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

Lignin is an alkyl-aromatic polymer present in plant cell walls for defense, structure, and water transport. Despite exhibiting a high-energy content, lignin is typically slated for combustion in modern biorefineries due to its inherent heterogeneity and recalcitrance, whereas cellulose and hemicellulose are converted to renewable fuels and chemicals. However, it is critical for the viability of third-generation biorefineries to valorize lignin alongside polysaccharides. To that end, we employ metabolic engineering, separations, and catalysis to convert lignin-derived species into cis,cis-muconic acid, for subsequent hydrogenation to adipic acid, the latter being the most widely produced dicarboxylic acid. First, Pseudomonas putida KT2440 was metabolically engineered to funnel lignin-derived aromatics to cis,cis-muconate, which is an atom-efficient biochemical transformation. This engineered strain was employed in fed-batch biological cultivation to demonstrate a cis,cis-muconate titer of 13.5 g/L in 78.5 h from a model lignin-derived compound. cis,cis-Muconic acid was recovered in high purity (>97%) and yield (74%) by activated carbon treatment and crystallization (5°C, pH 2). Pd/C was identified as a highly active catalyst for cis,cis-muconic acid hydrogenation to adipic acid with high conversion (>97%) and selectivity (>97%). Under surface reaction controlling conditions (24°C, 24 bar, ethanol solvent), purified cis,cis-muconic acid exhibits a turnover frequency of 23-30 sec -1 over Pd/C, with an apparent activation energy of 70 kJ/mol. Lastly, cis,cis-muconate was produced with engineered P. putida grown on a biomass-derived, lignin-enriched stream, demonstrating an integrated strategy towards lignin valorization to an important commodity chemical.

Catalytic reduction of water contaminants using palladium (Pd)-based catalysts and hydrogen gas as a reductant has been extensively studied at the bench-scale, but due to technical challenges it has only been limitedly applied at the field-scale. To motivate research that can overcome these technical challenges, this review critically analyzes the published research in the area of Pd-based catalytic reduction of priority drinking water contaminants (i.e., halogenated organics, oxyanions, and nitrosamines), and identifies key research areas that should be addressed. Specifically, the review summarizes the state of knowledge related to (1) proposed reaction pathways for important classes of contaminants, (2) rates of contaminant reduction with different catalyst formulations, (3) long-term sustainability of catalyst activity with respect to natural water foulants and regeneration strategies, and (4) technology applications. Critical barriers hindering implementation of the technology are related to catalyst activity (for some contaminants), stability, fouling, and regeneration. New developments overcoming these limitations will be needed for more extensive field-scale application of this technology.

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Self-assembly of nanoparticles is an important mechanism of particle growth in the solution-phase synthesis of oxides and oxyhydroxides. In this work, particle growth in aqueous colloidal suspensions of anatase (TiO 2 ), hematite (Fe 2 O 3 ), feroxyhite (FeOOH), and heterogenite (CoOOH) was observed to occur by two primary mechanisms: coarsening and growth by topotactic assembly. Coarsening is governed by the growth of larger particles at the expense of smaller particles, and topotactic assembly results in single crystals of unique morphology. The hematite nanocrystals are nominally equidimensional crystals that are usually constructed from more than 10 primary building blocks. The heterogenite particles are hexagonal plates that are, on average, 0.7 µm across and 20-30 nm thick. These plates are porous and are assemblies of hundreds of oriented nanocrystalline building blocks. The feroxyhite nanocrystals attach to form ∼30 nm porous flakes that are several nanometers thick. The anatase nanocrystals assemble to form elongated, bent, or nominally equidimensional single crystals with ultimate morphologies that frequently violate crystal-symmetry rules. Kinetic experiments, using anatase particles, show that the number of isolated primary particles decreases with time and that the assembly order, which reflects the average number of primary particles per secondary particle, increases with time. Growth by oriented aggregation is highly dependent on solution chemistry and may provide a means by which intricate assemblies can be achieved without the use of organic additives.