Lignin Stabilization and Carbohydrate Nature in H-transfer Reductive Catalytic Fractionation: The Role of Solvent Fractionation of Lignin Oil in Structural Profiling.

Reductive Catalytic Fractionation (RCF) of lignocellulosic materials produces lignin oil rich in monomer products and high-quality cellulosic pulps. RCF lignin oil also contains lignin oligomers/polymers and hemicellulose-derived carbohydrates. The variety of components makes lignin oil a complex matrix for analytical methods. As a result, the signals are often convoluted and overlapped, making detecting and quantifying key intermediates challenging. Therefore, to investigate the mechanisms underlining lignin stabilization and elucidate the structural features of carbohydrates occurring in the RCF lignin oil, fractionation methods reducing the RCF lignin oil complexity are required. This report examines the solvent fractionation of RCF lignin oil as a facile method for producing lignin oil fractions for advanced characterization. Solvent fractionation uses small volumes of environmentally benign solvents (methanol, acetone, and ethyl acetate) to produce multigram lignin fractions comprising products in different molecular weight ranges. This feature allows the determination of structural heterogeneity across the entire molecular weight distribution of the RCF lignin oil by high-resolution HSQC NMR spectroscopy. This study provides detailed insight into the role of the hydrogenation catalyst (Raney Ni) in stabilizing lignin fragments and defining the structural features of hemicellulose-derived carbohydrates in lignin oil obtained by the H-transfer RCF process.

Ischemia-guided vs routine non-culprit vessel angioplasty for patients with ST segment elevation myocardial infarction and multi-vessel disease: the IAEA SPECT STEMI trial.

BACKGROUND: In patients with multi-vessel disease presenting with ST elevation myocardial infarction (STEMI), the efficacy and safety of ischemia-guided, vs routine non-culprit vessel angioplasty has not been adequately studied. METHODS: We conducted an international, randomized, non-inferiority trial comparing ischemia-guided non-culprit vessel angioplasty to routine non-culprit vessel angioplasty, following primary PCI for STEMI. The primary outcome was the between-group difference in percent ischemic myocardium at follow-up stress MPI. All MPI images were processed and analyzed at a central core lab, blinded to treatment allocation. RESULTS: In all, 109 patients were enrolled from nine countries. In the ischemia-guided arm, 25/48 (47%) patients underwent non-culprit vessel PCI following stress MPI. In the routine non-culprit PCI arm, 43/56 (77%) patients underwent angioplasty (86% within 6 weeks of randomization). The median percentage of ischemic myocardium on follow-up imaging (mean 16.5 months) was low, and identical (2.9%) in both arms (difference 0.13%, 95%CI - 1.3%-1.6%, P < .0001; non-inferiority margin 5%). CONCLUSION: A strategy of ischemia-guided non-culprit PCI resulted in low ischemia burden, and was non-inferior to a strategy of routine non-culprit vessel PCI in reducing ischemia burden. Selective non-culprit PCI following STEMI offers the potential for cost-savings, and may be particularly relevant to low-resource settings. (CTRI/2018/08/015384).

Comparison between skeletal muscle and adipose tissue measurements with high-dose CT and low-dose attenuation correction CT of 18F-FDG PET/CT in elderly Hodgkin lymphoma patients: a two-centre validation.

OBJECTIVES: High-dose CT (HDCT) is considered the gold-standard imaging for the measurements of skeletal muscle area (SMA), visceral adipose tissue (VAT), subcutaneous adipose tissue (SAT) and intramuscular adipose tissue (IMAT) areas in the abdomen. These parameters may reflect sarcopenia, which can have a prognostic impact in several oncological diseases. The aim of this study was to compare the agreement of measurements of SMA, VAT, SAT and IMAT areas between HDCT and low-dose CT (LDCT) of 18-fludeoxyglucose positron emission tomography (18F-FDG PET)/CT in elderly patients affected by Hodgkin lymphoma (HL). METHODS: We retrospectively included 90 patients affected by HL who underwent baseline 18F-FDG-PET/CT and HDCT within a mean interval of 7 days. HDCT and LDCT images were analysed by two blinded observers using segmentation software (Slice-O-Matic, Tomovision) to quantify the areas. HDCT and LDCT measurements were compared using Bland-Altman plots and Passing-Bablock regression analyses. Pearson correlation coefficient (r) was used to correlate measurements from the two imaging modalities. RESULTS: Comparison of HDCT and LDCT data demonstrated a strong correlation for measurement of VAT(r = 0.942, p < 0.0001), SAT (r = 0.894, p < 0.0001) and SMA (r = 0.934, p < 0.0001). Instead considering IMAT, correlation was good but less significant (r = 0.742). The mean difference between the two methods was found to be very small, with a difference of 1% for SAT,+6.1% for VAT,+2.5% for SMA and -1.9% for IMAT. CONCLUSION: LDCT of PET/CT is a safe, accurate and precise method for the measurements of skeletal muscle area, visceral and subcutaneous adipose tissue. Their measurements are reproducible and correlate closely with HDCT. ADVANCES IN KNOWLEDGE: LLDCT of PET/CT is a safe and accurate method for the measurements of SMA, VAT and SAT; their measurements are closely correlated with HDCT. LDCT can be considered an accurate alternative tool for measuring abdominal fat and muscles in the clinical practice.

Long-Term Iron and Vitamin B12 Deficiency Are Present after Bariatric Surgery, Despite the Widespread Use of Supplements.

There are few long-term nutritional studies in subjects undergoing bariatric surgery that have assessed weight regain and nutritional deficiencies. In this study, we report data 8 years after surgery on weight loss, use of dietary supplements and deficit of micronutrients in a cohort of patients from five centres in central and northern Italy. The study group consisted of 52 subjects (age: 38.1 ± 10.6 y, 42 females): 16 patients had Roux-en-Y gastric bypass (RYGB), 25 patients had sleeve gastrectomy (SG) and 11 subjects had adjustable gastric banding (AGB). All three bariatric procedures led to sustained weight loss: the average percentage excess weight loss, defined as weight loss divided by excess weight based on ideal body weight, was 60.6% ± 32.3. Despite good adherence to prescribed supplements, 80.7% of subjects (72.7%, AGB; 76.7%, SG; 93.8 %, RYGB) reported at least one nutritional deficiency: iron (F 64.3% vs. M 30%), vitamin B12 (F 16.6% vs. M 10%), calcium (F 33.3% vs. M 0%) and vitamin D (F 38.1% vs. M 60%). Long-term nutritional deficiencies were greater than the general population among men for iron and among women for vitamin B12.

Kinetic Energy Dose as a Unified Metric for Comparing Ball Mills in the Mechanocatalytic Depolymerization of Lignocellulose.

Mechanochemistry utilizes mechanical forces to activate chemical bonds. It offers environmentally benign routes for both (bio) organic and inorganic syntheses. However, direct comparison of mechanochemistry results is often very challenging. In mechanochemical synthetic protocols, ball mill setup (mechanical design and grinding vessel geometry) in addition to experimental parameters (milling frequency, duration, ball count and size) vary broadly. This fact poses a severe issue to further progress in this exciting research area because ball mill setup and experimental parameters govern how much kinetic energy is transferred to a chemical reaction. In this work, we address the challenge of comparing mechanochemical reaction results by taking the energy dose provided by ball mills as a unified metric into account. In this quest, we applied kinematic modeling to two ball mills functioning under distinct working principles to express the energy dose as a mathematical function of the experimental parameters. By examining the effect of energy dose on the extent of the mechanocatalytic depolymerization (MCD) of lignocellulosic biomass (beechwood), we found linear correlations between yield of water-soluble products (WSP) and energy dose for both ball mills. Interestingly, when a substrate layer is formed on the grinding jar wall and/or grinding medium, a weak non-linear correlation between water-soluble products yield and energy dose is identified. We demonstrate that the chemical reaction's best utilization of kinetic energy is achieved in the linear regime, which presents improved WSP yields for given energy doses. In the broader context, the current analysis outlines the usefulness of the energy dose as a unified metric in mechanochemistry to further the understanding of reaction results obtained from different ball mills operating under varied experimental conditions.

Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation.

Reductive catalytic fractionation (RCF) is a promising approach to fractionate lignocellulose and convert lignin to a narrow product slate. To guide research towards commercialization, cost and sustainability must be considered. Here we report a techno-economic analysis (TEA), life cycle assessment (LCA), and air emission analysis of the RCF process, wherein biomass carbohydrates are converted to ethanol and the RCF oil is the lignin-derived product. The base-case process, using a feedstock supply of 2000 dry metric tons per day, methanol as a solvent, and H2 gas as a hydrogen source, predicts a minimum selling price (MSP) of crude RCF oil of $1.13 per kg when ethanol is sold at $2.50 per gallon of gasoline-equivalent ($0.66 per liter of gasoline-equivalent). We estimate that the RCF process accounts for 57% of biorefinery installed capital costs, 77% of positive life cycle global warming potential (GWP) (excluding carbon uptake), and 43% of positive cumulative energy demand (CED). Of $563.7 MM total installed capital costs, the RCF area accounts for $323.5 MM, driven by high-pressure reactors. Solvent recycle and water removal via distillation incur a process heat demand equivalent to 73% of the biomass energy content, and accounts for 35% of total operating costs. In contrast, H2 cost and catalyst recycle are relatively minor contributors to operating costs and environmental impacts. In the carbohydrate-rich pulps, polysaccharide retention is predicted not to substantially affect the RCF oil MSP. Analysis of cases using different solvents and hemicellulose as an in situ hydrogen donor reveals that reducing reactor pressure and the use of low vapor pressure solvents could reduce both capital costs and environmental impacts. Processes that reduce the energy demand for solvent separation also improve GWP, CED, and air emissions. Additionally, despite requiring natural gas imports, converting lignin as a biorefinery co-product could significantly reduce non-greenhouse gas air emissions compared to burning lignin. Overall, this study suggests that research should prioritize ways to lower RCF operating pressure to reduce capital expenses associated with high-pressure reactors, minimize solvent loading to reduce reactor size and energy required for solvent recovery, implement condensed-phase separations for solvent recovery, and utilize the entirety of RCF oil to maximize value-added product revenues.

Performing an Additional Lateral Decubitus PET/CT Scan to Resolve a Respiratory Motion Artifact.

Respiratory motion artifacts may affect interpretation of whole-body 18F-FDG PET/CT scans, especially when lesions are localized between the liver and the lung. We report a case of a patient with breast cancer who underwent PET/CT after therapy and in whom focal 18F-FDG uptake of equivocal interpretation was observed between the liver and the pleura. A subsequent imaging acquisition of the right lateral decubitus showed that the lesion had a pleural location, thus improving the diagnostic accuracy of the PET/CT finding.

18F-FDG PET/CT Metabolic Behavior of COVID-19 Pneumonia: A Series of 4 Patients With RT-PCR Confirmation.

Between March 26 and April 6, among 80 patients who underwent F-FDG PET/CT in our department (Brescia, Italy), 4 showed the presence of an interstitial pneumonia suspected for COVID-19 with reverse transcriptase polymerase chain reaction confirmation. All patients except one had bilateral ground-glass opacities and/or lung consolidations in at least 2 pulmonary lobes. Inferior lobes and basal segments were the most frequent site of disease. All lung lesions had an increased FDG uptake corresponding to the interstitial pneumonia, and in one case, mediastinal nodal involvement was registered.

Design of Nickel Supported on Water-Tolerant Nb2O5 Catalysts for the Hydrotreating of Lignin Streams Obtained from Lignin-First Biorefining.

In biomass conversion, Nb2O5 has attracted increasing attention as a catalyst support presenting water-tolerant Lewis acid sites. Herein, we address the design of Ni/Nb2O5 catalysts for hydrotreating of lignin to hydrocarbons. To optimize the balance between acidic and hydrogenating properties, the catalysts were first evaluated in the hydrotreating of diphenyl ether. The best catalyst candidate was further explored in the conversion of lignin oil obtained by catalytic upstream biorefining of poplar. As primary products, cycloalkanes were obtained, demonstrating the potential of Ni/Nb2O5 catalysts for the lignin-to-fuels route. However, the Lewis acidity of Nb2O5 also catalyzes coke formation via lignin species condensation. Thereby, an acidity threshold should be found so that dehydration reactions essential to the hydrotreatment are not affected, but the condensation of lignin species prevented. This article provides a critical "beginning-to-end" analysis of aspects crucial to the catalyst design to produce lignin biofuels.

Membrane Fractionation of Liquors from Lignin-First Biorefining.

For the utilization of each lignin fraction in the lignin liquors, the development of separation strategies to fractionate the lignin streams by molecular weight ranges constitutes a timely challenge to be tackled. Herein, membrane filtration was applied to the refining of lignin streams obtained from a lignin-first biorefining process based on H-transfer reactions catalyzed by Raney Ni, by using 2-PrOH as a part of the lignin extraction liquor and as an H-donor. A two-stage membrane cascade was considered to separate and concentrate the monophenol-rich fraction from the liquor. Building on the results, an economic evaluation of the potential of membrane filtration for the refining of lignin streams was undertaken. In this proof-of-concept report, a detailed analysis is presented of future developments in the performance required for the utilization of membrane filtration for lignin refining and, more aspiringly, solvent reclamation.

A Convergent Approach for a Deep Converting Lignin-First Biorefinery Rendering High-Energy-Density Drop-in Fuels.

Herein, a lignin-centered convergent approach to produce either aliphatic or aromatic bio-hydrocarbons is introduced. First, poplar or spruce wood was deconstructed by a lignin-first biorefining process, a technique based on the early-stage catalytic conversion of lignin, yielding lignin oils along with cellulosic pulps. Next, the lignin oils were catalytically upgraded in the presence of a phosphidated Ni/SiO2 catalyst under H2 pressure. Notably, selectivity toward aliphatics or aromatics can simply be adjusted by changes in H2 pressure and temperature. The process renders two distinct main cuts of branched hydrocarbons (gasoline: C6-C10, and kerosene/diesel: C14-C20). As the approach is H2-intensive, we examined the utilization of pulp as an H2 source via gasification. For several biomass sources, the H2 obtainable by gasification stoichiometrically meets the H2 demand of the deep converting lignin-first biorefinery, making this concept plausible for the production of high-energy-density drop-in biofuels.

Promoting positive youth development: a psychosocial intervention evaluation / La promoción del desarrollo positivo en la juventud: evaluación de una intervención psicosocial

Convergence among treatment, prevention, and developmental psychosocial intervention approaches has led to the recognition of the need for evaluation models and research designs that employ a full range of evaluation information to provide an empirical basis for enhancing the efficiency, efficacy, and effectiveness of prevention and psychosocial positive youth development interventions (PYD). This study reports an investigation of a PYD psychosocial program using an Outcome Mediation Cascade (OMC) evaluation model, which is an integrated model for evaluating the empirical intersection between intervention and developmental processes. The Changing Lives Program (CLP) is a community engaged PYD psychosocial intervention for multi-ethnic, multi-problem at risk youth in urban alternative high schools. Findings indicated that the hypothesized model fit the data, χ2 (7) = 6.991, p= .43, RMSEA = .00, CFI = 1.00, WRMR = .459. Findings also provided preliminary evidence consistent with the hypothesis that, in addition to having effects on targeted positive outcomes, PYD interventions are likely to have progressive cascading effects on untargeted problem outcomes (in this case, behavioral outcomes) that operate through effects on positive outcomes

La convergencia entre enfoques de tratamiento, prevención e intervención psicosocial evolutiva ha dado lugar a que se reconozca que se necesitan modelos de evaluación y diseños de investigación que utilicen una gama completa de información sobre evaluación que siente la base empírica para mejorar la eficiencia, la eficacia y la efectividad de la prevención y de las intervenciones psicosociales en el desarrollo positivo de la juventud (DPJ). Este estudio trata de la investigación sobre un programa psicosocial sobre DPJ utilizando el Outcome Mediation Cascade (OMC), modelo integrado para evaluar la intersección empírica entre la intervención y los procesos de desarrollo. El Changing Lives Program (CLP) es una intervención psicosocial de DPJ en la que está implicada la comunidad para jóvenes multiétnicos en riesgo en colegios urbanos de secundaria alternativos. Los resultados indican que el modelo postulado se ajusta a los datos, χ2 (7) = 6.991, p= .43, RMSEA = .00, CFI = 1.00, WRMR = .459. Igualmente, los resultados aportan pruebas preliminares consistentes con la hipótesis de que además de tener influencia en los resultados positivos planeados es probable que las intervenciones DPJ tengan efectos progresivos en cascada en los resultados no previstos de los problemas (en este caso, resultados en el comportamiento) que operan a través de sus efectos en los resultados positivos

Hybrid Organic-Inorganic Anatase as a Bifunctional Catalyst for Enhanced Production of 5-Hydroxymethylfurfural from Glucose in Water.

Hybrid organic-inorganic anatase (hybrid-TiO2 ) is prepared by a facile hydrothermal synthesis method employing citric acid. The synthetic approach results in a high surface-area nanocrystalline anatase polymorph of TiO2 . The uncalcined hybrid-TiO2 is directly studied as a catalyst for the conversion of glucose into 5-hydroxymethylfurfural (HMF). In the presence of the hybrid-TiO2 , HMF yields up to 45 % at glucose conversions up to 75 % were achieved in water at 130 °C in a monophasic batch reactor. As identified by Ti K-edge XANES, hybrid-TiO2 contains a large fraction of fivefold coordinatively unsaturated TiIV sites, which act as the Lewis acid catalyst for the conversion of glucose into fructose. As citric acid is anchored in the structure of hybrid-TiO2 , carboxylate groups seem to catalyze the sequential conversion of fructose into HMF. The fate of citric acid bound to anatase and the TiIV Lewis acid sites throughout recycling experiments is also investigated. In a broader context, this contribution outlines the importance of hydrothermal synthesis for the creation of water-resistant Lewis acid sites for the conversion of sugars. Importantly, the use of the hybrid-TiO2 with no calcination step contributes to dramatically decreasing the energy consumption in the catalyst preparation.

Kinematic Modeling of Mechanocatalytic Depolymerization of α-Cellulose and Beechwood.

Mechanocatalytic depolymerization of lignocellulose presents a promising method for the solid-state transformation of acidified raw biomass into water-soluble products (WSPs). However, the mechanisms underlining the utilization of mechanical forces in the depolymerization are poorly understood. A kinematic model of the milling process is applied to assess the energy dose transferred to cellulose during its mechanocatalytic depolymerization under varied conditions (rotational speed, milling time, ball size, and substrate loading). The data set is compared to the apparent energy dose calculated from the kinematic model and reveals key features of the mechanocatalytic process. At low energy doses, a rapid rise in the WSP yield associated with the apparent energy dose is observed. However, at a higher energy dose obtained by extended milling duration or high milling speeds, the formation of a substrate cake layer on the mill vials appear to buffer the mechanical forces, preventing full cellulose conversion into WSPs. By contrast, for beechwood, there exists a good linear dependence between the WSP yield and the energy dose provided to the substrate over the entire range of WSP yields. As the formation of a substrate cake in depolymerization of beechwood is less severe than that for the cellulose experiments, the current results verify the hypothesis regarding the negative effect of a substrate layer formed on the mill vials upon the depolymerization process. Overall, the current findings provide valuable insight into relationships between the energy dose and the extent of cellulose depolymerization effected by the mechanocatalytic process.

1D and 2D NMR Spectroscopy of Bonding Interactions within Stable and Phase-Separating Organic Electrolyte-Cellulose Solutions.

Organic electrolyte solutions (i.e. mixtures containing an ionic liquid and a polar, molecular co-solvent) are highly versatile solvents for cellulose. However, the underlying solvent-solvent and solvent-solute interactions are not yet fully understood. Herein, mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate, the co-solvent 1,3-dimethyl-2-imidazolidinone, and cellulose are investigated using 1D and 2D NMR spectroscopy. The use of a triply-13 C-labelled ionic liquid enhances the signal-to-noise ratio for 13 C NMR spectroscopy, enabling changes in bonding interactions to be accurately pinpointed. Current observations reveal an additional degree of complexity regarding the distinct roles of cation, anion, and co-solvent toward maintaining cellulose solubility and phase stability. Unexpectedly, the interactions between the dialkylimidazolium ring C2 -H substituent and cellulose become more pronounced at high temperatures, counteracted by a net weakening of acetate-cellulose interactions. Moreover, for mixtures that exhibit critical solution behavior, phase separation is accompanied by the apparent recombination of cation-anion pairs.

Effect of methanol in controlling defunctionalization of the propyl side chain of phenolics from catalytic upstream biorefining.

In recent years, lignin valorization has gained upward momentum owing to advances in both plant bioengineering and catalytic processing of lignin. In this new horizon, catalysis is now applied to the 'pulping process' itself, creating efficient methods for lignocellulose fractionation or deconstruction (here referred to as Catalytic Upstream Biorefining or 'CUB'). These processes render, together with delignified pulps, lignin streams of low molecular weight (Mw) and low molecular diversity. Recently, we introduced a CUB process based on Early-stage Catalytic Conversion of Lignin (ECCL) through H-transfer reactions catalyzed by RANEY® Ni. This approach renders a lignin stream obtained as a viscous oil, comprising up to 60 wt% monophenolic compounds (Mw < 250 Da). The remaining oil fraction (40 wt%) is mainly composed of lignin oligomers, and as minor products, holocellulose-derived polyols and lignin-derived species of high Mw (0.25-2 kDa). Simultaneously, the process yields a holocellulose pulp with a low content of residual lignin (<5 wt%). Despite the efficiency of aqueous solutions of 2-propanol as a solvent for lignin fragments and an H-donor, there is scant information regarding the CUB process carried out in the presence of primary alcohols, which often inhibit the catalytic activity of RANEY® Ni, as revealed in model compound studies performed at low temperature. Considering the composition of the lignin oils obtained from CUB based on ECCL, the processes commonly render ortho-(di)methoxy-4-propylphenol derivatives with a varied degree of defunctionalization of the propyl side chain. In this contribution, we present the role of the alcohol solvent (methanol or 2-propanol) and Ni catalyst (Ni/C or RANEY® Ni) in control over selectivity of phenolic products. The current results indicate that solvent effects on the catalytic processes could hold the key for improving control over the degree of functionalization of the propyl side-chain in the lignin oil obtained from CUB, offering new avenues for lignin valorization at the extraction step.

Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil.

A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoCx /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules.

Thermally Triggered Phase Separation of Organic Electrolyte-Cellulose Solutions.

Organic electrolyte solutions (OES)-binary mixtures of an ionic liquid (IL) with a neutral polar aprotic co-solvent-are being recognized as excellent candidate solvents for the dissolution, derivatization, and sustainable processing of cellulose. These solutions exhibit the beneficially combined properties of rapid-to-instantaneous cellulose dissolution, raised thermal stability, and reduced viscosity, compared to cellulose solutions in the parent ILs. Herein, we report the reversible, thermally triggered phase separation of cellulose solutions in 1-ethyl-3-methylimidazolium acetate with 1,3-dimethyl-2-imidazolidinone. In these solutions, cellulose drives the process of phase separation, resulting in a lower, IL-rich layer in which the biopolymer is segregated. In turn, the upper phase is enriched in the neutral co-solvent. We show that the temperature of phase separation can be fine-tuned by modification of mole fractions of IL, co-solvent, and cellulose. This finding holds promise for the design of strategies for separation and solvent recycling in cellulose chemistry.