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Bioelectrorefinery of furfural to furfuryl alcohol in aqueous media

Electrocatalytic hydrogenation of furfural to furfuryl alcohol represents a sustainable approach to utilizing renewable energy for producing bio-based platform chemicals. However, low Faraday efficiencies (FEs) and the use of organic solvents with high environmental impacts often render the process less sustainable than classical catalytic hydrogenation. In this study, a two-compartment and three-electrode setup at ambient temperature and atmospheric pressure, featuring various electrodes (Ag, Au, CP, Cu, Pt, Sn, and a gold-coated silver wire (AucAg)), and biomass-derived electrolytes (acetic acid, levulinic acid, and sodium acetate), was tested. AucAg, serving as an electrocatalyst with 1 M sodium acetate as electrolyte, exhibited the best combination of FE and furfuryl alcohol yield with 82% and 37%, respectively. The optimum conditions were achieved at 100 rpm and −0.8 V vs. RHE. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) analyzes indicated no significant influence of the substances on the working electrode during the reaction. Since the identity of the cation of the electrolyte influences the electrode-electrolyte microenvironment, multiple alkali metals were trialed. Sodium ion as the counter ion emerged on top, surpassing potassium, and cesium ions for the electroreduction of furfural to furfuryl alcohol. This preference could be attributed to the competing hydrogen evolution reaction favored by Cs over K and Na. In this perspective, the highlights of a bioelectrorefinery concept for creating a bio-derived platform chemical in a sustainable solvent with green electrons are demonstrated and optimized.

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Heavy antiretroviral exposure and exhausted/limited antiretroviral options: predictors and clinical outcomes.

People with HIV and extensive antiretroviral exposure may have limited/exhausted treatment options (LExTO) due to resistance, comorbidities, or antiretroviral-related toxicity. Predictors of LExTO were investigated in the RESPOND cohort. Participants on ART for at least 5 years were defined as having LExTO when switched to at least two anchor agents and one third antiretroviral (any class), a two-drug regimen of two anchor agents (excluding rilpivirine with dolutegravir/cabotegravir), or at least three nucleoside reverse transcriptase inhibitors. Baseline was the latest of January 1, 2012, cohort enrolment or 5 years after starting antiretrovirals. Poisson regression modeled LExTO rates and clinical events (all-cause mortality, non-AIDS malignancy, cardiovascular disease [CVD], and chronic kidney disease [CKD]). Of 23 827 participants, 2164 progressed to LExTO (9.1%) during 130 061 person-years follow-up (PYFU); incidence 1.66/100 PYFU (95% CI 1.59-1.73). Predictors of LExTO were HIV duration more than 15 years (vs. 7.5-15; adjusted incidence rate ratio [aIRR] 1.32; 95% CI 1.19-1.46), development of CKD (1.84; 1.59-2.13), CVD (1.64; 1.38-1.94), AIDS (1.18; 1.07-1.30), and current CD4 + cell count of 350 cells/μl or less (vs. 351-500 cells/μl, 1.51; 1.32-1.74). Those followed between 2018 and 2021 had lower rates of LExTO (vs. 2015-2017; 0.52; 0.47-0.59), as did those with baseline viral load of 200 cp/ml or less (0.46; 0.40-0.53) and individuals under 40. Development of LExTO was not significantly associated with clinical events after adjustment for age and current CD4, except CKD (1.74; 1.48-2.05). Despite an aging and increasingly comorbid population, we found declining LExTO rates by 2018-2021, reflecting recent developments in contemporary ART options and clinical management. Reassuringly, LExTO was not associated with a significantly increased incidence of serious clinical events apart from CKD.

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Conversion of xylose into D-xylitol using catalytic transfer hydrogenation with formic acid as H-donor

d-Xylitol, a biomass-derived sweetener, is increasingly used in cosmetics and pharmaceutical products. The raw material for d-xylitol production, d-xylose, is easily accessible from dissolving pulp production. d-xylitol production involves the heterogeneously catalyzed hydrogenation of d-xylose; this process is energy intensive, as the use of H2 requires high pressure and temperature. This work examined catalytic transfer hydrogenation for xylose conversion into xylitol. Formic acid (FA) was used to replace H2 as the H-donor, as it is easily available, inexpensive, may be obtained from renewable sources, and it avoids the risks associated with the use of high-pressure inflammable gas. A variety of commercially available catalysts were screened to reveal the one enabling the highest yield. The experiments were performed at 40, 80, and 140 °C, with pure xylose as a model compound. Triethylamine (Et3N) was added to ensure sufficient conversion rates. Based on the preliminary studies an experimental design was created (Design Expert®), including the two best performing catalysts Ru/Al2O3 and Ru/C, to investigate the influence of temperature and H-donor and base concentration on xylitol yield. Ru/C resulted in maximum d-xylitol yield of 73.2 % at 100 °C, FA to d-xylose ratio 5:1 and Et3N to FA ratio 0.4.

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Simultaneous posthydrolysis and liquid–liquid extraction: a SIMPLLE process to detoxify eucalyptus prehydrolysis liquor

AbstractThe prehydrolysis liquor from the prehydrolysis Kraft process is rich in sugars and could thus serve as a sustainable feedstock for the production of various chemicals. However, its industrial utilization is impeded by the presence of fermentation inhibitors and extensive lignin precipitation, the latter receiving only little attention in the literature.In order to provide a feedstock suitable for biotechnological or chemical conversion, the prehydrolysis liquor from eucalyptus wood must be detoxified whilst preventing the precipitation of lignin. To increase the yield of monomeric sugars, acid posthydrolysis should be investigated.Various solvents and solvent mixtures were screened for the high temperature liquid–liquid extraction of isothermally separated prehydrolysis liquor. Their capability to prevent lignin precipitation and to extract fermentation inhibitors was assessed using mass balances and size-exclusion chromatography. Based on the solvent screening, a process for simultaneous posthydrolysis and liquid–liquid extraction of eucalyptus prehydrolysis liquor was proposed and investigated using statistic experimental design.Liquid–liquid extraction using aliphatic alcohols effectively prevents lignin precipitation, and the addition of 25% (w/w) tri-n-octylamine was found to increase the overall inhibitor extraction efficiency. The conditions for the simultaneous posthydrolysis were investigated using a Box-Behnken experimental design, allowing for a maximum monomeric sugar yield of 83.0% at a sugar purity of 91.6%.The simultaneous posthydrolysis and liquid-liquid extraction (SIMPLLE) process thus avoids industrial-level problems associated with lignin precipitation. It provides a carbohydrate-rich stream with low levels of fermentation inhibitors, enabling further conversion to value added products.

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Supranormal lung function: Prevalence, associated factors and clinical manifestations across the lifespan.

It is now well established that there are different life-long lung function trajectories in the general population, and that some are associated with better or worse health outcomes. Yet, the prevalence, clinical characteristics and risk factors of individuals with supranormal FEV1 or FVC values (above the upper-limit of normal [ULN]) in different age-bins through the lifetime in the general population are poorly understood. To address these questions, we investigated the prevalence of supranormal FEV1 and FVC values in the LEAD (Lung, hEart, sociAl and boDy) study, a general population cohort in Austria that includes participants from 6 to 82 years of age. We found that: (1) the prevalence of supranormal pre-bronchodilator FEV1 and FVC values was 3.4% and 3.1%, respectively, and that these figures remained relatively stable through different age-bins except for participants >60 years., in whom they increased (5.0% and 4.2%, respectively). Approximately 50% of supranormal individuals had both increased FEV1 and FVC values; (2) supranormal spirometric values were consistently accompanied by higher static lung volumes and lower specific airway resistance through the lifespan, indicating better overall lung function; and (3) multivariate regression analysis identified that female sex, higher muscle mass (FFMI), less diabetes and fewer respiratory symptoms were consistently associated with supranormal FEV1 and FVC values. Supranormal FEV1 and/or FVC values occur in about 3% of the general population in different age bins and are associated with better health markers.

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Development of multi-material hybrid yarns consisting of steel, glass and polypropylene filaments for fiber hybrid composites

With the increased use of fiber-reinforced composites (FRPs), the design of a new generation of composite structures with high stiffness and a ductile material behavior is required to cope with complex load scenarios and high damage tolerances. This can be achieved, in particular, by a combination of conventional FRPs, which possess high stiffness and strength, with metallic materials characterized by their high ductility and associated higher energy absorption capacity. Currently, there are no solutions for the hybridization of high-performance filament yarns, metal filament yarns or thermoplastic filament yarns at the micro level. Therefore, the aim of this paper is the hybridization of multi-fiber components intermixed at the micro scale. For this purpose, three hybridization processes were investigated. They are conventional air-jet technology, air-jet technology based on a modified air nozzle and an additional pre-spreading device and a process based on a newly developed multi-level-intermixing device. The effect of different processing parameters, such as air pressure, air nozzle and type of manufacturing, on the tensile properties, appearance and damage of multi-material hybrid yarn was analyzed. The results show that the developed multi-material hybrid yarns have high potential for use in composites with high requirements for crash and impact properties.

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Not so biodegradable: Polylactic acid and cellulose/plastic blend textiles lack fast biodegradation in marine waters.

The resistance of plastic textiles to environmental degradation is of major concern as large portions of these materials reach the ocean. There, they persist for undefined amounts of time, possibly causing harm and toxicity to marine ecosystems. As a solution to this problem, many compostable and so-called biodegradable materials have been developed. However, to undergo rapid biodegradation, most compostable plastics require specific conditions that are achieved only in industrial settings. Thus, industrially compostable plastics might persist as pollutants under natural conditions. In this work, we tested the biodegradability in marine waters of textiles made of polylactic acid, a diffused industrially compostable plastic. The test was extended also to cellulose-based and conventional non-biodegradable oil-based plastic textiles. The analyses were complemented by bio-reactor tests for an innovative combined approach. Results show that polylactic acid, a so-called biodegradable plastic, does not degrade in the marine environment for over 428 days. This was also observed for the oil-based polypropylene and polyethylene terephthalate, including their portions in cellulose/oil-based plastic blend textiles. In contrast, natural and regenerated cellulose fibers undergo complete biodegradation within approximately 35 days. Our results indicate that polylactic acid resists marine degradation for at least a year, and suggest that oil-based plastic/cellulose blends are a poor solution to mitigate plastic pollution. The results on polylactic acid further stress that compostability does not imply environmental degradation and that appropriate disposal management is crucial also for compostable plastics. Referring to compostable plastics as biodegradable plastics is misleading as it may convey the perception of a material that degrades in the environment. Conclusively, advances in disposable textiles should consider the environmental impact during their full life cycle, and the existence of environmentally degradable disposal should not represent an alibi for perpetuating destructive throw-away behaviors.

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