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 carbohydratederived 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. biofuels | lignocellulose | biorefinery | aromatic degradation

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Microalgae offer great promise to contribute a signifi cant portion of the renewable fuels that will be required by the Renewable Fuels Standard described in the 2007 Energy Independence and Security Act of the United States. Algal biofuels would be based mainly on the high lipid content of the algal cell and thus would be an ideal feedstock for high energy density transportation fuels, such as biodiesel as well as green diesel, green jet fuel and green gasoline. A comprehensive research and development program for the development of algal biofuels was initiated by the US Department of Energy (DoE) more than 30 years ago, and although great progress was made, the program was discontinued in 1996, because of decreasing federal budgets and low petroleum costs. Interest in algal biofuels has been growing recently due to increased concern over peak oil, energy security, greenhouse gas emissions, and the potential for other biofuel feedstocks to compete for limited agricultural resources. The high productivity of algae suggests that much of the US transportation fuel needs can be met by algal biofuels at a production cost competitive with the cost of petroleum seen during the early part of 2008. Development of algal biomass production technology, however, remains in its infancy. This perspective provides a brief overview of past algal research sponsored by the DoE, the potential of microalgal biofuels and a discussion of the technical and economic barriers that need to be overcome before production of microalgal-derived diesel-fuel substitutes can become a large-scale commercial reality. Published in

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Natural gas is a mixture of low molecular weight hydrocarbon gases that can be generated from either fossil or anthropogenic resources. Although natural gas is used as a transportation fuel, constraints in storage, relatively low energy content (MJ/L), and delivery have limited widespread adoption. Advanced utilization of natural gas has been explored for biofuel production by microorganisms. In recent years, the aerobic bioconversion of natural gas (or primarily the methane content of natural gas) into liquid fuels (Bio-GTL) by biocatalysts (methanotrophs) has gained increasing attention as a promising alternative for drop-in biofuel production. Methanotrophic bacteria are capable of converting methane into microbial lipids, which can in turn be converted into renewable diesel via a hydrotreating process. In this paper, biodiversity, catalytic properties and key enzymes and pathways of these microbes are summarized. Bioprocess technologies are discussed based upon existing literature, including cultivation conditions, fermentation modes, bioreactor design, and lipid extraction and upgrading. This review also outlines the potential of Bio-GTL using methane as an alternative carbon source as well as the major challenges and future research needs of microbial lipid accumulation derived from methane, key performance index, and techno-economic analysis. An analysis of raw material costs suggests that methane-derived diesel fuel has the potential to be competitive with petroleum-derived diesel.