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The fiber in corn kernels, currently unutilized in the corn to ethanol process, represents an opportunity for introduction of cellulose conversion technology. We report here that Clostridium thermocellum can solubilize over 90% of the carbohydrate in autoclaved corn fiber, including its hemicellulose component glucuronoarabinoxylan (GAX). However, Thermoanaerobacterium thermosaccharolyticum or several other described hemicellulose-fermenting thermophilic bacteria can only partially utilize this GAX. We describe the isolation of a previously undescribed organism, Herbinix spp. strain LL1355, from a thermophilic microbiome that can consume 85% of the recalcitrant GAX. We sequence its genome, and based on structural analysis of the GAX, identify six enzymes that hydrolyze GAX linkages. Combinations of up to four enzymes are successfully expressed in T. thermosaccharolyticum. Supplementation with these enzymes allows T. thermosaccharolyticum to consume 78% of the GAX compared to 53% by the parent strain and increases ethanol yield from corn fiber by 24%.

Many seeds are green during development, and light has been shown to play a role in the efficiency with which maternally supplied substrates are converted into storage compounds. However, the effects of light on the fluxes through central metabolism that determine this efficiency are poorly understood. Here, we used metabolic flux analysis to determine the effects of light on central metabolism in developing embryos of false flax (Camelina sativa). Metabolic efficiency in C. sativa is of interest because, despite its growing importance as a model oilseed and engineering target and its potential as a biofuel crop, its yields are lower than other major oilseed species. Culture conditions under which steady-state growth and composition of developing embryos match those in planta were used to quantify substrate uptake and respiration rates. The carbon conversion efficiency (CCE) was 21% 6 3% in the dark and 42% 6 4% under high light. Under physiological illumination, the CCE (32% 6 2%) was substantially lower than in green and nongreen oilseeds studied previously. 13C and 14C isotopic labeling experiments were used together with computer-aided modeling to map fluxes through central metabolism. Fluxes through the oxidative pentose phosphate pathway (OPPP) were the principal source of CO2 production and strongly negatively correlated with CCE across light levels. OPPP fluxes were greatly in excess of demand for NAD(P)H for biosynthesis and larger than those measured in other systems. Excess reductant appears to be dissipated via cyanide-insensitive respiration. OPPP enzymes therefore represent a potential target for increasing efficiency and yield in C. sativa.

Perennial grasses are promising feedstocks for biofuel production, with potential for leveraging their native microbiomes to increase their productivity and resilience to environmental stress. Here, we characterize the 16S rRNA gene diversity and seasonal assembly of bacterial and archaeal microbiomes of two perennial cellulosic feedstocks, switchgrass (Panicum virgatum L.) and miscanthus (Miscanthus x giganteus). We sample leaves and soil every three weeks from pre-emergence through senescence for two consecutive switchgrass growing seasons and one miscanthus season, and identify core leaf taxa based on occupancy. Virtually all leaf taxa are also detected in soil; source-sink modeling shows non-random, ecological filtering by the leaf, suggesting that soil is an important reservoir of phyllosphere diversity. Core leaf taxa include early, mid, and late season groups that were consistent across years and crops. This consistency in leaf microbiome dynamics and core members is promising for microbiome manipulation or management to support crop production.

The development of precious-metal-free catalysts to promote the sustainable production of fuels and chemicals from biomass remains an important and challenging target. Here, we report the efficient hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran over a unique core-shell structured catalyst, Co@CoO that affords the highest productivity among all catalysts, including noble-metal-based catalysts, reported to date. Surprisingly, we find that the catalytically active sites reside on the shell of CoO with oxygen vacancies rather than the metallic Co. The combination of various spectroscopic experiments and computational modelling reveals that the CoO shell incorporating oxygen vacancies not only drives the heterolytic cleavage, but also the homolytic cleavage of H 2 to yield more active H δ− species, resulting in the exceptional catalytic activity. Co@CoO also exhibits excellent activity toward the direct hydrodeoxygenation of lignin model compounds. This study unlocks, for the first time, the potential of simple metal-oxide-based catalysts for the hydrodeoxygenation of renewable biomass to chemical feedstocks. The development of precious-metal-free catalysts to promote the sustainable production of fuels and chemicals from biomass challenging. Here the authors report a unique core-shell structured Co@CoO catalyst which exhibits excellent performance in the hydrogenolysis of biomass-derived compounds.

Lignin is an energy-dense, heterogeneous polymer comprised of phenylpropanoid monomers used by plants for structure, water transport, and defense, and it is the second most abundant biopolymer on Earth after cellulose. In production of fuels and chemicals from biomass, lignin is typically underused as a feedstock and burned for process heat because its inherent heterogeneity and recalcitrance make it difficult to selectively valorize. In nature, however, some organisms have evolved metabolic pathways that enable the utilization of lignin-derived aromatic molecules as carbon sources. Aromatic catabolism typically occurs via upper pathways that act as a “biological funnel” to convert heterogeneous substrates to central intermediates, such as protocatechuate or catechol. These intermediates undergo ring cleavage and are further converted via the β-ketoadipate pathway to central carbon metabolism. Here, we use a natural aromatic-catabolizing organism, Pseudomonas putida KT2440, to demonstrate that these aromatic metabolic pathways can be used to convert both aromatic model compounds and heterogeneous, lignin-enriched streams derived from pilot-scale biomass pretreatment into medium chain-length polyhydroxyalkanoates (mcl -PHAs). mcl -PHAs were then isolated from the cells and demonstrated to be similar in physicochemical properties to conventional carbohydrate-derived mcl -PHAs, which have applications as bioplastics. In a further demonstration of their utility, mcl -PHAs were catalytically converted to both chemical precursors and fuel-range hydrocarbons. Overall, this work demonstrates that the use of aromatic catabolic pathways enables an approach to valorize lignin by overcoming its inherent heterogeneity to produce fuels, chemicals, and materials.

How much carbon does it take to make nitric acid? The counterintuitive answer nowadays is quite a lot. Nitric acid is manufactured by ammonia oxidation, and all the hydrogen to make ammonia via the Haber-Bosch process comes from methane. That's without even accounting for the fossil fuels burned to power the process. Chen et al. review research prospects for more sustainable routes to nitrogen commodity chemicals, considering developments in enzymatic, homogeneous, and heterogeneous catalysis, as well as electrochemical, photochemical, and plasma-based approaches. Science , this issue p. eaar6611 Nitrogen is fundamental to all of life and many industrial processes. The interchange of nitrogen oxidation states in the industrial production of ammonia, nitric acid, and other commodity chemicals is largely powered by fossil fuels. A key goal of contemporary research in the field of nitrogen chemistry is to minimize the use of fossil fuels by developing more efficient heterogeneous, homogeneous, photo-, and electrocatalytic processes or by adapting the enzymatic processes underlying the natural nitrogen cycle. These approaches, as well as the challenges involved, are discussed in this Review.

Caffeoyl-coenzyme A 3-O-methyltransferase (CCoAOMT) is an S-adenosyl methionine (SAM)-dependent O-methyltransferase responsible for methylation of the meta-hydroxyl group of caffeoyl-coenzyme A (CoA) on the pathway to monolignols, with their ring methoxylation status characteristic of guaiacyl or syringyl units in lignin. In order to better understand the unique class of type 2 O-methyltransferases from monocots, we have characterized CCoAOMT from sorghum (Sorghum bicolor; SbCCoAOMT), including the SAM binary complex crystal structure and steady-state enzyme kinetics. Key amino acid residues were validated with site-directed mutagenesis. Isothermal titration calorimetry data indicated a sequential binding mechanism for SbCCoAOMT, wherein SAM binds prior to caffeoyl-CoA, and the enzyme showed allosteric behavior with respect to it. 5-Hydroxyferuloyl-CoA was not a substrate for SbCCoAOMT. We propose a catalytic mechanism in which lysine-180 acts as a catalytic base and deprotonates the reactive hydroxyl group of caffeoyl-CoA. This deprotonation is facilitated by the coordination of the reactive hydroxyl group by Ca2+ in the active site, lowering the pKa of the 3'-OH group. Collectively, these data give a new perspective on the catalytic mechanism of CCoAOMTs and provide a basis for the functional diversity exhibited by type 2 plant OMTs that contain a unique insertion loop (residues 208–231) conferring affinity for phenylpropanoid-CoA thioesters. In conclusion, the structural model of SbCCoAOMT can serve as the basis for protein engineering approaches to enhance the nutritional, agronomic, and industrially relevant properties of sorghum.

Core Ideas Fermentable sugars were greatest in corn stover > perennial grasses > polycultures. Corn stover had the highest ethanol content. Miscanthus had the highest ethanol yield potential on a per hectare basis. Ethanol yield potential per hectare of switchgrass ≥ corn stover. Biomass yield was the strongest driver of per hectare ethanol yield. Many crops have been proposed as feedstocks for the emerging cellulosic ethanol industry, but information is lacking about the relative importance of feedstock production and quality. We compared yield and sugar content for seven bioenergy cropping systems in south‐central Wisconsin (ARL) and southwestern Michigan (KBS) during three growing seasons (2012 through 2014). The cropping systems were (i) continuous corn stover ( Zea mays L.), (ii) switchgrass ( Panicum virgatum L.), (iii) giant miscanthus ( Miscanthus × giganteus Greef & Deuter ex Hodkinson & Renvoize), (iv) hybrid poplar ( Populus nigra × P. maximowiczii A. Henry ‘NM6’), (v) native grass mix, (vi) early successional community, and (vii) restored prairie. A high‐throughput pretreatment and fermentation assay showed corn stover with the highest sugar content (213 g glucose kg −1 [Glc] and 115 g xylose kg −1 [Xyl]) followed by the two monoculture perennial grass treatments (154 [Glc] and 88 [Xyl]) and then the herbaceous polycultures (135 [Glc] and 77 [Xyl]). Biomass production and sugar content were combined to calculate ethanol yields. Miscanthus had the highest per hectare ethanol yields (1957 l ha −1 yr −1 ARL, 2485 l ha −1 yr −1 KBS) followed by switchgrass (1091 l ha −1 yr −1 ARL, 1017 l ha −1 yr −1 KBS) and corn stover (1121 l ha −1 yr −1 ARL, 878 l ha −1 yr −1 KBS). Perennial grass cropping systems (i.e., switchgrass and miscanthus) had higher per hectare ethanol yields at both sites relative to diverse systems that included dicots. Despite feedstock differences in fermentable sugars, biomass production was the strongest driver of per hectare ethanol yield.

Decelerating global warming is one of the predominant challenges of our time and will require conversion of CO2 to usable products and commodity chemicals. Of particular interest is the production of fuels, because the transportation sector is a major source of CO2 emissions. Here, we review recent technological advances in metabolic engineering of the hydrogen-oxidizing bacterium Cupriavidus necator H16, a chemolithotroph that naturally consumes CO2 to generate biomass. We discuss recent successes in biofuel production using this organism, and the implementation of electrolysis/artificial photosynthesis approaches that enable growth of C. necator using renewable electricity and CO2. Last, we discuss prospects of improving the nonoptimal growth of C. necator in ambient concentrations of CO2. Cupriavidus necator has a wide metabolic range and naturally creates a biopolymer, poly[(R)-3 hydroxybutyrate] (PHB). Using metabolic engineering techniques, carbon flux can be directed away from PHB synthesis toward the generation of biofuels and bioproducts.Researchers demonstrated the production of many biofuel products using C. necator, including methyl ketones, isoprenoids and terpenes, isobutanol, alkanes and alkenes, and a wide variety of commodity chemicals from CO2.Growth of C. necator and bioproduct production using electrolysis was recently demonstrated, including the use of an artificial leaf system.While genetic engineering of C. necator remains a laborious process, synthetic biology tools for this organism are being expanded with new technologies that will allow for large alterations to its genome.

Harnessing lipogenic pathways and rewiring acyl-CoA and acyl-ACP (acyl carrier protein) metabolism in Yarrowia lipolytica hold great potential for cost-efficient production of diesel, gasoline-like fuels, and oleochemicals. Here we assessed various pathway engineering strategies in Y. lipolytica toward developing a yeast biorefinery platform for sustainable production of fuel-like molecules and oleochemicals. Specifically, acyl-CoA/acyl-ACP processing enzymes were targeted to the cytoplasm, peroxisome, or endoplasmic reticulum to generate fatty acid ethyl esters and fatty alkanes with tailored chain length. Activation of endogenous free fatty acids and the subsequent reduction of fatty acyl-CoAs enabled the efficient synthesis of fatty alcohols. Engineering a hybrid fatty acid synthase shifted the free fatty acids to a medium chain-length scale. Manipulation of alternative cytosolic acetyl-CoA pathways partially decoupled lipogenesis from nitrogen starvation and unleashed the lipogenic potential of Y. lipolytica. Taken together, the strategies reported here represent promising steps to develop a yeast biorefinery platform that potentially upgrades low-value carbons to high-value fuels and oleochemicals in a sustainable and environmentally friendly manner.