Dataset Search Results

The presence of free fatty acids interferes with the conversion of plant oils to biodiesel. Four strong and weak base resins were evaluated for the removal of free fatty acids (FFA) from oil. Amberlite FPA 51 showed the highest adsorption capacity of FFA. A resin concentration above 3% could enable a higher percentage FFA adsorption. The adsorption process fitted a pseudo-first-order kinetic model and achieved equilibrium in approximately 8 h. A full factorial design was used to optimize the resin and FFA concentrations at a fixed temperature (40° C). A ratio of resin to fatty acid concentrations above 1.875 was sufficient for 70% adsorption and the amount adsorbed continued to increase with further added resin. A two-step washing of resin using hexane and ethanol recovered approximately 67.55% ± 4.05% of the initially added fatty acid. The resin that was used was regenerated with 5% NaOH and re-used for a minimum of three consecutive cycles. However, the adsorption capacity diminished to 75% of the initial cycle in cycles 2 and 3. Thus, the work presents a resin-based process for deacidification of oil to reduce fatty acid content of oil for biodiesel production.

Plant architecture influences the microenvironment throughout the canopy layer. Plants with a more erect leaf architecture allow for an increase in planting densities and allow more light to reach lower canopy leaves. This is predicted to increase crop carbon assimilation. Frictional resistance to wind reduces air movement in the lower canopy, resulting in higher humidity. By increasing the proportion of canopy photosynthesis in the more humid lower canopy, gains in the efficiency of water use might be expected, although this may be slightly offset by the more open erectophile form canopy. An anatomical feature in members of the Poaceae family that impacts leaf angle is the articulated junction of the sheath and blade, which also bares the ligule and auricles. Mutants, which lack ligules and auricles, show no articulation at this junction, resulting in leaves that are near vertical. In maize, these phenotypes termed liguleless result from null mutations of genes: ZmLG1 (Zm00001eb67740) and ZmLG2 (Zm00001eb147220). In sorghum, SbiRTx430.06G264300 (SbLG1) and SbiRTx430.03G392300 (SbLG2) are annotated as the respective maize homologues. A hair-pin element designed to down-regulate both SbLG1 and SbLG2 was introduced into the grain sorghum genotype RTx430. Derived transgenic events harbouring the hair-pin failed to develop ligules and displayed reduced leaf angles to the vertical, but less vertical than in null mutations. Under field settings, plots sown with these sorghum events having an erect architecture phenotype displayed an increase in photosynthesis in lower canopy levels, which led to increases in above-ground biomass and seed yield, without an increase in water use.

This zip file contains a UNIX-format DayCent model executable, input files, automation code, and associated directory structure necessary to re-produce the DayCent analysis underlying the manuscript. The main script “autodaycent.py” (written for Python 2.7) opens an interactive command line routine that facilitates: Calibrating the DayCent pine growth model; Initializing DayCent for a set of case studies sites; Executing an ensemble of model runs representing case study site reforestation, grassland restoration, or conversion to switchgrass cultivation; and Results analysis & generation of manuscript Fig. 3. Note that the interactive analysis code requires that all input files to be contained in the directory structure as uploaded, without modification. Executable versions of the DayCent model compatible with other operating systems are available upon request.

β‐Carotene is a natural pigment and health‐promoting metabolite, and has been widely used in the nutraceutical, feed, and cosmetic industries. Here, we engineered a GRAS yeast Saccharomyces cerevisiae to produce β‐carotene from xylose, the second most abundant and inedible sugar component of lignocellulose biomass. Specifically, a β‐carotene biosynthetic pathway containing crtYB, crtI, and crtE from Xanthophyllomyces dendrorhous was introduced into a xylose‐fermenting S. cerevisiae. The resulting strain produced β‐carotene from xylose at a titer threefold higher than from glucose. Interestingly, overexpression of tHMG1, which has been reported as a critical genetic perturbation to enhance metabolic fluxes in the mevalonate pathway and β‐carotene production in yeast when glucose is used, did not further improve the production of β‐carotene from xylose. Through fermentation profiling, metabolites analysis, and transcriptional studies, we found the advantages of using xylose as a carbon source, instead of glucose, for β‐carotene production to be a more respiratory feature of xylose consumption, a larger cytosolic acetyl‐CoA pool, and an upregulated expression level of rate‐limiting genes in the β‐carotene‐producing pathway, including ACS1 and HMG1. As a result, 772.8 mg/L of β‐carotene was obtained in a fed‐batch bioreactor culture with xylose feeding. Considering the inevitable large scale production of xylose when cellulosic biomass‐based bioeconomy is implemented, our results suggest xylose utilization is a promising strategy for overproduction of carotenoids and other isoprenoids in engineered S. cerevisiae.

The nonconventional yeast Issatchenkia orientalis has emerged as a potential platform microorganism for production of organic acids due to its ability to grow robustly under highly acidic conditions. However, lack of efficient genetic tools remains a major bottleneck in metabolic engineering of this organism. Here we report that the autonomously replicating sequence (ARS) from Saccharomyces cerevisiae (ScARS) was functional for plasmid replication in I. orientalis, and the resulting episomal plasmid enabled efficient genome editing by the CRISPR/Cas9 system. The optimized CRISPR/Cas9-based system employed a fusion RPR1′-tRNA promoter for single guide RNA (sgRNA) expression and could attain greater than 97% gene disruption efficiency for various gene targets. Additionally, we demonstrated multiplexed gene deletion with disruption efficiencies of 90% and 47% for double gene and triple gene knockouts, respectively. This genome editing tool can be used for rapid strain development and metabolic engineering of this organism for production of biofuels and chemicals.

Aging-related yield decline in Miscanthus × giganteus (miscanthus) remains a major constraint to sustainable biomass production. This study evaluated how nitrogen (N) management and soil fertility influence yield-component traits and productivity in aging miscanthus. Trials were conducted at two sites established in 2008 at the University of Illinois Energy Farm, Urbana, IL. (i) The Sun Grant trial received 0, 60, and 120 kg N ha−1 annually until 2015. Starting 2021, half of each plot received 60 or 120 kg N ha−1, resulting in six legacy-contemporary treatments: 0N–0N, 0N–120N, 60N–0N, 60N–60N, 120N–0N, 120N–120N. (ii) The Energy Farm trial remained unfertilized until 2014, when one half of each plot received 56 kg N ha−1, forming two treatments: 0N–0N, 0N–56N. Sun Grant trial results showed N fertilization increased tiller density (tillers m−2) and tiller weight (g tiller−1) in juvenile to early-mature miscanthus (2011–2015). After N withdrawal, both traits declined (20 % and 40 %), though legacy effects persisted in tiller weight in the aging stands (2020–2023). Contemporary N had little effect on tiller density but increased tiller weight by 34 %–77 %, resulting in 23 %–106 % higher machine-harvested biomass yield in 0–120N, 60-60N, and 120-120N plots. At the Energy Farm trial, 0N–56N plots yielded 59 %–108 % more biomass than 0N–0N. Soil total N increased (Sun Grant: 47 % by 2020; Energy Farm: 58 % by 2023), while Mehlich-3 P (42 %–44 %) and K (21 %–46 %) declined. These findings identify tiller weight as a key determinant of biomass yield in aging miscanthus and highlight the need for P and K management for long-term productivity.

Yarrowia lipolytica was found natively to produce erythritol, mannitol, and arabitol during growth on glucose, fructose, mannose, and glycerol. Osmotic stress is known to increase sugar alcohol production, and was found to significantly increase erythritol production during growth on glycerol. To better understand erythritol production from glycerol, since it was the most promising sugar alcohol, we measured the expression of key genes and intracellular metabolites. Osmotic stress increased the expression of several key genes in the glycerol catabolic pathway and the pentose phosphate pathway. Analysis of intracellular metabolites revealed that amino acids, sugar alcohols, and polyamines are produced at higher levels in response to osmotic stress. Heterologous overexpression of the sugar alcohol phosphatase increased erythritol production and glycerol utilization in Y. lipolytica. We further increased erythritol production by increasing the expression of native glycerol kinase (GK), and transketolase (TKL). These data show the growth and titers produced.

This dataset accompanies the research paper "Nine circles of elastic brittle fracture: A series of challenge problems to assess fracture models" by Kamarei, Zeng, Dolbow, and Lopez-Pamies, CMAME (2026). The dataset contains computational mesh files, figure data, and supporting materials for nine standardized challenge problems designed to assess fracture models in isotropic elastic brittle materials under quasi-static loading conditions. The nine challenge problems span the complete range of fracture nucleation and propagation mechanisms: strength nucleation (uniaxial tension, biaxial tension, torsion), Griffith nucleation (pure-shear, double cantilever beam, trousers), and strength-Griffith mediated nucleation (single edge notch, indentation, poker-chip). The dataset includes: High-quality mesh files for all nine challenge problems Figure data and results for both linear elastic (soda-lime glass) and non-linear elastic (PU elastomer) brittle materials

Plant cell wall hydrolysates contain not only sugars but also substantial amounts of acetate, a fermentation inhibitor that hinders bioconversion of lignocellulose. Despite the toxic and non-consumable nature of acetate during glucose metabolism, we demonstrate that acetate can be rapidly co-consumed with xylose by engineered Saccharomyces cerevisiae. The co-consumption leads to a metabolic re-configuration that boosts the synthesis of acetyl-CoA derived bioproducts, including triacetic acid lactone (TAL) and vitamin A, in engineered strains. Notably, by co-feeding xylose and acetate, an engineered strain produces 23.91 g/L TAL with a productivity of 0.29 g/L/h in bioreactor fermentation. This strain also completely converts a hemicellulose hydrolysate of switchgrass into 3.55 g/L TAL. These findings establish a versatile strategy that not only transforms an inhibitor into a valuable substrate but also expands the capacity of acetyl-CoA supply in S. cerevisiae for efficient bioconversion of cellulosic biomass.

This dataset contains the following to replicate figures from "TChem-atm (v2.0.0): Scalable Performance-Portable Multiphase Atmospheric Chemistry" submitted to Geophysical Model Development (GMD). It contains (1) the simulation inputs, outputs and analysis notebook for recreating the PartMC-CAMP and PartMC-TChem-atm comparison and (2) scripts, timing results and analysis tools for recreating the performance evaluation. Users can either inspect the raw output to verify the results of the manuscript or rerun simulations using the provided inputs. Additionally, modifiying the inputs allows for for further exploration of both model simulation and performance characteristics.

The selection of pretreatment methods is critical to achieving high product yields during bioconversion of lignocellulosic biomass. Hydrothermal, soaking-in-aqueous ammonia, and ionic liquid pretreatment methods are viable candidates for minimizing sugar decomposition, permitting the effective hydrolysis of structural carbohydrates, and producing a fermentable substrate suitable for achieving industrial ethanol titers and yields. In this study, the effect of these three pretreatment methods on non-modified sugarcane cultivar CP88-1762 and two transgenic lipid-accumulating sugarcane lines, oilcane 1565 and oilcane 1566, were investigated and compared in terms of lipid recovery, sugar yield, and ethanol yields within the lignocellulosic biomass conversion pipeline. Fed-batch enzymatic hydrolysis at high solid loading yielded hydrolysates capable of supporting industrial bioethanol titers across all conditions. The highest sugar yields were obtained on ammonia-pretreated biomass hydrolysate (253.73 g L−1), followed by hydrothermally pretreated hydrolysate (213.10 g L−1) and ionic liquid-pretreated hydrolysate (154.20 g L−1). Commercially viable ethanol titers of 100.62 g L−1, 64.47 g L−1, and 52.95 g L−1 were achieved from ammonia, hydrothermal, and ionic liquid pretreated hydrolysate with the corresponding ethanol productivities of 2.08 g L−1 h−1, 0.53 g L−1 h−1, and 0.36 g L−1 h−1. The lower acetic acid concentration in ammonia-pretreated hydrolysate may have enhanced its fermentability relative to the hydrothermal pretreatment condition, as indicated by the differences in ethanol titer and productivity. Lower sugar yields and ethanol productivities under the ionic liquid conditions likely resulted from the inhibitory effect of cholinium lysinate. Oilcane 1565 and oilcane 1566 bagasse accumulated over 16- and 3 times higher lipids than the non-modified sugarcane CP88-1762. The total fatty acid content in the oilcane samples was reduced in ammonia and ionic liquid-pretreated bagasse relative to the hydrothermal pretreatment condition. While all pretreatment techniques tested are industrially viable, the observed differences in titer, productivity, and lipid content indicate that careful selection and validation of upstream processing methods can contribute to improved economic and environmental outcomes.

Base catalysts were studied for the dehydration of fatty alcohols to linear alpha olefins (LAOs). For the gas phase dehydration of 1-octanol to 1-octene, 15% Cs/SiO2 catalyst was 56% selective at 10% conversion. Diluting a feed of C8, C10, and C14 fatty alcohols to 50% in undecane increased the selectivity to alpha olefins to 77–99%. 15% Cs/SiO2 was further investigated for the gas phase dehydration of a 4.2 g L−1 mixed C8–C14 fatty alcohol in tridecane feed and showed linear alpha olefin selectivities of 78–100% at initial conversions of 51–91% with the conversion lowering to 32–77% over 30 h. Catalytic activity was totally regenerated through calcination. A feed of biologically derived alcohols was produced with E. coli strain CM24 transformed with three plasmids (pBTRCk–pVHb–maACR, pACYC–pVHb–seFadBA, pTRC99A–pVHb–tdTER–fdh) which yielded a 5.5 g L−1 of C8–C14 fatty alcohol in tridecane. This biologically-derived feed was successfully dehydrated to linear alpha olefins over 15% Cs/SiO2 at selectivities of 60–100% with initial conversions of 35–75% which decreased to 22–55% over 30 h. Techno-economic analysis (TEA) of the integrated process for fatty alcohol production and subsequent dehydration to alpha olefins was conducted across the potential fermentation TRY (titer, rate, yield) landscape. Baseline fermentation performance resulted in a minimum product selling price (MPSP) double the market price for LAOs due to low titers and high costs associated with managing water and tridecane solvent flows through the system. However, targeted improvements in fermentation performance (e.g., achieving 40 g L−1 titer, 0.5 g L−1 h−1 productivity, 80% theoretical yield) can enable financially viable production of biologically derived LAOs.

L-malic acid is widely used in the food, chemical, and pharmaceutical industries. Here, we report on production of malic acid from xylose, the second most abundant sugar in lignocellulosic hydrolysates, by engineered Saccharomyces cerevisiae. To enable malic acid production in a xylose-assimilating S. cerevisiae, we overexpressed PYC1 and PYC2, coding for pyruvate carboxylases, a truncated MDH3 coding for malate dehydrogenase, and SpMAE1, coding for a Schizosaccharomyces pombe malate transporter. Additionally, both the ethanol- and glycerol-producing pathways were blocked to enhance malic acid production. The resulting strain produced malic acid from both glucose and xylose, but it produced much higher titers of malic acid from xylose than glucose. Interestingly, the engineered strain had higher malic acid yield from lower concentrations (10 g L‒1) of xylose, with no ethanol production, than from higher xylose concentrations (20 and 40 g L‒1). As such, a fed-batch culture maintaining xylose concentrations at low levels was conducted and 61.2 g L‒1 of malic acid was produced, with a productivity of 0.32 g L‒1 h. These results represent successful engineering of S. cerevisiae for the production of malic acid from xylose, confirming that that xylose offers the efficient production of various biofuels and chemicals by engineered S. cerevisiae.

For economic and sustainable biomanufacturing, the oleaginous yeast Rhodotorula toruloides has emerged as a promising platform for producing biofuels, pharmaceuticals, and other valuable chemicals. However, genetic manipulation of R. toruloides has been limited by its high GC content and the lack of a replicating plasmid, necessitating gene integration into the genome of the yeast. To address these challenges, we developed the RT-EZ (R. toruloides Efficient Zipper) toolkit, a versatile tool based on Golden Gate assembly, designed to streamline R. toruloides engineering with improved efficiency and flexibility. The RT-EZ toolkit simplifies vector construction by incorporating new features such as bidirectional promoters and 2A peptides, color-based screening using RFP, and sequences optimized for both Agrobacterium tumefaciens-mediated transformation (ATMT) and easy linearization, enabling straightforward selection and transformation. Notably, the RT-EZ kit can be used to construct an expression cassette with four different genes in one assembly reaction, significantly improving vector construction speed and efficiency. The utility of the RT-EZ toolkit was demonstrated through the successful synthesis of arachidonic acid in R. toruloides by coexpressing fatty acid elongases and desaturases. This result underscores the potential of the RT-EZ toolkit to advance synthetic biology in R. toruloides, providing a streamlined method for addressing genetic engineering challenges in the yeast.

There is a growing interest in developing cooperative chemoenzymatic reactions to harness the reactivity of chemical catalysts and the selectivity of enzymes for the synthesis of nonracemic chiral compounds. However, existing chemoenzymatic systems with more than one chemical reaction and one enzymatic reaction working cooperatively are rare. Moreover, the application of oxidoreductases in cooperative chemoenzymatic reactions is limited by the necessity of using expensive and unstable redox equivalents such as nicotinamide cofactors. Here, we report a light-driven cooperative chemoenzymatic system comprised of a photoinduced electron transfer reaction (PET) and a photosensitized energy transfer reaction (PEnT) with an enzymatic reduction in one-pot to synthesize chiral building blocks of bioactive compounds. As a proof of concept, ene-reductase was directly regenerated by PET in the absence of external cofactors. Meanwhile, enzymatic reduction worked cooperatively with photocatalyst-catalyzed energy transfer that continuously replenished the reactive isomer from the less reactive one. The whole system stereoconvergently reduced E/Z mixtures of alkenes to the enantiopure products. Additionally, enantioselective enzymatic reduction worked competitively with photocatalyst-catalyzed racemic background reaction and side reactions to channel the overall electron flow to the single enantiopure product. Such a light-driven cooperative chemoenzymatic system holds great potential for asymmetric synthesis using inexpensive petroleum or biomass-derived alkenes.

Gigatonne-scale atmospheric carbon dioxide removal (CDR), alongside deep emission cuts, is critical to stabilizing the climate. However, some of the most scalable CDR technologies are also the most land intensive. Here, we examine whether adequate land resources exist in the contiguous United States to meet CDR targets when prioritizing grid emissions reduction, food production, and the protection of sensitive ecosystems. We focus on biomass carbon removal and storage (BiCRS) and direct air capture and storage (DACS) and show that suitable lands exceed the expected needs: 37.6 million hectares of land are available for BiCRS, resulting in 0.26 GtCO2 of CDR/year, and 34 million hectares are suitable for wind- and solar-powered DACS, resulting in 4.8 GtCO2 of CDR/year if facilities are co-located with geologic CO2 storage. We identify biomass and energy supply hotspots to meet CDR targets while ensuring land protection and minimizing land competition.

DNAzymes have been widely used in many sensing and imaging applications but have rarely been used for genetic engineering since their discovery in 1994, because their substrate scope is mostly limited to single-stranded DNA or RNA, whereas genetic information is stored mostly in double-stranded DNA (dsDNA). To overcome this major limitation, we herein report peptide nucleic acid (PNA)-assisted double-stranded DNA nicking by DNAzymes (PANDA) as the first example to expand DNAzyme activity toward dsDNA. We show that PANDA is programmable in efficiently nicking or causing double strand breaks on target dsDNA, which mimics protein nucleases and can act as restriction enzymes in molecular cloning. In addition to being much smaller than protein enzymes, PANDA has a higher sequence fidelity compared with CRISPR/Cas under the condition we tested, demonstrating its potential as a novel alternative tool for genetic engineering and other biochemical applications.

Recently introduced photoperiod-sensitive (PS) biomass sorghum (Sorghum bicolor L. Moench) needs to be investigated for yield potential under different cultivation environments with reasonable nitrogen (N) inputs. The objectives of this study were to (1) evaluate the biomass yield and feedstock quality of four sorghum hybrids with different levels of PS ranging from very PS (VPS) hybrids and to moderate PS (MPS) hybrids, and (2) determine the optimal N inputs (0~168 kg N ha−1) under four environments: combinations of both temperate (Urbana, IL) and subtropical (College Station, TX) regions during 2018 and 2019. Compared to TX, the PS sorghums in central IL showed higher yield potential and steady feedstock production with an extended day length and with less precipitation variability, especially for the VPS hybrids. The mean dry matter (DM) yields of VPS hybrids were 20.5 Mg DM ha−1 and 17.7 Mg DM ha−1 in IL and TX, respectively. The highest N use efficiency occurred at a low N rate of 56 kg N ha−1 by improving approximately 33 kg DM ha−1 per 1.0 kg N ha−1 input. Approximately 70% of the PS sorghum biomass can be utilized for biofuel production, consisting of 58-65% of the cell-wall components and 4-11% of the soluble sugar. This study demonstrated that the rainfed temperate area (e.g., IL) has a great potential for the sustainable cultivation of PS energy sorghum due to their observed high yield potential, stable production, and low N requirements.

This dataset contains the values directly shown in the figures of the article "The impact of aerosol mixing state on immersion freezing: Insights from classical nucleation theory and particle-resolved simulations". This article is in preparation for submission to the journal Atmospheric Chemistry and Physics. The dataset consists of 15 NetCDF files processed from the raw output of the PartMC model. It does not include the theoretical values of frozen fraction, which can be computed using the equations provided in the paper.

This dataset contains the raw Florida bonneted bat echolocation calls recorded in southern Florida, USA from the years 2021 and 2022. This dataset also includes our artificial roost microclimate data (2021 only) and observations of bats recorded in our artificial roosts (2021 and 2022). Lastly, we include the R script required to analyze the Florida bonneted bat echolocation calls and the R script to produce the supplemental table and supplemental figure for our microclimate data.

Tab-separated value (TSV) file. 14745 data rows. Each data row represents publication metadata as retrieved from Crossref (http://crossref.org) 2023-04-05 when searching for retracted publications. Each row has the following columns: Index - Our index, starting with 0. DOI - Digital Object Identifier (DOI) for the publication Year - Publication year associated with the DOI. URL - Web location associated with the DOI. Title - Title associated with the DOI. May be blank. Author - Author(s) associated with the DOI. Journal - Publication venue (journal, conference, ...) associated with the DOI RetractionYear - Retraction Year associated with the DOI. May be blank. Category - One or more categories associated with the DOI. May be blank. Our search was via the Crossref REST API and searched for: Update_type=( 'retraction', 'Retraction', 'retracion', 'retration', 'partial_retraction', 'withdrawal','removal')

Data were collected from agronomy fields in Urbana and Ewing, IL, during the 2022 and 2023 growing seasons. The dataset includes dry biomass yield, nitrogen, phosphorus, and potassium concentrations and removals, and chemical composition elements (cellulose, hemicellulose, lignin, and soluble fractions) for 13 high-biomass sorghum hybrids. data_sharing.xlsx contains 20 columns and 104 rows. Below is the explanation of all variables in the file: Year: 2022; 2023 Location: Urbana, IL; Ewing, IL N rate (kg-N/ha): 0; 112 Hybrid #: H1-H13 Pedigree: Pedigree for 13 hybrids Dry biomass yield (Mg/ha): Aboveground dry biomass yield N (g/kg): Nitrogen concentration in plant tissue P (g/kg): Phosphorus concentration in plant tissue K (g/kg): Potassium concentration in plant tissue N (kg/ha): Nitrogen removal by aboveground biomass P (kg/ha): Phosphorus removal by aboveground biomass K (kg/ha): Potassium removal by aboveground biomass Cellulose (g/kg): Cellulose concentration in plant tissue Hemicellulose (g/kg): Hemicellulose concentration in plant tissue Lignin (g/kg): Lignin concentration in plant tissue Soluble (g/kg): Soluble concentration in plant tissue Cellulose (Mg/ha): Cellulose content in aboveground biomass Hemicellulose (Mg/ha): Hemicellulose content in aboveground biomass Lignin (Mg/ha): Lignin content in aboveground biomass Soluble (Mg/ha): Soluble content in aboveground biomass

This study advances the production of potassium sorbate (KS) from triacetic acid lactone (TAL) utilizing food-grade solvents, ethanol (EtOH) and isopropyl alcohol (IPA). We have previously demonstrated the route to produce KS from TAL in tetrahydrofuran (THF) as the main solvent, but the use of THF is associated with environmental and health risks especially for food applications. The process employs a catalytic approach in food-grade solvents and includes three main steps: hydrogenation, etherification and hydrolysis, and ring-opening hydrolysis to produce KS from TAL. In the synthesis of KS from TAL, the use of IPA leads to higher yields and reduced reaction times compared to EtOH. As a result, the overall reaction time in IPA was reduced to 35.7 h, compared to 42.1 h in our previous study using THF and EtOH, while achieving a comparable KS yield of 84% from TAL. The synthesized KS exhibits a trans-2, trans-4 geometrical configuration, identical to that of commercially available KS. Through techno-economic analysis (TEA) and life cycle assessment (LCA), we estimated full-scale production of KS from sugarcane with the developed process in IPA could achieve a minimum product selling price (MPSP) of $8.27 per kg with a range of $7.06–10.16 per kg [5th–95th percentiles from 6000 Monte Carlo simulations] and a carbon intensity (CI) of 13.7 [9.6–18.6] kg CO2-eq per kg. This study highlights the synthesis of KS from TAL using food-grade solvents, demonstrating improved economic viability and environmental sustainability compared to our previous research (MPSP of $9.68 per kg [$8.47–11.45 per kg] and CI of 16.2 [12.0–21.2] kg CO2-eq per kg), as the total required reaction decreases while achieving the comparable overall yield of KS from TAL.

The coproduction of high-value anthocyanin extract in the cellulosic ethanol process would diversify the co-product market, increase revenue, and potentially improve the economics of the process. The high anthocyanin concentration in the cob and structural carbohydrates in residual stover make purple corn stover an attractive source for anthocyanin and ethanol coproduction. This study aimed to develop simulation models for processes integrating ethanol production and anthocyanin extraction using purple corn stover, to evaluate their techno-economic feasibility, and to compare their performance with the conventional ethanol production process using corn stover. The annual ethanol production for plants processing 2000 MT dry feedstock / day was 148.6 million L/year for the integrated processes compared with 222.6 million L/year for the conventional process. Anthocyanin production in the modified processes using dilute acid-based and water-based anthocyanin extraction processes was 1779 and 1099 MT/year, respectively. Capital investments for the integrated processes ($448.1 to $443.8 million) were higher than the conventional process ($371.9 million). Due to high revenue from anthocyanin extract, the ethanol production cost for the integrated process using acid-based anthocyanin extraction ($0.36/L) was 34.5% lower than conventional ethanol production ($0.55/L). The ethanol production cost for the integrated process using water-based anthocyanin extraction ($0.68/L) was higher than conventional ethanol production due to low ethanol and anthocyanin yields. The minimum ethanol selling price for the integrated process using acid-based anthocyanin extraction ($0.65/L) was also lower than the conventional process ($0.72/L), indicating an improvement in economic performance.

Oxidative cleavage of carbon–carbon double bonds (C═C) in alkenes and fatty acids produces aldehydes and acids valued as chemical intermediates. Solid tungsten oxide catalysts are low cost, nontoxic, and selective for the oxidative cleavage of C═C bonds with hydrogen peroxide (H2O2) and are, therefore, a promising option for continuous processes. Despite the relevance of these materials, the elementary steps involved and their sensitivity to the form of W sites present on surfaces have not been described. Here, we combine in situ spectroscopy and rate measurements to identify significant steps in the reaction and the reactive species present on the catalysts and examine differences between the kinetics of this reaction on isolated W atoms grafted to alumina and on those exposed on crystalline WO3 nanoparticles. Raman spectroscopy shows that W–peroxo complexes (W–(η2-O2)) formed from H2O2 react with alkenes in a kinetically relevant step to produce epoxides, which undergo hydrolysis at protic surface sites. Subsequently, the CH3CN solvent deprotonates diols to form alpha-hydroxy ketones that react to form aldehydes and water following nucleophilic attack of H2O2. Turnover rates for oxidative cleavage, determined by in situ site titrations, on WOx–Al2O3 are 75% greater than those on WO3 at standard conditions. These differences reflect the activation enthalpies (ΔH‡) for the oxidative cleavage of 4-octene that are much lower than those for the isolated WOx sites (36 ± 3 and 60 ± 6 kJ·mol–1 for WOx–Al2O3 and WO3, respectively) and correlate strongly with the difference between the enthalpies of adsorption for epoxyoctane (ΔHads,epox), which resembles the transition state for epoxidation. The WOx–Al2O3 catalysts mediate oxidative cleavage of oleic acid with H2O2 following a mechanism comparable to that for the oxidative cleavage of 4-octene. The WO3 materials, however, form only the epoxide and do not cleave the C–C bond or produce aldehydes and acids. These differences reflect the distinct site requirements for these reaction pathways and indicate that acid sites required for diol formation are strongly inhibited by oleic acids and epoxides on WO3 whereas the Al2O3 support provides sites competent for this reaction and increase the yield of the oxidative cleavage products.