Jack M. Carraher

Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar.

Biorefineries aim to convert biomass into a spectrum of products ranging from biofuels to specialty chemicals. To achieve economically sustainable conversion, it is crucial to streamline the catalytic and downstream processing steps. In this work, a route that combines bio- and electrocatalysis to convert glucose into bio-based unsaturated nylon-6,6 is reported. An engineered strain of Saccharomyces cerevisiae was used as the initial biocatalyst for the conversion of glucose into muconic acid, with the highest reported muconic acid titer of 559.5 mg L(-1) in yeast. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid in 94 % yield despite the presence of biogenic impurities. Bio-based unsaturated nylon-6,6 (unsaturated polyamide-6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine.

cis,cis-Muconic acid isomerization and catalytic conversion to biobased cyclic-C6-1,4-diacid monomers

Renewable terephthalic and 1,4-cyclohexanedicarboxylic acids can be produced from biomass via muconic acid using a combination of biological and chemical processes. In this conversion scheme, cis,cis-mucononic acid is first obtained by fermentation using either sugar or lignin monomers as a feedstock. The diunsaturated cis,cis-diacid is then isomerized to trans,trans-muconic acid, reacted with biobased ethylene through Diels–Alder cycloaddition, and further hydrogenated or dehydrogenated to yield the desired 100% renewable cyclic dicarboxylic acid. The isomerization of cis,cis- to trans,trans-muconic acid represents the main bottleneck in this process due to undesired side reactions that promote ring closing to form lactones. Therefore, new technologies for the selective isomerization of muconic acid are urgently needed. Here, we studied the corresponding reaction kinetics to elucidate the mechanisms involved in both the isomerization and cyclization reactions with the objective to identify conditions that favor the selective formation of trans,trans-muconic acid. We demonstrate that the reactivity of muconic acid in aqueous media strongly depends on pH. Under alkaline conditions, cis,cis-muconic acid is deprotonated to the corresponding muconate dianion. This species is stable for extended periods of time and does not isomerize. Conversely, cis,cis-muconic acid readily isomerizes to its cis,trans-isomer under acidic conditions. Prolonged heating further triggers the intramolecular cyclizations through reaction of the carboxylic acid and alkene functionalities. The formation of the muconolactone and its dilactone is kinetically favored over the isomerization to trans,trans-muconic acid over a broad range of conditions. However, strategies involving the chelation of the carboxylates with inorganic salts or their solvation using polar aprotic solvents were found to hamper the ring closing reactions and allow the isomerization to trans,trans-muconic acid to proceed with high selectivity (88%). The obtained compound was further reacted with ethylene and hydrogenated to 1,4-cyclohexanedicarboxylic acid, an important monomer for the polyester and polyamide industries.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

A new selective route towards benzoic acid and derivatives from biomass-derived coumalic acid

The selective production of aromatics from bio-based sources is an area of interest to expand the potential for greener alternatives to petroleum-derived chemicals. A scalable, efficient route to produce bio-based benzoates is demonstrated by carrying out heterogeneous catalytic reactions in non-toxic bio-based solvents at 180 °C obtaining yields of up to 100 mol%. This approach extends the 2-pyrone (coumalic acid/methyl coumalate) Diels–Alder platform by utilizing a bioavailable co-reactant ethylene. A detailed investigation using a combination of kinetic experiments, DFT calculations, and multi-dimensional NMR was carried out to determine the detailed reaction network, and the corresponding activation energies for critical steps. Additionally, a series of experiments were conducted to maximize the yields by comparing different solvents, for both coumalic acid and methyl coumalate. Our results show that the choice of solvent was a significant factor when coumalic acid was the reactant (yields 71–92 mol%), while methyl coumalate was only minimally affected by the solvent (yields 95–100 mol%). Interestingly, the reaction network and kinetic analysis showed that the Diels–Alder reactions were not significantly different between coumalic acid and methyl coumalate, with the rate limiting step for both being decarboxylation with an activation barrier of 141 kJ mol−1 compared to 77 kJ mol−1 for the formation of the bicyclic adduct. Finally, the reaction cascade was found to be highly susceptible to by-product formation when as little as 5 vol% water was present in the solvent, which demonstrates that the absence of water is essential for high yielding benzoate production.

Intramolecular Conversion of Pentaaquahydroperoxidochromium(III) Ion to Aqueous Chromium(V): Potential Source of Carcinogenic Forms of Chromium in Aerobic Organisms

The decomposition of the title compound (H(2)O)(5)CrOOH(2+) (hereafter Cr(aq)OOH(2+)) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Cr(aq)(3+), HCrO(4)(-), H(2)O(2), and O(2)). Relative yields of individual products vary greatly with reaction conditions and initial concentrations of Cr(aq)OOH(2+). At pH 5.5 in the presence of O(2), the reaction was complete in less than a minute and generated chromate in about 70% yield. These findings, in addition to poor reproducibility of kinetic data, are indicative of the involvement of one or more reactive intermediates that consume additional amounts of Cr(aq)OOH(2+) in post-rate-determining steps. The kinetics were simplified in the presence of H(2)O(2) or ABTS(2-), both of which are capable of scavenging strongly oxidizing intermediates. The measured rate constant in 0.10 M HClO(4) at low O(2) concentrations (≤0.03 mM) was independent of the concentration of the scavengers and was, within error, the same for ABTS(2-), k = 4.9 (±0.2) × 10(-4) s(-1), and H(2)O(2), k = 5.3 (±0.7) × 10(-4) s(-1). At a constant ionic strength of 1.0 M, the reaction in the presence of either H(2)O(2) or ABTS(2-) obeyed a two-term rate law, k(obs)/s(-1) = 6.7 (±0.7) × 10(-4) + 7.6 (±1.1) × 10(-4) [H(+)]. Both in the presence and absence of ABTS(2-) as the scavenger, the yields of H(2)O(2) increased with increasing [H(+)]. These results are discussed in terms of a dual-pathway mechanism for the decay of Cr(aq)OOH(2+). The H(+)-catalyzed path leads to the dissociation of H(2)O(2) from Cr(III), while in the H(+)-independent reaction, Cr(aq)OOH(2+) is transformed to Cr(V). Both scavengers rapidly remove Cr(V) and simplify both the kinetics and products.

Kinetic and mechanistic studies of reactive intermediates in photochemical and transition- metal assisted oxidation, decarboxylation, and alkyl transfer reactions

Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III) The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter CraqOOH ) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq , HCrO4 , H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2′azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (kABTS2= (4.9  0.2) × 10 -4 s and kH2O2 = (5.3  0.7) × 10 -4 s); indicating involvement of the scavengers in post-rate determining steps. In the presence