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Biogenic volatile organic compounds (VOCs) emitted by plants can reveal information about plant adaptation, defense processes, and biological pathways. Thus, such VOC data may be utilized to capture phenotypic plant responses to the environment. In this study, the main objective was to evaluate the potential of biogenic compounds, including VOCs, to phenotype two pea cultivars, Ariel (susceptible) and Hampton (high levels of partial resistance) for resistance to Aphanomyces root rot disease. Plants were monitored non-destructively for VOC emission at three-time points (15, 20, and 30 days after inoculation, DAI) using dynamic headspace sampling with gas chromatography-flame ionization detection (GC-FID) system, as well as destructively at the end of the experiments, using solvent extraction and pyrolysis of both shoot and root tissues. A non-inoculated control (mock-inoculated with distilled water) was utilized to compare the plant responses within a cultivar. The common chemical peaks between control and inoculated samples of both cultivars (RTcm) were analyzed after normalizing the relative peak intensity of inoculated samples with those of control samples, prior to a comparison between cultivars. In addition, unique chemical peaks (RTuq) present in inoculated samples, but not in control samples were also identified and their relative peak intensities were compared. Among the released green leaf volatiles (RTcm), the normalized relative peak intensity of hexanal emission, at 20 DAI, was higher in Ariel than that of Hampton. In addition, several putative chemical peaks (both RTcm and RTuq), previously known as indicators for disease response, exhibited some differences in their emission rates between pea cultivars in at least one of the time points. The destructive sampling revealed that shoot samples produced more putative unique biomarkers (RTuq) than the root samples. Based on the differences in putative chemical peaks between cultivars, this initial study supports the concept of utilization of biogenic biomarker-based phenotyping in distinguishing levels of resistance in the evaluated pea cultivars. More research is needed to further this approach for phenotyping other plant cultivars. Upon validation, the VOC profile integrated with high-throughput VOC sensing techniques can serve as a novel mechanism for phenotyping disease responses in crops.

Silicone gel-filled implants exist in a wide range of shapes and textures, and yet there are relatively few long-term large-scale studies, particularly on recently developed "semi-smooth" implants. The present study fills this gap by presenting the 3-year findings from an ongoing 10-year multicenter prospective study on breast implants with four different surface types: smooth, semi-smooth, microtextured, and macrotextured. A total of 908 patients were recruited in 15 investigational sites across Europe and divided into three groups: 653 primary augmentations in Group 1, 144 revision augmentations in Group 2, and 111 reconstructions in Group 3. All 4 types of implant shells were manufactured by the same company using the same silicone material. Surgeons were free to choose their preferred technique and implant surface, but data were collected using a standardized software and included all complications, and satisfaction levels reported by the patients at each visit. The incidence of post-operative complications was estimated based on Kaplan-Meier risk rates, on a per patient basis. At 3 years post implantation, capsular contracture (Baker grade III/IV) was the most common complication, with a per-patient risk rate of 1.5% in Group 1. Interestingly, there was no capsular contracture in this group when semi-smooth implants were used. The risk of implant rupture in Group 1 was 0.2%. The preliminary findings of this 10-year prospective study indicate that, 3 years after the operation, the four types of silicone gel-filled implants investigated were safe, with a low complication rate in comparison with the most favorable results published in other similar studies.

Introduction The TROPHIES observational study enrolled patients with type 2 diabetes mellitus (T2DM) initiating their first injectable treatment with the glucagon-like peptide 1 receptor agonists (GLP-1 RAs) dulaglutide or liraglutide. This manuscript focuses on the study design, baseline characteristics of the enrolled population, and factors associated with GLP-1 RA choice. Methods TROPHIES is a prospective, observational, 24-month study conducted in France, Germany, and Italy. Inclusion criteria include adult patients with T2DM, naïve to injectable antihyperglycemic treatments, initiating dulaglutide or liraglutide per routine clinical practice. The primary outcome is the duration of treatment on dulaglutide or liraglutide without a significant treatment change. Results The analysis included 2181 patients (dulaglutide, 1130; liraglutide, 1051) (cutoff date May 15, 2019). The population was 56% male with mean [standard deviation (SD)] patient characteristics at baseline as follows: age, 59.2 (11.0) years; body mass index (BMI), 33.9 (6.6) kg/m2; T2DM duration, 8.5 (6.9) years; and glycated hemoglobin (HbA1c), 8.2 (1.3)%. Between-cohort demographic and clinical characteristics were balanced. The mean (SD) HbA1c and BMI values for French, German, and Italian patients were, respectively, 8.6 (1.4)%, 8.2 (1.4)%, 8.0 (0.8)%; 33.3 (6.1) kg/m2, 36.0 (7.2) kg/m2, and 32.6 (5.9) kg/m2. Conclusion This study analysis at baseline provides an opportunity to evaluate between-country differences in baseline HbA1c, weight, macrovascular complications, and factors driving GLP-1 RA selection for patients with T2DM in daily practice. Supplementary Information The online version contains supplementary material available at 10.1007/s13300-021-01076-0., Plain Language Summary Dulaglutide and liraglutide are medications that can help people with type 2 diabetes mellitus (T2DM) to control their blood sugar levels. These medications may also reduce body weight and reduce the risk of major cardiovascular disease. Given these treatment effects, it is essential to know how they are used in everyday clinical practice. Therefore, a study is being performed in three countries (France, Germany, and Italy) in people with T2DM who had a first-ever injectable therapy for T2DM with dulaglutide or liraglutide. Here, we present the study design, the patient characteristics at the start of treatment, and the factors driving the choice of one or the other medication. We analyzed data from 2181 people with T2DM. On average, it was shown that they were middle-aged and obese. On average, these people were diagnosed with T2DM 8.5 years before the start of dulaglutide or liraglutide and had high blood sugar levels when these medications were started. The patient characteristics were slightly different between the three countries. Country-specific factors driving the choice of either medication were also identified. Supplementary Information The online version contains supplementary material available at 10.1007/s13300-021-01076-0.

Anaerobic digestion (AD) is an important technology to produce biogas from dairy manure. Although the AD of dairy manure results in the harnessing of the energy contained in manure, most of the nutrients (phosphorous and nitrogen) remain in the liquid effluent, representing an important source of pollution. Additionally, the biogas produced contains H2S and CO2, limiting its practical use as fuel. In this paper, we report the production and use of a carbonaceous adsorbent from AD fibers for the removal of hydrogen sulfide (H2S) from biogas and phosphate (PO43−) from aqueous liquid effluents. The adsorbents studied were produced via slow pyrolysis between 350 and 800 °C followed by CO2 activation. The elemental and proximate analyses, surface area and pore size distribution of each of the adsorbents studied are reported. Their adsorption capacities were assessed using H2S breakthrough and PO43− batch equilibrium tests. The sorption capacity varied between 21.9 and 51.2 mg g−1 for H2S and between 4.9 mg g−1 and 37.4 mg g−1 for PO43−. Commercially available activated carbon studied adsorbed 23.1 mg g−1 H2S and 15.7 mg g−1 PO43−. The results show that the retention of H2S and PO43− compounds were governed by the ash content, surface area and pH. Adsorption mechanisms for H2S and PO43− sorption are proposed.

Separating bio-oil by fractionation with different chemical compositions is a critical step to refine these oils and obtain high-value products. Cold water precipitation of pyrolytic lignin from bi...

The pyrolysis of lignocellulosic materials is a promising technique to produce fuels and chemicals. It is well known that the most abundant products of lignin pyrolysis are oligomeric molecules, kn...

International audience; Nitrogen-doped materials are known to possess unique functional properties, making these materials potentially useful for environmental applications, heterogeneous catalysis, and electronics. In this paper we constructed first principles-based models of various polyaromatic structures containing N functionalities to better understand the effect of these functional groups on char Raman spectra. The presence of N functional groups induces active vibrations in the regions between 1400 and 1550 cm−1 and 1605-1650 cm−1. We used these insights to inform the deconvolution of N-doped cellulose char produced between 350 and 700 °C using cellulose/melamine blends 2:1. A consistent increase in the intensity of the D and G bands is observed with temperature, which is related to an increase in size of the aromatic cluster. A consistent decrease in the A (the valley region) band is related to the loss of heteroatoms (mainly N and O) as the carbonization temperature increases from 350 to 700 °C. Although the modeling results reported in this manuscript are used to inform the deconvolution of N-doped char Raman spectra, they are also relevant to study other nanocarbon-based materials.

Among the most prominent challenges for the analysis of biomass pyrolysis products is the characterization of the abundant oligomer fraction of bio-oil. This fraction is principally made up of pyrolytic lignins and dehydrated, highly modified sugar oligomers, called humins, in liquid phase. An emerging technique for analysis of this oligomer fraction is high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which allows for accurate determination of CxHyOz formulas for detected oligomers. Additionally, using simple dehydration and fragmentation reaction schemes, similar formulas can be developed from cellulose-, hemicellulose-, and lignin-derived oligomers, which are primary depolymerization products. In this study, FT-ICR MS analysis is coupled with combinatoric dehydration and fragmentation modeling to match experimentally detected bio-oil oligomers with hypothetical pathways for their formation during pyrolysis. In this way, we present a novel strategy by which oligomeric structures can be proposed for bio-oils. Using this approach, it becomes possible to advance the understanding of both the molecular structures comprising the bio-oil oligomer fraction and the pathways by which these structures form during biomass pyrolysis reactions.

Quantifying the content of surface nitrogen and oxygen containing functional groups in amorphous nitrogen doped carbons via deconvolution of C 1s x-ray photoelectron (XPS) spectra remains difficult due to limited information in the literature. To improve the interpretation of XPS spectra of nitrogen-doped carbons, the C 1s, N 1s and O 1s core level energy shifts have been calculated for various nitrogenated carbon structures via DFT. Furthermore, we propose an expanded method to improve the self-consistency of the XPS interpretation based on a seven-peak C 1s deconvolution (3 C–C peaks, 3 C–N/-O peaks, and π-π∗ transition peaks). With the DFT calculations, spectral components arising from surface-defect carbons could be distinguished from aromatic sp2 carbon. The deconvolution method proposed provides C/(N + O) ratios in very good agreement (error less than 5%) with those obtained from total C 1s, N 1s and O 1s peaks. Our deconvolution strategy provides a simple guideline for obtaining high-quality fits to experimental data on the basis of a careful evaluation of experimental conditions and results.

Introduction The impact of prior therapies, especially chemotherapy, on overall survival (OS) in patients with castration-resistant prostate cancer (CRPC) receiving [177Lu]Lu-PSMA-617 therapy has been the subject of controversy. Therefore, WARMTH decided to plan a multicenter retrospective analysis (the “617 trial”) to evaluate response rate and OS as well as the impact of prior therapies on OS in more than 300 patients treated with 177Lu-PSMA-617. Materials and methods The data of 631 metastatic CRPC (mCRPC) patients from 11 different clinics were evaluated. According to the inclusion and exclusion criteria, all patients had to have received at least abiraterone or enzalutamide prior to [177Lu]Lu-PSMA-617 therapy. The patients were divided into three groups: patients who had received prior chemotherapy, patients who avoided chemotherapy, and patients for whom a chemotherapy was contraindicated. Results The analysis included the data of 416 patients, with a median age of 71.9 years. At the time of analysis, 87 patients (20,9%) were still alive. A total of 53.6% of patients had received both abiraterone and enzalutamide; 75.5% and 26.4% had a history of chemotherapy with docetaxel and cabazitaxel, respectively. A total of 20.4% had had Ra-223. The median OS was 11.1 months. Prior chemotherapy, the existence of bone and liver metastases, as well as Eastern Cooperative Oncology Group (ECOG) status, were significant prognosticators of worse overall survival in both univariate and multivariate analyses. Patients without any prior chemotherapy showed a significantly longer OS (14.6 months). The median OS in patients who received one or two lines of chemotherapy with docetaxel or docetaxel followed by cabazitaxel, respectively, was 10.9 months and 8.9 months. There was no difference in OS between patients who had not received chemotherapy and patients for whom chemotherapy was contraindicated. The other prior therapies did not have any significant impact on OS. Conclusion In the present multicenter analysis, chemotherapy-naïve mCRPC patients receiving [177Lu]Lu-PSMA-617 therapy had a significantly longer OS than patients with a history of chemotherapy. This remained independent in the multivariate analysis besides presence of bone and liver metastases as negative prognosticators for survival, whereas an ECOG of 0–1 is associated with a longer OS.

The aim of this work was to evaluate biomethane production by anaerobic digestion using aqueous phase from Fast Pyrolysis of Douglas Fir Wood as substrate. The effect of biomass acid treatment and condensation temperature on the bio-oil chemical composition and aqueous phase separation with a fractional condensation system coupled to Auger reactor during pyrolysis at 500 °C was reported. As the first condenser temperature was augmented from 40 and 80 °C, the bio-oil yield obtained decreased from 30 to 16 wt% and the aqueous phase yield in the second condenser (kept at 25 °C) increased from 27 till 37 wt%. When the untreated biomass was pyrolyzed, the aqueous phase collected in the second condenser (at the first condenser operated at 80 °C) was anaerobically digested at 100 ppm for 400 h results in 31.3 NmL of CH4/batch. However, the best result was attained after washed biomass with acetic acid (10%) previously to fast pyrolysis, obtaining 86.8 NmL of CH4/batch using just 10 ppm, perhaps due to halved of formed hydroxyacetaldehyde and estimated levoglucosan content increases by more than three times at this condition. Thus, the attained results confirmed the viability of the adopted strategy to improve the anaerobic digestion of the aqueous phase obtained by fractional condensation systems for biomethane production.

Lignin liquefaction microkinetics is a move toward a more first-principles (i.e., ab initio)-based understanding at the molecular level in reaction engineering. While the microkinetic modeling of r...

Blends of lignin-rich oil (LRO) and vegetable oil (1:8, 1:4, 1:2, and 1:1) were prepared and hydrotreated over CoMo/Al2O3 (catalyst liquid ratio of 1:50) at 623 K and 500 rpm, with 9.3 MPa of cold ...

The potential for petroleum refineries (PRs) to integrate sustainable aviation fuel (SAF) technologies is manifold, unlike with other existing industrial infrastructures that lack such technical similarities. A midsize PR with a crude oil capacity of 120,000 barrels per day was analyzed in this study to determine the feasibility of integrating five well-known lignocellulosic SAF technologies, namely, Virent’s BioForming (VB), alcohol to jet (ATJ), direct sugar to hydrocarbon (DSHC), fast pyrolysis (FP), and gasification and Fischer–Tropsch (GFT) methods, as well as one novel concept referred to as integrated carbonization-gasification-Fischer–Tropsch (ICGFT). The following three integrated scenarios were studied to derive the costs and environmental impact reductions: sharing of infrastructures from outside battery limits (OSBL), co-processing of SAF technology-derived intermediates with PR-derived gas oil inside battery limits (ISBL) and repurposing of an idle or shutdown PR. Sharing OSBL infrastructures resulted in reductions of the minimum fuel selling price (MFSP) by 3–14% relative to the corresponding standalone cases. Co-processing of intermediate products such as VB-derived long chain hydrocarbons, ATJ-derived ethanol, DSHC-derived farnesene, pyrolysis-derived bio-oil, and GFT-derived FT products reduced the MFSP by 10–19% from corresponding standalone cases. Moreover, repurposing scenarios reduced the costs by 16–34%. Greenhouse gas (GHG) estimations showed that 17 of 21 integrated scenarios resulted in GHG savings (7–92%). Lignocellulosic SAF technologies are limited by low fuel yields, which are governed by the high oxygen content of the feedstock. However, ICGFT was found to be advantageous in terms of fuel production at a maximized fuel yield.

CRISPR-based programmable transcriptional activators (PTAs) are used in plants for rewiring gene networks. Better tuning of their activity in a time and dose-dependent manner should allow precise control of gene expression. Here, we report the optimization of a Copper Inducible system called CI-switch for conditional gene activation in Nicotiana benthamiana. In the presence of copper, the copper-responsive factor CUP2 undergoes a conformational change and binds a DNA motif named copper-binding site (CBS). In this study, we tested several activation domains fused to CUP2 and found that the non-viral Gal4 domain results in strong activation of a reporter gene equipped with a minimal promoter, offering advantages over previous designs. To connect copper regulation with downstream programable elements, several copper-dependent configurations of the strong dCasEV2.1 PTA were assayed, aiming at maximizing activation range, while minimizing undesired background expression. The best configuration involved a dual copper regulation of the two protein components of the PTA, namely dCas9:EDLL and MS2:VPR, and a constitutive RNA pol III-driven expression of the third component, a guide RNA with anchoring sites for the MS2 RNA-binding domain. With these optimizations in place, the CI/dCasEV2.1 system resulted in copper-dependent activation rates of 2,600-fold for the endogenous N. benthamiana DFR gene, with negligible expression in the absence of the trigger. The tight regulation of copper over CI/dCasEV2.1 makes this system ideal for the conditional production of plant-derived metabolites and recombinant proteins in the field.

Anaerobically digested fibrous solid (AD fiber) is an abundant material that offers potential to produce value-added products such as biochar. The objective of this paper is to better understand how thermochemical processing conditions affect the capacity of biochars derived from AD fiber to adsorb H 2 S from biogas. AD fiber was pyrolyzed in an electric tube reactor at temperatures up to 600° C and 60 min. The chars were employed for H 2 S scrubbing tests from a synthetic biogas. Results showed that the chars' capacity for H 2 S removal is comparable to that of activated carbon. An additional step consisting of impregnation of the chars with Na 2 CO 3 resulted in an improved capacity for H 2 S removal. To study the effect of ash, the AD fiber was also subjected to an alternative thermal treatment, hot water extraction (HWE), at 200° C for 60 min. The resulting HWE material …

Nitrogen functionalization of graphene significantly enhances the physical and chemical properties of graphitic materials, increasing their applicability as sorbents, heterogeneous catalysts, and electronic components. Being able to selectively induce different nitrogen functionalities via treatment conditions is key to the design and optimization of such materials. Here, we use density functional theory to study the thermodynamic stability of nitrogen functionalities in three graphene structures as a function of temperature and pressure, providing atomistic insight into the most favorable functionalized configurations. Phase diagrams show that nitrogen incorporation is most exergonic at graphene edges, with pyridinic groups dominating under the majority of conditions studied. For all nitrogen functionalities, lower temperatures and higher pressures result in the greater incorporation of nitrogen into the graphene structures. A density of states analysis shows that the stable pyridinic nitrogen structures induce new electronic states just below the Fermi level whose energy is tunable via nitrogen concentration and hence treatment temperature and pressure. Overall, we have characterized the thermodynamic stability of nitrogen functionalities within graphene and graphene nanoribbons, allowing for the directed tuning of such nitrogen groups experimentally and enabling the construction of more realistic models of nitrogenated graphene structures.

The solubility and hydrolysis of U(VI) were investigated in 0.10–5.6 m NaCl solutions with 4 ≤ pHm ≤ 14.3 (pHm = −log [H+]) at T = 25, 55 and 80 °C. Batch experiments were conducted under Ar atmosphere in the absence of carbonate. Solubility was studied from undersaturation conditions using UO3 · 2H2O(cr) and Na2U2O7 · H2O(cr) solid phases, equilibrated in acidic (4 ≤ pHm ≤ 6) and alkaline (8.2 ≤ pHm ≤ 14.3) NaCl solutions, respectively. Solid phases were previously tempered in solution at T = 80 °C to avoid changes in the crystallinity of the solid phase in the course of the solubility experiments. Starting materials and solid phases isolated at the end of the solubility experiments were characterized by powder XRD, SEM-EDS, TRLFS and quantitative chemical analysis. The enthalpy of dissolution of Na2U2O7 · H2O(cr) at 25–80 °C was measured independently by means of solution-drop calorimetry. Solid phase characterization indicates the transformation of UO3 · 2H2O(cr) into a sodium uranate-like phase with a molar ratio Na:U ≈ 0.4–0.5 in acidic solutions with [NaCl] ≥ 0.51 m at T = 80 °C. In contrast, Na2U2O7 · H2O(cr) equilibrated in alkaline NaCl solutions remains unaltered within the investigated pHm, NaCl concentration and temperature range. The solubility of Na2U2O7 · H2O(cr) in the alkaline pHm-range is noticeably enhanced at T = 55 and 80 °C relative to T = 25 °C. Combined results from solubility and calorimetric experiments indicate that this effect results from the increased acidity of water at elevated temperature, together with an enhanced hydrolysis of U(VI) and a minor contribution due to a decreased stability of Na2U2O7 · H2O(cr) under these experimental conditions. A thermodynamic model describing the solubility and hydrolysis equilibria of U(VI) in alkaline solutions at T = 25–80 °C is developed, including log * K s , 0 ° { Na 2 U 2 O 7 ⋅ H 2 O ( cr ) } , log * β 1 , 4 ∘ $\log^* {\rm K}_{\rm s,0}^{\circ} \ \{{\rm Na}_{2}{\rm U}_{2}{\rm O}_{7} \cdot {\rm H}_{2}{\rm O}({\rm cr})\}, \log^{*} \beta _{1,4}^{\circ} $ and related reaction enthalpies. The standard free energy and enthalpy of formation of Na2U2O7 · H2O(cr) calculated from these data are also provided. These data can be implemented in thermodynamic databases and allow accurate solubility and speciation calculations for U(VI) in dilute to concentrated alkaline NaCl solutions in the temperature range T = 25–80 °C.

ObjectiveTo investigate the underlying mechanisms behind changes in glucose homeostasis with delivery of propionate to the human colon by comprehensive and coordinated analysis of gut bacterial composition, plasma metabolome and immune responses.DesignTwelve non-diabetic adults with overweight and obesity received 20 g/day of inulin-propionate ester (IPE), designed to selectively deliver propionate to the colon, a high-fermentable fibre control (inulin) and a low-fermentable fibre control (cellulose) in a randomised, double-blind, placebo-controlled, cross-over design. Outcome measurements of metabolic responses, inflammatory markers and gut bacterial composition were analysed at the end of each 42-day supplementation period.ResultsBoth IPE and inulin supplementation improved insulin resistance compared with cellulose supplementation, measured by homeostatic model assessment 2 (mean±SEM 1.23±0.17 IPE vs 1.59±0.17 cellulose, p=0.001; 1.17±0.15 inulin vs 1.59±0.17 cellulose, p=0.009), with no differences between IPE and inulin (p=0.272). Fasting insulin was only associated positively with plasma tyrosine and negatively with plasma glycine following inulin supplementation. IPE supplementation decreased proinflammatory interleukin-8 levels compared with cellulose, while inulin had no impact on the systemic inflammatory markers studied. Inulin promoted changes in gut bacterial populations at the class level (increased Actinobacteria and decreased Clostridia) and order level (decreased Clostridiales) compared with cellulose, with small differences at the species level observed between IPE and cellulose.ConclusionThese data demonstrate a distinctive physiological impact of raising colonic propionate delivery in humans, as improvements in insulin sensitivity promoted by IPE and inulin were accompanied with different effects on the plasma metabolome, gut bacterial populations and markers of systemic inflammation.

Pyrolysis of cellulose mixed with blowing agent additives containing high nitrogen content has been investigated in this work. The additives used are dicyandiamide (DCD), 5-aminotetrazole (5AT) and 5-phenyl-1H-tetrazole (5PT), in concentrations of 0.25, 0.50, 1.0, 2.0 and 4.0% (weight). Blowing agents are of particular interest as a cellulose pyrolysis additive for two reasons: as a first case, if these additives and their decomposition products are chemically inert with respect to cellulose pyrolysis reactions, then they can serve to enhance the ejection of high-molecular weight aerosols from the liquid intermediate phase that is known to form during pyrolysis; as a second case, if these additives are not chemically inert, then the reactions between blowing agent decomposition products (e.g., NH3 and HN3) can provide a pathway by which nitrogen-doped carbonaceous char structures can be readily produced. Pyrolysis studies were carried out using thermogravimetric analysis and analytical Py-GC/MS of the pure compounds (DCD, 5AT, 5PT) and mixtures with cellulose, as well as proximate/ultimate analyses of the resulting chars from slow pyrolysis. Experiments showed that there is a reactive interaction between the additives and cellulose during pyrolysis, leading to greater char yields. Analysis of slow pyrolysis chars showed that DCD is promising for producing biochar with higher nitrogen content. This was attributed to the evolution of ammonia from DCD and due to its thermal decomposition occurring in a temperature range coincident with that of cellulose pyrolysis reactions.

Mo–W carbide was synthesized via temperature-programmed reduction to generate a β-Mo2C phase with bulk morphology. The catalyst was characterized using X-ray diffraction (XRD), N2 physisorption, X-ray photoelectron spectroscopy (XPS), H2-chemisorption, and ammonia temperature programmed desorption (NH3-TPD) to investigate the synergistic effect of the combination of molybdenum and tungsten in carbide. Due to the interaction of Mo–W, the bimetallic carbide exhibited a significantly higher density of H2-activating sites than the corresponding monometallic carbides prepared using the same method. In the HDO of guaiacol at 350 °C, MoWC exhibited the highest hydrodeoxygenation (HDO) activity and produced completely deoxygenated products with a selectivity of 92 mol% in which the benzene selectivity was ∼70 mol%. The superior catalytic activity is attributed to the presence of H2-activating sites and oxophilic sites. Under the testing conditions, the HDO of guaiacol over monometallic molybdenum carbide followed both direct deoxygenation (DDO) and hydrogenation–dehydration (HYD) pathways, while MoWC strongly favored the DDO route. Over 8 h on stream, the catalyst still retained a high catalytic stability.

In this paper, nitrogen-doped (ND) and nitrogen-magnesium co-doped (NMD) chars were synthesized by different combinations of pyrolysis-activation steps of anaerobically digested fiber (ADF), wheat straw (WS), and Douglas fir wood (DFW) to adsorb phosphate from aqueous solutions. Five different series of char were produced through different methods: (1) biomass pyrolyzed under N2, (2) biomass pyrolyzed under N2 followed by activation with ammonia, (3) biomass pyrolyzed and char activated both in the presence of NH3, (4) biomass impregnated with MgCl2 pyrolyzed under N2, and (5) biomass impregnated with MgCl2 pyrolyzed under NH3. Proximate analysis, elemental composition, gas physisorption, inductively coupled plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) techniques were used to characterize the resulting chars. All the chars derived from ADF (independent of the procedure used) showed the best phosphate adsorption capacity, likely due to their higher ash content. Pyrolysis of ADF under NH3 resulted in char with phosphate adsorption capacity of 95 mg/g (254% higher than char produced under N2). Results from kinetic study show almost all phosphate adsorption by ND-ADF (one step) char occurred within 2 h. Richie nth-order model fits well the sorption process indicating that phosphate adsorption on the surface of the ND-ADF (one step) char was mediated by multiple mechanisms. Equilibrium data were fitted to different adsorption isotherms and the Langmuir-Freundlich and Redlich Peterson adsorption models provided the best fit. We hypothesized that the presence of Ca and Mg in the ADF enhanced N fixation and leads to higher phosphate adsorption. Therefore, we studied the effect of MgCl2 impregnation on DFW and WS pyrolyzed and activated under NH3. Our hypothesis was confirmed, and DFW and WS chars doped with Mg and N showed phosphate adsorption of 216 and 122 mg/g, respectively (37- and 24-fold increase compared with chars produced only under N2).

Catalytic wet oxidation (CWO) of aqueous effluents rich in organic compounds is a very promising technology for the treatment of liquid wastes from biomass conversion processes. CWO reactions occur through the formation of free radical species, produced in the presence of an oxidant, which act on organic contaminates in the effluent. Although the reaction is well known, there exists a lack of affordable catalysts to conduct this process at the lower temperatures and pressures in novel bioenergy processes. This study assessed the catalytic effect of nitrogen-doped chars as such an option. Phenol in aqueous solution was used as a model waste effluent. Treatment was conducted at moderate temperatures (190 to 260 °C), oxygen partial pressure of 1 MPa, and reaction times of 15, 30, and 45 min in stainless steel and glass-lined tube reactors. High pressure liquid chromatography (HPLC) analyses of the products quantified phenol and by-product concentrations used in the calculation of reaction activation energy. The char catalyst was studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) in order to gain insight into its structure and surface composition. The results indicate that nitrogen-doped char catalysts accelerate the oxidation of phenol by decreasing its reaction activation energy from 82.2 kJ/mol (non-catalyzed) to 40.4 kJ/mol (catalyzed). An analysis from first principles using density functional theory (DFT) was conducted to ascertain which N functional group has the most significant impact on free radical formation in the presence of oxygen. Among all the N functional groups studied, the dipyridinic functional groups showed the most promising characteristics to facilitate the formation of hydroxyl free radicals.

International audience; Inappropriate stimulation or defective negative regulation of the type I interferon response can lead to autoinflammation. In genetically uncharacterized cases of the type I interferonopathy Aicardi-Goutières syndrome, we identified biallelic mutations in LSM11 and RNU7-1, which encode components of the replication-dependent histone pre-mRNA-processing complex. Mutations were associated with the misprocessing of canonical histone transcripts and a disturbance of linker histone stoichiometry. Additionally, we observed an altered distribution of nuclear cyclic guanosine monophosphate-adenosine monophosphate synthase (cGAS) and enhanced interferon signaling mediated by the cGAS-stimulator of interferon genes (STING) pathway in patient-derived fibroblasts. Finally, we established that chromatin without linker histone stimulates cyclic guanosine monophosphate-adenosine monophosphate (cGAMP) production in vitro more efficiently. We conclude that nuclear histones, as key constituents of chromatin, are essential in suppressing the immunogenicity of self-DNA.

ObjectiveThe composition and metabolic function of the gut microbiome in the elite athlete differs from that of non-athletes. However, short-term fitness improvement in the sedentary adult does not replicate the microbiome characteristics seen in the athlete. Whether sustained fitness improvement over a prolonged period can lead to pronounced and beneficial alteration in the gut microbiome is unknown. The objective was to explore this possibility.MethodsThis study used a repeated-measures, case-study approach to explore changes in the gut microbiome of two unfit volunteers undertaking progressive exercise training over a 6-month period. Training was to culminate in the completion of a marathon or Olympic-distance triathlon. The volunteers were sampled every two weeks for six months and microbiome, metabolome, diet, body composition, and cardiorespiratory fitness data were recorded.ResultsBoth participants completed their respective goals with improved body composition and fitness parameters over the training period. Increases in α-diversity of the gut microbiota occurred with sustained training and fluctuations occurred in response to training events (e.g., injury, illness and training peaks). Participants’ fat mass and BMI reduced during the study and was significantly associated with increased urinary measurements of N-methyl nicotinate (P value < 0.001) and hippurate (P value < 0.05), and decreased phenylacetylglutamine (P value < 0.05).ConclusionThese results suggest that sustained fitness improvements result in alterations to gut microbiota and physiologically-relevant metabolites. This study provides longitudinal analysis of the response of the gut microbiome to real-world events during progressive fitness training, including intercurrent illness and injury.

Elevated postprandial glucose (PPG) is a significant risk factor for non-communicable diseases globally. Currently, there is a limited understanding of how starch structures within a carbohydrate-rich food matrix interact with the gut luminal environment to control PPG. Here, we use pea seeds (Pisum sativum) and pea flour, derived from two near-identical pea genotypes (BC1/19RR and BC1/19rr) differing primarily in the type of starch accumulated, to explore the contribution of starch structure, food matrix and intestinal environment to PPG. Using stable isotope 13C-labelled pea seeds, coupled with synchronous gastric, duodenal and plasma sampling in vivo, we demonstrate that maintenance of cell structure and changes in starch morphology are closely related to lower glucose availability in the small intestine, resulting in acutely lower PPG and promotion of changes in the gut bacterial composition associated with long-term metabolic health improvements. Seeds, flour and food products derived from two near-identical pea genotypes (BC1/19RR and BC1/19rr) were utilized in a series of in vitro, ex vivo and in vivo studies to explore the contribution of starch structure, food matrix and intestinal environment to postprandial glycaemia.

International audience; Recent advancements in composite production and processing are making thermoplastics a viable option in a wider array of aerospace applications. In particular, Carbon Fibre Reinforced Plastics (CFRP) with thermoplastic resin are believed to have better damage tolerance properties than thermosets. However, few studies have been conducted regarding the numerical modelling of the behaviour of such materials submitted to low energy impacts. Here the Discrete Ply Model (DPM), that predicts the failure of laminated composites with the help of cohesive elements, is used to compare thermosetting and thermoplastics impact damage tolerances. The DPM is improved to take into account the strain rate effect of the fracture toughness (FT) in mode II of interlaminar interfaces. First, the End Notched Flexure (ENF) test that induces unstable crack growth is used both to experimentally measure the value of FT in mode II for high speed crack growth and to identify the strain rate effect used in the model. Second, the DPM is then used to simulate impact tests for various stacking sequences ([45 2 , − 45 2 , 0 2 , 90 2 ] 2S , [0 2 , 45 2 , 90 2 , − 45 2 ] 2S , [0 2 , 30 2 , 90 2 , − 30 2 ] 2S and [90 2 , − 45 2 , 0 2 , 45 2 ] 2S ) and impact energy levels (10, 20 and 30 J). Good correlations with experiment are observed in terms of force/displacement curves and delaminated areas. The numerical model correctly describes the asymmetry of the delaminated interfaces and the propagation of groups of interfaces located near the mid-thickness of the laminated plates. Finally, the damage associated with a 30 J impact is compared for the carbon/PEEK of this study and classical carbon/epoxy plates using numerical simulations (DPM). No significant difference has been found. The results corroborate those obtained in previous studies showing the relatively low value of FT in mode II, using an ENF test and infrared thermography (IRT). This article therefore questions the apparent superiority of carbon/PEEK laminated composites over carbon/epoxy laminated composites in terms of impact damage tolerance.

Background: Dietary advice remains the cornerstone of prevention and management of type 2 diabetes (T2D). However, understanding the efficacy of dietary interventions is confounded by the challenges inherent in assessing free living diet. Here we profiled dietary metabolites to investigate glycaemic deterioration and cardiometabolic risk in people at risk of or living with T2D. Methods: We analysed data from plasma collected at baseline and 18-month follow-up in individuals from the Innovative Medicines Initiative (IMI) Diabetes Research on Patient Stratification (DIRECT) cohort 1 n = 403 individuals with normal or impaired glucose regulation (prediabetic) and cohort 2 n = 458 individuals with new onset of T2D. A dietary metabolite profile model (Tpred) was constructed using multivariable regression of 113 plasma metabolites obtained from targeted metabolomics assays. The continuous Tpred score was used to explore the relationships between diet, glycaemic deterioration and cardio-metabolic risk via multiple linear regression models. Findings: A higher Tpred score was associated with healthier diets high in wholegrain (β=3.36 g, 95% CI 0.31, 6.40 and β=2.82 g, 95% CI 0.06, 5.57) and lower energy intake (β=-75.53 kcal, 95% CI -144.71, -2.35 and β=-122.51 kcal, 95% CI -186.56, -38.46), and saturated fat (β=-0.92 g, 95% CI -1.56, -0.28 and β=–0.98 g, 95% CI -1.53, -0.42 g), respectively for cohort 1 and 2. In both cohorts a higher Tpred score was also associated with lower total body adiposity and favourable lipid profiles HDL-cholesterol (β=0.07 mmol/L, 95% CI 0.03, 0.1), (β=0.08 mmol/L, 95% CI 0.04, 0.1), and triglycerides (β=-0.1 mmol/L, 95% CI -0.2, -0.03), (β=-0.2 mmol/L, 95% CI -0.3, -0.09), respectively for cohort 1 and 2. In cohort 2, the Tpred score was negatively associated with liver fat (β=-0.74%, 95% CI -0.67, -0.81), and lower fasting concentrations of HbA1c (β=-0.9 mmol/mol, 95% CI -1.5, -0.1), glucose (β=-0.2 mmol/L, 95% CI -0.4, -0.05) and insulin (β=-11.0 pmol/mol, 95% CI -19.5, -2.6). Longitudinal analysis showed at 18-month follow up a higher Tpred score was also associated lower total body adiposity in both cohorts and lower fasting glucose (β=-0.2 mmol/L, 95% CI -0.3, -0.01) and insulin (β=-9.2 pmol/mol, 95% CI -17.9, -0.4) concentrations in cohort 2. Interpretation: Plasma dietary metabolite profiling provides objective measures of diet intake, showing a relationship to glycaemic deterioration and cardiometabolic health. Funding: This work was supported by the Innovative Medicines Initiative Joint Undertaking under grant agreement no. 115,317 (DIRECT), resources of which are composed of financial contribution from the European Union's Seventh Framework Programme (FP7/2007–2013) and EFPIA companies.

Exosomes are 50- to 150-nm-diameter extracellular vesicles secreted by all mammalian cells except mature red blood cells and contribute to diverse physiological and pathological functions within the body. Many methods have been used to isolate and analyze exosomes, resulting in inconsistencies across experiments and raising questions about how to compare results obtained using different approaches. Questions have also been raised regarding the purity of the various preparations with regard to the sizes and types of vesicles and to the presence of lipoproteins. Thus, investigators often find it challenging to identify the optimal exosome isolation protocol for their experimental needs. Our laboratories have compared ultracentrifugation and commercial precipitation- and column-based exosome isolation kits for exosome preparation. Here, we present protocols for exosome isolation using two of the most commonly used methods, ultracentrifugation and precipitation, followed by downstream analyses. We use NanoSight nanoparticle tracking analysis and flow cytometry (Cytek® ) to determine exosome concentrations and sizes. Imaging flow cytometry can be utilized to both size exosomes and immunophenotype surface markers on exosomes (ImageStream® ). High-performance liquid chromatography followed by nano-flow liquid chromatography-mass spectrometry (LCMS) of the exosome fractions can be used to determine the presence of lipoproteins, with LCMS able to provide a proteomic profile of the exosome preparations. We found that the precipitation method was six times faster and resulted in a ∼2.5-fold higher concentration of exosomes per milliliter compared to ultracentrifugation. Both methods yielded extracellular vesicles in the size range of exosomes, and both preparations included apoproteins. © 2020 Wiley Periodicals LLC. Basic Protocol 1: Pre-analytic fluid collection and processing Basic Protocol 2: Exosome isolation by ultracentrifugation Alternate Protocol 1: Exosome isolation by precipitation Basic Protocol 3: Analysis of exosomes by NanoSight nanoparticle tracking analysis Alternate Protocol 2: Analysis of exosomes by flow cytometry and imaging flow cytometry Basic Protocol 4: Downstream analysis of exosomes using high-performance liquid chromatography Basic Protocol 5: Downstream analysis of the exosome proteome using nano-flow liquid chromatography-mass spectrometry.

Dietary assessment traditionally relies on self-reported data which are often inaccurate and may result in erroneous diet-disease risk associations. We illustrate how urinary metabolic phenotyping can be used as alternative approach for obtaining information on dietary patterns. We used two multi-pass 24-hr dietary recalls, obtained on two occasions on average three weeks apart, paired with two 24-hr urine collections from 1,848 U.S. individuals; 67 nutrients influenced the urinary metabotype measured with (1)H-NMR spectroscopy characterized by 46 structurally identified metabolites. We investigated the stability of each metabolite over time and showed that the urinary metabolic profile is more stable within individuals than reported dietary patterns. The 46 metabolites accurately predicted healthy and unhealthy dietary patterns in a free-living U.S. cohort and replicated in an independent U.K. cohort. We mapped these metabolites into a host-microbial metabolic network to identify key pathways and functions. These data can be used in future studies to evaluate how this set of diet-derived, stable, measurable bioanalytical markers are associated with disease risk. This knowledge may give new insights into biological pathways that characterize the shift from a healthy to unhealthy metabolic phenotype and hence give entry points for prevention and intervention strategies.

IL-22 has dual functions during tumorigenesis. Short term IL-22 production protects against genotoxic stress, whereas uncontrolled IL-22 activity promotes tumor growth; therefore, tight regulation of IL-22 is essential. TGF-β1 promotes the differentiation of Th17 cells, which are known to be a major source of IL-22, but the effect of TGF-β signaling on the production of IL-22 in CD4+ T cells is controversial. Here we show an increased presence of IL-17+IL-22+ cells and TGF-β1 in colorectal cancer compared to normal adjacent tissue, whereas the frequency of IL-22 single producing cells is not changed. Accordingly, TGF-β signaling in CD4+ T cells (specifically Th17 cells) promotes the emergence of IL-22-producing Th17 cells and thereby tumorigenesis in mice. IL-22 single producing T cells, however, are not dependent on TGF-β signaling. We show that TGF-β, via AhR induction, and PI3K signaling promotes IL-22 production in Th17 cells., Poly-functional helper T cells can have a stronger effect than mono-functional T cells, but whether the response is qualitatively different is not clear. Here the authors show that a population of IL-17+IL-22+, but not single IL-22+, CD4+ T cells are induced by TGF-β, enriched in patients with colorectal cancer (CRC) and drive CRC progression in mice.

International audience; The lack of standards to identify oligomeric molecules is a challenge for the analysis of complex organic mixtures. High‐resolution mass spectrometry—specifically, Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR MS)—offers new opportunities for analysis of oligomers with the assignment of formulae (CxHyOz) to detected peaks. However, matching a specific structure to a given formula remains a challenge due to the inability of FT‐ICR MS to distinguish between isomers. Additional separation techniques and other analyses (e.g., NMR spectroscopy) coupled with comparison of results to those from pure compounds is one route for assignment of MS peaks. Unfortunately, this strategy may be impractical for complete analysis of complex, heterogeneous samples. In this study we use computational stochastic generation of lignin oligomers to generate a molecular library for supporting the assignment of potential candidate structures to compounds detected during FT‐ICR MS analysis. This approach may also be feasible for other macromolecules beyond lignin.

Mitochondria participate in metabolism and signaling. They adapt to the requirements of various cell types. Publicly available expression data permit to study expression dynamics of genes with mitochondrial function (mito-genes) in various cell types, conditions and organisms. Yet, we lack an easy way of extracting these data for mito-genes. Here, we introduce the visual data mining platform mitoXplorer, which integrates expression and mutation data of mito-genes with a manually curated mitochondrial interactome containing ∼1200 genes grouped in 38 mitochondrial processes. User-friendly analysis and visualization tools allow to mine mitochondrial expression dynamics and mutations across various datasets from four model species including human. To test the predictive power of mitoXplorer, we quantify mito-gene expression dynamics in trisomy 21 cells, as mitochondrial defects are frequent in trisomy 21. We uncover remarkable differences in the regulation of the mitochondrial transcriptome and proteome in one of the trisomy 21 cell lines, caused by dysregulation of the mitochondrial ribosome and resulting in severe defects in oxidative phosphorylation. With the newly developed Fiji plugin mitoMorph, we identify mild changes in mitochondrial morphology in trisomy 21. Taken together, mitoXplorer (http://mitoxplorer.ibdm.univ-mrs.fr) is a user-friendly, web-based and freely accessible software, aiding experimental scientists to quantify mitochondrial expression dynamics.

Overcoming obstacles to commercialization of algal-based processes for biofuels and co-products requires not just piecemeal incremental improvements, but rather a comprehensive and fundamental re-consideration starting with the selected algae and its associated cultivation, harvesting, biomass conversion, and refinement. A novel two-stage process designed to address challenges of mass outdoor microalgal cultivation for biofuels and co-products was previously demonstrated using an oleaginous, haloalkaline-tolerant, and multi-trophic green Chlorella vulgaris. ALP2 from a soda lake. This involved cultivating the microalgae in a fermenter heterotrophically or photobioreactor mixotrophically (first-stage) to rapidly obtain high cell densities and inoculate an open-pond phototrophic culture (second-stage) featuring high levels of NaHCO3, pH, and salinity. An improved two-stage cultivation that instead sustainably used as more cheap and sustainable inputs the organic carbon, nitrogen, and phosphorous from fractionation of waste was here demonstrated in a small-scale biorefinery process. The first cultivation stage consisted of two simultaneous batch flask cultures featuring (1) mixotrophic cell productivity of 7.25 × 107 cells mL−1 day−1 on BG-110 medium supplemented with 1.587 g L−1 urea and an enzymatic hydrolysate of pre-treated (torrefaction + grinding + ozonolysis + soaking ammonia) wheat-straw that corresponded to 10 g L−1 glucose, and (2) mixotrophic cell productivity of 2.25 × 107 cells mL−1 day−1 on BG-110 medium supplemented with 1.587 g L−1 urea and a purified and de-toxified condensate of pre-treated (torrefaction + grinding) wheat straw that corresponded to 0.350 g L−1 of potassium acetate. The second cultivation stage featured 1H NMR-determined phototrophic lipid productivity of 0.045 g triacylglycerides (TAG) L−1 day−1 on BG-110 medium supplemented with 16.8 g L−1 NaHCO3 and fed batch-added 22% (v/v) anaerobically digested food waste effluent at HCl-mediated pH 9.

Lipids are a biorefinery platform to prepare fuel, food and health products. They are traditionally obtained from plants, but those of microbial origin allow for a better use of land and C resources, among other benefits. Several (thermo)chemical and biochemical strategies are used for the conversion of C contained in lignocellulosic biomass into lipids. In particular, pyrolysis can process virtually any biomass and is easy to scale up. Products offer cost-effective, renewable C in the form of readily fermentable molecules and other upgradable intermediates. Although the production of microbial lipids has been studied for 30 years, their incorporation into biorefineries was only described a few years ago. As pyrolysis becomes a profitable technology to depolymerize lignocellulosic biomass into assimilable C, the number of investigations on it raises significantly. This article describes the challenges and opportunities resulting from the combination of lignocellulosic biomass pyrolysis and lipid biosynthesis with oleaginous microorganisms. First, this work presents the basics of the individual processes, and then it shows state-of-the-art processes for the preparation of microbial lipids from biomass pyrolysis products. Advanced knowledge on separation techniques, structure analysis, and fermentability is detailed for each biomass pyrolysis fraction. Finally, the microbial fatty acid platform comprising biofuel, human food and animal feed products, and others, is presented. Literature shows that the microbial lipid production from anhydrosugars, like levoglucosan, and short-chain organic acids, like acetic acid, is straightforward. Indeed, processes achieving nearly theoretical yields form the latter have been described. Some authors have shown that lipid biosynthesis from different lignin sources is biochemically feasible. However, it still imposes major challenges regarding strain performance. No report on the fermentation of pyrolytic lignin is yet available. Research on the microbial uptake of pyrolytic humins remains vacant. Microorganisms that make use of methane show promising results at the proof-of-concept level. Overall, despite some issues need to be tackled, it is now possible to conceive new versatile biorefinery models by combining lignocellulosic biomass pyrolysis products and robust oleaginous microbial cell factories.

This paper investigates the optimized sputtering conditions for high quality gallium oxide (Ga2O3) thin films while maintaining a strong uniformity within a specific surface area. The research also analyzes the crystal structure and the morphology of gallium oxide (Ga2O3) thin films. We report a comprehensive investigation of two different types of Ga2O3 synthetization processes: (1) direct deposition using radio frequency (RF) magnetron sputter technique and (2) thermal oxidation of gallium nitride (GaN) samples. A detailed comparison is presented in terms of material characterization, surface analysis and electrical performance for each of the synthetization processes. X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy and x-ray diffraction (XRD) are employed to study the gallium oxide (Ga2O3) epi-layers on each of the samples. Based on the analysis, Ga2O3 compound is found on all samples with a binding energy ranging from 21 eV to 21.38 eV. Depending on the synthetization process, the thickness varied from 20 nm to 100 nm for RF sputtering process and a maximum of ~ 400 nm for thermal oxidation method. Additionally, the observations revealed that Ga2O3 is formed on the surface, as well as inside the gallium nitride (GaN) film after thermal oxidation. Crystal features are observed on the surface of each of the samples after annealing treatment while XRD analysis showed the presence of the beta (β) polymorph for the annealed samples. After thorough characterization, radio frequency sputtering technique proved to be superior due to its higher purity level and ability to create polycrystalline structures by adding temperature during deposition.

R-loops are nucleic acid structures formed by an RNA:DNA hybrid and unpaired single-stranded DNA that represent a source of genomic instability in mammalian cells1,2,3,4. Here we show that N6-methyladenosine (m6A) modification, contributing to different aspects of messenger RNA metabolism5,6, is detectable on the majority of RNA:DNA hybrids in human pluripotent stem cells. We demonstrate that m6A-containing R-loops accumulate during G2/M and are depleted at G0/G1 phases of the cell cycle, and that the m6A reader promoting mRNA degradation, YTHDF2 (ref. 7), interacts with R-loop-enriched loci in dividing cells. Consequently, YTHDF2 knockout leads to increased R-loop levels, cell growth retardation and accumulation of γH2AX, a marker for DNA double-strand breaks, in mammalian cells. Our results suggest that m6A regulates accumulation of R-loops, implying a role for this modification in safeguarding genomic stability.

The aim of this paper is to improve the conversion of sugarcane bagasse to pyrolytic sugar levoglucosan through its pretreatment with acetic acid (10 wt.%) at 90 °C for 10 min under 200 rpm. Then, acid treated biomass was rinsed with deionized water to a neutral pH and dried in a vacuum oven at 70 °C up to constant weight. After acid treatment, the samples were subjected to fast pyrolysis in a Py-GC/MS. Thus, the impact of the acetic acid on the levoglucosan yield as well as other pyrolytic compounds released during pyrolysis process at different temperatures (from 350 to 600 °C) is reported. The best results respect to levoglucosan yield were attained when pyrolysis was performed at 400 °C resulting in around nine folds levoglucosan production from sugarcane bagasse after biomass treatment with acid compared to the control (untreated biomass samples) while the yield of some undesirable lignin derived compounds decreases in acid washed samples. The effect observed is due to the removal of the catalytic activity of alkali and alkaline earth metals. The attained results are very attractive because this pyrolytic sugar exhibits great potential as renewable feedstock for biofuels production and other bioproducts.

Fatty acid and its derivatives have recently received considerable interest as a possible precursor for producing renewable hydrocarbon. Compared to the traditional hydrotreating method that consumes a significant amount of H2, this study developed a hydrothermal catalytic deoxygenation approach that produced hydrocarbon from fatty acids and bio-oil with in situ self-sustaining H2. The presence of H2O played a critical role in the generation of in situ H2 via enhancing water–gas shift and reforming reactions, thus promoting fatty acid decarbonylation and increased paraffin yields. Both saturated and unsaturated fatty acids (stearic acid (SA) and oleic acid (OA)) were employed as model compounds, where 100% conversion was achieved with 63.59% paraffin yield from SA and 47% n-paraffin yield from OA. By investigating the reaction pathway, fatty acid and glycerol reforming, and water–gas shift reactions, were determined to be the major reactions for the in situ H2 generation. Decarbonylation was found as the ...

The aim of this paper is to report fuel properties and torrefaction behavior of woody biomass from the Colombian highlands. Four wood species (Eucalyptus grandis, Pinus Maximinoi, Pinus patula, and Gmelina arborea) were selected due to their potential for expansion as bioenergy crops. Torrefaction of these feedstocks for the production of pellets for both domestic and international markets is a promising way to take advantage of these resources. Herein we report the impact of torrefaction temperature (between 200 and 300 °C) on the proximate and ultimate composition, heating value, thermal stability, and volatile products of the resulting solids. Although, all samples studied have similar volatile contents (70 wt%), heating value (~ 18.7 MJ/kg), and ash content (

Prior investigation has suggested a positive association between increased colonic propionate production and circulating odd-chain fatty acids [(OCFAs; pentadecanoic acid (C15:0), heptadecanoic acid (C17:0)]. As the major source of propionate in humans is the microbial fermentation of dietary fiber, OCFAs have been proposed as candidate biomarkers of dietary fiber. The objective of this study is to critically assess the plausibility, robustness, reliability, dose-response, time-response aspects of OCFAs as potential biomarkers of fermentable fibers in two independent studies using a validated analytical method. OCFAs were first assessed in a fiber supplementation study, where 21 participants received 10g dietary fiber supplementation for 7 days with blood samples collected on the final day at a 420 minute study visit. OCFAs were then assessed in a highly controlled inpatient setting, which 19 participants consumed a high fiber (45.1g/day) and a low fiber diet (13.6g/day) for 4 days. Collectively in both studies, dietary intakes of fiber as fiber supplementations or having consumed a high fiber diet did not increase circulating levels of OCFAs. The dose and temporal relations were not observed. Current study has generated new insight on the utility of OCFAs as fiber biomarkers and highlighted the importance of critical assessment of candidate dietary biomarkers before application.

Unsupported transition metal sulfides with relatively high surface areas were synthesized by using mesoporous silicas as hard templates. The prepared catalysts were characterized by N 2 physisorption, TEM, and NH 3 -TPD method. The products from HDO of guaiacol over the catalysts were analyzed by GC–MS. The analysis results indicated that the acidity of catalysts facilitated the dehydration and transalkylation reactions to yield hydrocarbons and methylated products. Unsupported NiMoW catalyst performed the highest deoxygenation activity among catalysts studied, which were likely attributed to a large number of active sites exposed and the effect of W supplement.

Ochratoxin A (OTA) is one of the most important mycotoxins owing to its widespread occurrence and toxicity, including nephrotoxicity and potential carcinogenicity to humans. OTA has been detected in a wide range of agricultural commodities, including cereal grains and their processed products. In particular, oat-based products show a higher incidence and level of contamination. Extrusion cooking is widely used in the manufacturing of breakfast cereals and snacks and may reduce mycotoxins to varying degrees. Hence, the effects of extrusion cooking on the stability of OTA in spiked (100 μg/kg) oat flake was investigated by using a laboratory-scale twin-screw extruder with a central composite design. Factors examined were moisture content (20, 25, and 30% dry weight basis), temperature (140, 160, and 180°C), screw speed (150, 200, and 250 rpm), and die size (1.5, 2, and 3 mm). Both nonextruded and extruded samples were analyzed for reductions of OTA by high-performance liquid chromatography, coupled with fluorescence detection. The percentage of reductions in OTA in the contaminated oat flakes upon extrusion processing were in the range of 0 to 28%. OTA was partially stable during extrusion, with only screw speed and die size having significant effect on reduction (P0.005). The highest reduction of 28% was achieved at 180°C, 20% moisture, 250 rpm screw speed, and a 3-mm die with 193 kJ/kg specific mechanical energy. According to the central composite design analyses, up to 28% of OTA can be reduced by a combination of 162°C, 30% moisture, and 221 rpm, with a 3-mm die.

The effect of pyrolysis temperature on the morphology, bulk and surface chemistry of cellulose, xylan and lignin chars has been examined. Chars were produced between 300 and 700 °C. Raman, X-ray photoelectron, nuclear magnetic resonance spectroscopic techniques, scanning electron microscopy and surface area analysis were used to characterize each sample. Formation of polyaromatic structures were found to be prevalent at 400 °C for both cellulose and lignin chars, and showed development at 300 °C for Xylan. The low A bands identified in the lignin char produced at 400 °C indicate that crosslinking at low temperatures preferentially forms hexagonal or larger rings. Aromatic condensation increased until 500 °C, and remained stable up to 700 °C. The sharp drop in oxygen content as temperature is increased up to 500 °C and the formation of ether (C-O-C) groups indicates that oxygen is a primary reaction component for crosslinking and polycondensation. Despite the considerable increase in ring size for char produced at 700 °C compared to 500 °C, only very mild loss of oxygen is identified, suggesting that C-C bonds are forming with minimal oxygen mediation The increased broadness of the NMR peak and the Raman G band suggest that at these temperatures the increase in ring size occurs largely in a 3 dimensional manner rather than planar with contributions from non-hexagonal rings and out-of-plane distortion. By comparing the NMR dephasing data to the I(D)/I(G) ratio an approximate relation between this Raman data and cluster size has also been derived.