall composition was studied during the development of apple cultivars (14-161/182 days after full bloom, DAA) maintaining firm fruit (Ariane) or evolving to mealy texture (Rome Beauty) when ripe and in sweet cherry cultivars (21/26-70/75 DAA) to assess their skin-cracking susceptibility (tolerant Regina and susceptible Garnet). Pectin sugar composition and hemicellulose fine structure assessed by enzymatic degradation coupled to MALDI-TOF MS analysis were shown to vary markedly between apples and cherries during fruit development. Apple showed decreasing rhamnogalacturonan I (RGI) and increasing homogalacturonan (HG) pectic domain proportions from young to mature fruit. Hemicellulose-cellulose (HC) sugars peaked at the beginning of fruit expansion corresponding to the maximum cell wall content of glucose and mannose. In contrast, HG peaked very early in the cell wall of young developing cherries and remained constant until ripening whereas RGI content continuously increased. HC content decreased very early and remained low in cell walls. Only the low content of mannose and to a lesser extent fucose increased and then slowly decreased from the beginning of the fruit expansion phase. Hemicellulose structural profiling showed strong varietal differences between cherry cultivars. Both apples and cherries demonstrated a peak of glucomannan oligomers produced by β-glucanase hydrolysis of the cell wall at the onset of cell expansion. The different glucomannan contents and related oligomers released from cell walls are discussed with regard to the contribution of glucomannan to cell wall mechanical properties. These hemicellulose features may prove to be early markers of apple mealiness and cherry skin-cracking susceptibility., (Copyright © 2021 Elsevier Masson SAS. All rights reserved.)

The data were collected from a brown mustard seeds collection of 18 accessions during two years and in three distinct sites of production in France. The 18 accessions of mustard seeds were selected to be representative of genetic, agronomical and technological variabilities. All accessions were produced in the " Bourgogne " area. This article describes agronomical data (PMG, yield), genotyping data, global composition of mustard seeds (lipids, proteins and polysaccharides) and fine composition of the previous macronutrients potentially involved in the technological properties (fatty acids, storage proteins and osidic composition of polysaccharides). Additional data regarding the potential rheological property of each accessions were also reported. These data can be reused by food industries, breeders and geneticists in order to understand pedoclimatic effects (year and location) and the relation between mustard seed composition and the end-uses properties (paste mustard quality)., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2021 The Author(s).)

Breastmilk is known to be very important for infants because it provides nutrients and immunological compounds. Among these compounds, human milk oligosaccharides (HMOs) represent the third most important component of breastmilk after lipids and lactose. Several experiments demonstrated the beneficial effects of these components on the microbiota, the immune system and epithelial barriers, which are three major biological systems. Indeed, HMOs induce bacterial colonization in the intestinal tract, which is beneficial for health. The gut bacteria can act directly and indirectly on the immune system by stimulating innate immunity and controlling inflammatory reactions and by inducing an adaptive immune response and a tolerogenic environment. In parallel, HMOs directly strengthen the intestinal epithelial barrier, protecting the host against pathogens. Here, we review the molecular mechanisms of HMOs in these different compartments and highlight their potential use as new therapeutic agents, especially in allergy prevention., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Rousseaux, Brosseau, Le Gall, Piloquet, Barbarot and Bodinier.)

Fucoidans are a diverse class of sulfated polysaccharides integral to the cell wall of brown algae, and due to their various bioactivities, they are potential drugs. Standardized work with fucoidans is required for structure-function studies, but remains challenging since available fucoidan preparations are often contaminated with other algal compounds. Additionally, fucoidans are structurally diverse depending on species and season, urging the need for standardized purification protocols. Here, we use ion-exchange chromatography to purify different fucoidans and found a high structural diversity between fucoidans. Ion-exchange chromatography efficiently removes the polysaccharides alginate and laminarin and other contaminants such as proteins and phlorotannins across a broad range of fucoidans from major brown algal orders including Ectocarpales, Laminariales and Fucales. By monomer composition, linkage analysis and NMR characterization, we identified galacturonic acid, glucuronic acid and O-acetylation as new structural features of certain fucoidans and provided a novel structure of fucoidan from Durvillaea potatorum with α-1,3-linked fucose backbone and β-1,6 and β-1,3 galactose branches. This study emphasizes the use of standardized ion-exchange chromatography to obtain defined fucoidans for subsequent molecular studies., (© The Author(s) 2020. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

The assembly of the newborn's gut microbiota during the first months of life is an orchestrated process resulting in specialized microbial ecosystems in the different gut compartments. This process is highly dependent upon environmental factors, and many evidences suggest that early bacterial gut colonization has long-term consequences on host digestive and immune homeostasis but also metabolism and behavior. The early life period is therefore a "window of opportunity" to program health through microbiota modulation. However, the implementation of this promising strategy requires an in-depth understanding of the mechanisms governing gut microbiota assembly. Breastfeeding has been associated with a healthy microbiota in infants. Human milk is a complex food matrix, with numerous components that potentially influence the infant microbiota composition, either by enhancing specific bacteria growth or by limiting the growth of others. The objective of this review is to describe human milk composition and to discuss the established or purported roles of human milk components upon gut microbiota establishment. Finally, the impact of maternal diet on human milk composition is reviewed to assess how maternal diet could be a simple and efficient approach to shape the infant gut microbiota., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Boudry, Charton, Le Huerou-Luron, Ferret-Bernard, Le Gall, Even and Blat.)

Thermoresponsive hydrogels present unique properties, such as tunable mechanical performance or changes in volume, which make them attractive for applications including wound healing dressings, drug delivery vehicles, and implants, among others. This work reports the implementation of bioinspired thermoresponsive hydrogels composed of xyloglucan (XG) and cellulose nanocrystals (CNCs). Starting from tamarind seed XG (XGt), thermoresponsive XG was obtained by enzymatic degalactosylation (DG-XG), which reduced the galactose residue content by ∼50% and imparted a reversible thermal transition. XG with native composition and comparable molar mass to DG-XG was produced by an ultrasonication treatment (XGu) for a direct comparison of behavior. The hydrogels were prepared by simple mixing of DG-XG or XGu with CNCs in water. Phase diagrams were established to identify the ratios of DG-XG or XGu to CNCs that yielded a viscous liquid, a phase-separated mixture, a simple gel, or a thermoresponsive gel. Gelation occurred at a DG-XG or XGu to CNC ratio higher than that needed for the full surface coverage of CNCs and required relatively high overall concentrations of both components (tested concentrations up to 20 g/L XG and 30 g/L CNCs). This is likely a result of the increase in effective hydrodynamic volume of CNCs due to the formation of XG-CNC complexes. Investigation of the adsorption behavior indicated that DG-XG formed a more rigid layer on CNCs compared to XGu. Rheological properties of the hydrogels were characterized, and a reversible thermal transition was found for DG-XG/CNC gels at 35 °C. This thermoresponsive behavior provides opportunities to apply this system widely, especially in the biomedical field, where the mechanical properties could be further tuned by adjusting the CNC content.

Photoelectrochemical water splitting under harsh chemical conditions can be promoted by dispersed transition metal nanoparticles electrodeposited on n-Si surfaces, without the need for classical protection layers. Although this method is simple, it only allows for poor control of metal morphology and geometry on the photoanode surface. Herein, we introduce templated nanoscale electrodeposition on photoactive n-Si for the customization of nanoscale inhomogeneous Schottky junctions and demonstrate their use as stable photoanodes. The photoelectrochemical properties of the so-manufactured photoanodes exhibit a strong dependence on the photoanodes' geometrical features, and the obtained experimental trends are rationalized using simulation.

CD8 T cells provide limited protection against Mycobacterium tuberculosis (Mtb) infection in the mouse model. As Mtb causes chronic infection in mice and humans, we hypothesize that Mtb impairs T cell responses as an immune evasion strategy. TB10.4 is an immunodominant antigen in people, nonhuman primates, and mice, which is encoded by the esxH gene. In C57BL/6 mice, 30-50% of pulmonary CD8 T cells recognize the TB10.44-11 epitope. However, TB10.4-specific CD8 T cells fail to recognize Mtb-infected macrophages. We speculate that Mtb elicits immunodominant CD8 T cell responses to antigens that are inefficiently presented by infected cells, thereby focusing CD8 T cells on nonprotective antigens. Here, we leverage naturally occurring polymorphisms in esxH, which frequently occur in lineage 1 strains, to test this "decoy hypothesis". Using the clinical isolate 667, which contains an EsxHA10T polymorphism, we observe a drastic change in the hierarchy of CD8 T cells. Using isogenic Erd.EsxHA10T and Erd.EsxHWT strains, we prove that this polymorphism alters the hierarchy of immunodominant CD8 T cell responses. Our data are best explained by immunodomination, a mechanism by which competition for APC leads to dominant responses suppressing subdominant responses. These results were surprising as the variant epitope can bind to H2-Kb and is recognized by TB10.4-specific CD8 T cells. The dramatic change in TB10.4-specific CD8 responses resulted from increased proteolytic degradation of A10T variant, which destroyed the TB10.44-11epitope. Importantly, this polymorphism affected T cell priming and recognition of infected cells. These data support a model in which nonprotective CD8 T cells become immunodominant and suppress subdominant responses. Thus, polymorphisms between clinical Mtb strains, and BCG or H37Rv sequence-based vaccines could lead to a mismatch between T cells that are primed by vaccines and the epitopes presented by infected cells. Reprograming host immune responses should be considered in the future design of vaccines., Competing Interests: The authors have declared that no competing interests exist.

This article presents a study on Metal-Assisted Chemical Etching (MACE) of silicon in HF-H 2 O 2 using silver nanoparticles as catalysts. Our aim is a better understanding of the process to elaborate new 3D submicrometric surface structures useful for light management. We investigated MACE over the whole range of silicon doping, i.e., p ++ , p + , p, p - , n, n + , and n ++ . We discovered that, instead of the well-defined and straight mesopores obtained in p and n-type silicon, in p ++ and n ++ silicon MACE leads to the formation of cone-shaped macropores filled with porous silicon. We account for the transition between these two pore-formation regimes (straight and cone-shaped pores) by modeling (at equilibrium and under polarization) the Ag/Si/electrolyte (HF) system. The model simulates the system as two nanodiodes in series. We show that delocalized MACE is explained by a large tunnel current contribution for the p-Si/Ag and n-Si/HF diodes under reverse polarization, which increases with the doping level and when the size of the nanocontacts (Ag, HF) decreases. By analogy with the results obtained on heavily doped silicon, we finally present a method to form size-controlled cone-shaped macropores in p silicon with silver nanoparticles. This shape, instead of the usual straight mesopores, is obtained by applying an external anodic polarization during MACE. Two methods are shown to be effective for the control of the macropore cone angle: one by adjusting the potential applied during MACE, the other by changing the H 2 O 2 concentration. Under appropriate etching conditions, the obtained macropores exhibit optical properties (reflectivity ~3 %) similar to that of black silicon., (Copyright © 2020 Pinna, Le Gall, Torralba, Mula, Cachet-Vivier and Bastide.)

In this article, we have demonstrated a solid carbon source such as camphor as a natural precursor to synthesize a large area mono/bi-layer graphene (MLG) sheet to fabricate a nanowire junction-based near infrared photodetectors (NIRPDs). In order to increase the surface-to-volume ratio, we have developed Si-nanowire arrays (SiNWAs) of varying lengths by etching planar Si. Then, the camphor-based MLG/Si and MLG/SiNWAs Schottky junction photodetectors have been fabricated to achieve an efficient response with self-driven properties in the near infrared (NIR) regime. Due to a balance between light absorption capability and surface recombination centers, devices having SiNWAs obtained by etching for 30 min shows a better photoresponse, sensitivity and detectivity. Fabricated NIRPDs can also be functioned as self-driven devices which are highly responsive and very stable at low optical power signals up to 2 V with a fast rise and decay time of 34/13 ms. A tremendous enhancement has been witnessed from 36 μA W -1 to 22 mA W -1 in the responsivity at 0 V for MLG/30 min SiNWAs than planar MLG/Si PDs indicating an important development of self-driven NIRPDs based on camphor-based MLG for future optoelectronic devices.

Latency reversal agents (LRA) variably induce HIV re-expression in CD4 T cells but reservoirs are not cleared. Whether HIV epitope presentation is similar between latency reversal and initial infection of CD4 T cells is unknown yet crucial to define immune responses able to detect HIV-infected CD4 T cells after latency reversal. HIV peptides displayed by MHC comes from the intracellular degradation of proteins by proteasomes and post-proteasomal peptidases but the impact of LRAs on antigen processing is not known. Here we show that HDAC inhibitors (HDCAi) reduced cytosolic proteolytic activities while PKC agonists (PKCa) increased them to a lesser extent than that induced by TCR activation. During the cytosolic degradation of long HIV peptides in LRA-treated CD4 T cells extracts, HDACi and PKCa modulated degradation patterns of peptides and altered the production of HIV epitopes in often opposite ways. Beyond known HIV epitopes, HDACi narrowed the coverage of HIV antigenic fragments by 8-11aa degradation peptides while PKCa broadened it. LRAs altered HIV infection kinetics and modulated CD8 T cell activation in an epitope- and time-dependent manner. Interestingly the efficiency of endogenous epitope processing and presentation to CD8 T cells was increased by PKCa Ingenol at early time points despite low levels of antigens. LRA-induced modulations of antigen processing should be considered and exploited to enhance and broaden HIV peptide presentation by CD4 T cells and to improve immune recognition after latency reversal. This property of LRAs, if confirmed with other antigens, might be exploited to improve immune detection of diseased cells beyond HIV., Competing Interests: The authors have declared that no competing interests exist.

The viscoelastic mechanical properties are important quality traits for fleshy fruit uses. The contribution of cell wall polysaccharides chemistry and organization on their variability was studied in six varieties of apple. Correlation between damping and storage modulus of plasmolyzed tissue distinguished better apple varieties on their viscoelasticity than fresh samples. Galactose, arabinose and uronic acids correlated positively with the storage modulus of fresh apple samples (E' f ). These corresponded to 4-linked galactan but no specific arabinose linkage. Galacturonic acid branched on O-3 and terminal rhamnose correlated negatively with E' f . These correlations formed two groups of fruit except for branched methyl-esterified galacturonic. Solid-state 13 C NMR spectroscopy analyses showed that E' f correlated negatively with cellulose C4 T 1ρ H relaxation and positively with pectin methyl esters T HH proton diffusion. The results point to the key roles of pectin structure and hydration and cellulose microfibrils distribution on apple mechanical properties., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The use of next generation sequencing and bioinformatics has revealed the complexity and richness of the human oral microbiota. While some species are well known for their periodontal pathogenicity, the molecular-based approaches for bacterial identification have raised awareness about new putative periodontal pathogens. Although they are found increased in case of periodontitis, there is currently a lack of data on their interrelationship with the periodontal measures. We processed the sequencing data of the subgingival microbiota of 75 patients with hemochromatosis and chronic periodontitis in order to characterize the well-described and newly identified subgingival periodontal pathogens. We used correlation tests and statistical models to assess the association between the periodontal pathogens and mean pocket depth, and to determine the most relevant bacterial biomarkers of periodontitis severity. Based on correlation test results, nine taxa were selected and included in the statistical models. The multiple linear regression models adjusted for systemic and periodontal clinical variables showed that mean pocket depth was negatively associated with Aggregatibacter and Rothia, and positively associated with Porphyromonas. Furthermore, a bacterial ratio that was previously described as a signature of dysbiosis in periodontitis (%Porphyromonas+%Treponema+%Tannerella)/(%Rothia+%Corynebacterium) was the most significant predictor. In this specific population, we found that the best model in predicting the mean pocket depth was microbial dysbiosis using the dysbiosis ratio taxa formula. While further studies are needed to assess the validity of these results on the general population, such a dysbiosis ratio could be used in the future to monitor the subgingival microbiota., (© 2019 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

This work focuses on the extraction of the open circuit voltage (V OC ) on photovoltaic nanowires by surface photovoltage (SPV) based on Kelvin probe force microscopy (KPFM) measurements. In a first approach, P-I-N radial junction (RJ) silicon nanowire (SiNW) devices were investigated under illumination by KPFM and current-voltage (I-V) analysis. Within 5%, the extracted SPV correlates well with the V OC . In a second approach, local SPV measurements were applied on single isolated radial junction SiNWs pointing out shadowing effects from the AFM tip that can strongly impact the SPV assessment. Several strategies in terms of AFM tip shape and illumination orientation have been put in place to minimize this effect. Local SPV measurements on isolated radial junction SiNWs increase logarithmically with the illumination power and demonstrate a linear behavior with the V OC . The results show notably that contactless measurements of the V OC become feasible at the scale of single photovoltaic SiNW devices.

In plant cell walls, xylan chains present various substituents including acetate groups. The influence of the acetyl substitution on the organization of xylan-cellulose complexes remains poorly understood. This work combines in vitro and in silico approaches to decipher the functional role of acetyl groups on the xylan/cellulose interaction. Acetylated xylans were extracted from apple pomace with dimethyl sulfoxide-lithium chloride (DMSO-LiCl) and deacetylated using a mild alkali treatment. The adsorption behavior of acetylated and deacetylated xylan fractions was investigated using quartz crystal microbalance with dissipation (QCM-D) and molecular dynamics. Acetylated xylans form a dense and poorly hydrated and rigid layer on cellulose with xylan chains that have two residues per helical turn conformation, whereas the deacetylated fraction forms a swollen and more viscous layer in which only the xylan chains in direct contact with the cellulose surface have two residues per helical turn conformation. The other chains have three residues per turn conformation., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In wheat endosperm, mannan, is poorly documented. Nevertheless, this hemicellulosic polysaccharide might have a determinant role in wheat grain development since, in Arabidopsis thaliana, mutants with a reduced amount of mannan show an altered seed development. In order to gain knowledge about mannan in wheat, we have determined its biochemical structure in wheat endosperm where mannose content is about 0.2% (dry weight basis). We developed a method of enzymatic fingerprinting and isolated mannan-enriched fractions to decipher its fine structure. Although it is widely accepted that the class of mannan present in grass cell walls is glucomannan, our data indicate that, in wheat endosperm, this hemicellulose is only represented by short unsubstituted chains of 1,4 linked D-mannose residues and is slightly acetylated. Our study provides information regarding the interactions of mannan with other cell wall components and help to progress towards the understanding of monocot cell wall architecture and the mannan synthesis in wheat endosperm., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Development of microbiota-directed foods (MDFs) that selectively increase the abundance of beneficial human gut microbes, and their expressed functions, requires knowledge of both the bioactive components of MDFs and the mechanisms underlying microbe-microbe interactions. Here, gnotobiotic mice were colonized with a defined consortium of human-gut-derived bacterial strains and fed different combinations of 34 food-grade fibers added to a representative low-fiber diet consumed in the United States. Bioactive carbohydrates in fiber preparations targeting particular Bacteroides species were identified using community-wide quantitative proteomic analyses of bacterial gene expression coupled with forward genetic screens. Deliberate manipulation of community membership combined with administration of retrievable artificial food particles, consisting of paramagnetic microscopic beads coated with dietary polysaccharides, disclosed the contributions of targeted species to fiber degradation. Our approach, including the use of bead-based biosensors, defines nutrient-harvesting strategies that underlie, as well as alleviate, competition between Bacteroides and control the selectivity of MDF components., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The presentation of virus-derived peptides by MHC molecules constitutes the earliest signals for immune recognition by T cells. In HIV infection, immune responses elicited during infection do not enable to clear infection and correlates of immune protection are not well defined. Here we review features of antigen processing and presentation specific to HIV, analyze how HIV has adapted to the antigen processing machinery and discuss how advances in biochemical and computational protein degradation analyses and in immunopeptidome definition may help identify targets for efficient immune clearance and vaccine immunogen design., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The interface resistance at metal/semiconductor junctions has been a key issue for decades. The control of this resistance is dependent on the possibility to tune the Schottky barrier height. However, Fermi level pinning in these systems forbids a total control over interface resistance. The introduction of 2D crystals between semiconductor surfaces and metals may be an interesting route towards this goal. In this work, we study the influence of the introduction of a graphene monolayer between a metal and silicon on the Schottky barrier height. We used X-ray photoemission spectroscopy to rule out the presence of oxides at the interface, the absence of pinning of the Fermi level and the strong reduction of the Schottky barrier height. We then performed a multiscale transport analysis to determine the transport mechanism. The consistency in the measured barrier height at different scales confirms the good quality of our junctions and the role of graphene in the drastic reduction of the barrier height., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

The chloroplast is a major plant cell organelle that fulfills essential metabolic and biosynthetic functions. Located at the interface between the chloroplast and other cell compartments, the chloroplast envelope system is a strategic barrier controlling the exchange of ions, metabolites and proteins, thus regulating essential metabolic functions (synthesis of hormones precursors, amino acids, pigments, sugars, vitamins, lipids, nucleotides etc.) of the plant cell. However, unraveling the contents of the chloroplast envelope proteome remains a difficult challenge; many proteins constituting this functional double membrane system remain to be identified. Indeed, the envelope contains only 1% of the chloroplast proteins ( i.e. 0.4% of the whole cell proteome). In other words, most envelope proteins are so rare at the cell, chloroplast, or even envelope level, that they remained undetectable using targeted MS studies. Cross-contamination of chloroplast subcompartments by each other and by other cell compartments during cell fractionation, impedes accurate localization of many envelope proteins. The aim of the present study was to take advantage of technologically improved MS sensitivity to better define the proteome of the chloroplast envelope (differentiate genuine envelope proteins from contaminants). This MS-based analysis relied on an enrichment factor that was calculated for each protein identified in purified envelope fractions as compared with the value obtained for the same protein in crude cell extracts. Using this approach, a total of 1269 proteins were detected in purified envelope fractions, of which, 462 could be assigned an envelope localization by combining MS-based spectral count analyses with manual annotation using data from the literature and prediction tools. Many of such proteins being previously unknown envelope components, these data constitute a new resource of significant value to the broader plant science community aiming to define principles and molecular mechanisms controlling fundamental aspects of plastid biogenesis and functions., (© 2019 Bouchnak et al.)