Precursor prioritization for p-cymene production through synergistic integration of biology and chemistry.

The strategy of synergistic application of biological and chemical catalysis is an important approach for efficiently converting renewable biomass into chemicals and fuels. In particular, the method of determining the appropriate intermediate between the two catalytic methods is critical. In this work, we demonstrate p-cymene production through the integration of biosynthesis and heterogenous catalysis and show how a preferred biologically derived precursor could be determined. On the biological side, we performed the limonene and 1,8-cineole production through the mevalonate pathway. Titers of 0.605 g/L and a 1.052 g/L were achieved, respectively. This difference is in agreement with the toxicity of these compounds toward the producing microorganisms, which has implications for subsequent development of the microbial platform. On the heterogeneous catalysis side, we performed the reaction with both biological precursors to allow for direct comparison. Using hydrogenation/dehydrogenation metals on supports with acid sites, both limonene and 1,8-cineole were converted to p-cymene with similar yields under equivalent reaction conditions. Thus, we could determine that the most promising strategy would be to target 1,8-cineole, the higher titer and lower toxicity bio-derived precursor with subsequent catalytic conversion to p-cymene. We further optimized the biological production of 1,8-cineole via fed-batch fermentation and reached the titer of 4.37 g/L which is the highest known 1,8-cineole titer from microbial production. This work provides a valuable paradigm for early stage considerations to determine the best route for the high-efficiency production of a target biobased molecule using an integration of biology and chemistry.

Bioenabled Platform to Access Polyamides with Built-In Target Properties.

The diversification of platform chemicals is key to today's petroleum industry. Likewise, the flourishing of tomorrow's biorefineries will rely on molecules with next-generation properties from biomass. Herein, we explore this opportunity with a novel approach to monomers with custom property enhancements. Cyclic diacids with alkyl and aromatic decorations were synthesized from muconic acid by Diels-Alder cycloaddition, and copolymerized with hexamethylenediamine and adipic acid to yield polyamides with built-in hydrophobicity and flame retardancy. Testing shows a 70% reduction in water uptake and doubling of char production while largely retaining other key properties of the parent Nylon-6,6. The present approach can be generalized to access a wide range of performance-advantaged polyamides.

Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis.

Amidation is an important reaction for bioderived platform molecules, which can be upgraded for use in applications such as polymers. However, fundamental understanding of the reaction especially in the presence of multiple groups is still lacking. In this study, the amidation of dimethyl fumarate, maleate, and succinate through ester ammonolysis was examined. The reaction networks and significant side reactions, such as conjugate addition and ring closing, were determined. A preliminary kinetic comparison among additional C4 and C6 esters showed a significant correlation between molecular structure and ammonolysis reactivity. Esters with a C=C double bond in the molecule backbone were found to have higher ammonolysis reactivity. To improve the selectivity to unsaturated amides rather than byproducts, the effects of thermal conditions and additives in dimethyl fumarate ammonolysis were examined. Lower temperature and decreasing methoxide ion concentration in the solution relative to the base case conditions increased the fumaramide selectivity from 67.1 to 90.6%.

Bioprivileged Molecules: Integrating Biological and Chemical Catalysis for Biomass Conversion.

Further development of biomass conversions to viable chemicals and fuels will require improved atom utilization, process efficiency, and synergistic allocation of carbon feedstock into diverse products, as is the case in the well-developed petroleum industry. The integration of biological and chemical processes, which harnesses the strength of each type of process, can lead to advantaged processes over processes limited to one or the other. This synergy can be achieved through bioprivileged molecules that can be leveraged to produce a diversity of products, including both replacement molecules and novel molecules with enhanced performance properties. However, important challenges arise in the development of bioprivileged molecules. This review discusses the integration of biological and chemical processes and its use in the development of bioprivileged molecules, with a further focus on key hurdles that must be overcome for successful implementation.

A Robust Strategy for Sustainable Organic Chemicals Utilizing Bioprivileged Molecules.

Biobased chemicals will inevitably be an important part of a sustainable organic chemical industry. Current efforts in biobased chemicals are largely driven by opportunistic chemical product targets requiring complete technology development from feedstock to final product for a specific molecule. To enhance the development of biobased chemicals, it is important to create strategies that can be more systematic and can leverage advancements across multiple final products. Discussed here is the concept of bioprivileged molecules, which are chemical intermediates that have the potential to be efficiently converted into a range of product molecules that can both directly replace existing petrochemicals and are novel molecules that impart enhanced performance properties in end-use applications.

Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents.

The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts, specifically chlorides. Reaction kinetics studies of the Brønsted acid-catalyzed dehydration of fructose to hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab initio molecular dynamics simulations (AIMD) show that highly localized negative charge on Cl- allows the chloride anion to more readily approach and stabilize the oxocarbenium ion that forms and the deprotonation transition state. High concentrations of polar aprotic solvents form local hydrophilic environments near the reactive hydroxyl group which stabilize both the proton and chloride anions and promote the dehydration of fructose.

Characterizing Substrate-Surface Interactions on Alumina-Supported Metal Catalysts by Dynamic Nuclear Polarization-Enhanced Double-Resonance NMR Spectroscopy.

The characterization of nanometer-scale interactions between carbon-containing substrates and alumina surfaces is of paramount importance to industrial and academic catalysis applications, but it is also very challenging. Here, we demonstrate that dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) allows the unambiguous description of the coordination geometries and conformations of the substrates at the alumina surface through high-resolution measurements of 13C-27Al distances. We apply this new technique to elucidate the molecular-level geometry of 13C-enriched methionine and natural abundance poly(vinyl alcohol) adsorbed on γ-Al2O3-supported Pd catalysts, and we support these results with element-specific X-ray absorption near-edge measurements. This work clearly demonstrates a surprising bimodal coordination of methionine at the Pd-Al2O3 interface.

Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals.

Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach. More generally, we suggest that molecules with three distinct functionalities may represent a practical upper limit on the extent of functionality present in the platform molecules that serve as the bridge between biological and chemical catalysis.

Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR.

DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticle catalysts. By offering >2500-fold time savings, the technique enabled the observation of (13)C-(13)C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

Tailoring the Composition of Bio-oil by Vapor-Phase Removal of Organic Acids.

Selective removal of organic acids from biomass pyrolysis vapors was demonstrated. A broad adsorbent range was tested with CaCO3 showing the best selectivity. Extensive material characterization demonstrated that the acid removal occurred through monolayer adsorption on CaCO3. Adsorbent regeneration was achieved by in situ heat treatment of the postreaction adsorbent where the adsorbed acid was converted into a ketone. The mitigation of the loss of other products was achieved by using surface modified CaCO3 materials, resulting in a significant improvement in the selectivity toward organic acid removal. The surface modification appeared to lead to formation of a metal-carboxylate intermediate consisting of both acetate and carbonate groups. Acetate group on the CaCO3 surface resulted in the suppression of side reactions. Generally, a higher acid removal was accompanied with a greater loss of other compounds, which could be tuned by using CaCO3 with different surface modification.

Sodium ion interactions with aqueous glucose: insights from quantum mechanics, molecular dynamics, and experiment.

In the last several decades, significant efforts have been conducted to understand the fundamental reactivity of glucose derived from plant biomass in various chemical environments for conversion to renewable fuels and chemicals. For reactions of glucose in water, it is known that inorganic salts naturally present in biomass alter the product distribution in various deconstruction processes. However, the molecular-level interactions of alkali metal ions and glucose are unknown. These interactions are of physiological interest as well, for example, as they relate to cation-glucose cotransport. Here, we employ quantum mechanics (QM) to understand the interaction of a prevalent alkali metal, sodium, with glucose from a structural and thermodynamic perspective. The effect on ß-glucose is subtle: a sodium ion perturbs bond lengths and atomic partial charges less than rotating a hydroxymethyl group. In contrast, the presence of a sodium ion significantly perturbs the partial charges of α-glucose anomeric and ring oxygens. Molecular dynamics (MD) simulations provide dynamic sampling in explicit water, and both the QM and the MD results show that sodium ions associate at many positions with respect to glucose with reasonably equivalent propensity. This promiscuous binding nature of Na(+) suggests that computational studies of glucose reactions in the presence of inorganic salts need to ensure thorough sampling of the cation positions, in addition to sampling glucose rotamers. The effect of NaCl on the relative populations of the anomers is experimentally quantified with light polarimetry. These results support the computational findings that Na(+) interacts similarly with α- and ß-glucose.

Spectrally edited 2D 13C-13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials.

Two robust combinations of spectral editing techniques with 2D (13)C-(13)C NMR have been developed for characterizing the aromatic components of (13)C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by (13)C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, C-H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and C=O carbons, which is particularly useful for identifying furan and arene rings. The C=O carbons, whose chemical shifts vary strongly (between 212 and 165 ppm) and systematically depend on their two bonding partners, show particularly informative cross peaks, given that one bonding partner is defined by the other frequency coordinate of the cross peak. The new techniques and the information content of the resulting spectra are validated on sulfuric-acid treated low-temperature carbon materials and on products of the Maillard reaction. The crucial need for spectral editing for correct peak assignment is demonstrated in an example.

Understanding the fast pyrolysis of lignin.

In the present study, pyrolysis of corn stover lignin was investigated by using a micro-pyrolyzer coupled with a GC-MS/FID (FID=flame ionization detector). The system has pyrolysis-vapor residence times of 15-20 ms, thus providing a regime of minimal secondary reactions. The primary pyrolysis product distribution obtained from lignin is reported. Over 84 % mass balance and almost complete closure on carbon balance is achieved. In another set of experiments, the pyrolysis vapors emerging from the micro-pyrolyzer are condensed to obtain lignin-derived bio-oil. The chemical composition of the bio-oil is analyzed by using GC-MS and gel permeation chromatography techniques. The comparison between results of two sets of experiments indicates that monomeric compounds are the primary pyrolysis products of lignin, which recombine after primary pyrolysis to produce oligomeric compounds. Further, the effect of minerals (NaCl, KCl, MgCl(2), and CaCl(2)) and temperature on the primary pyrolysis product distribution is investigated. The study provides insights into the fundamental mechanisms of lignin pyrolysis and a basis for developing more descriptive models of biomass pyrolysis.

Product distribution from the fast pyrolysis of hemicellulose.

Hemicellulose is one of the major constituents of biomass. Surprisingly, only very limited information regarding its product distribution under fast pyrolysis conditions is available in the literature. In the present study, a combination of several analytical techniques, including micro-pyrolyzer-GC-MS/FID, gas analysis, and capillary electrophoresis, were used to study the primary pyrolysis product distribution of hemicelluloses extracted and purified from switchgrass. A total of 16 products were identified and quantified, which accounted for 85% of the overall mass balance. The pyrolysis behavior of hemicellulose was found to be considerably different than cellulose and was explained on the basis of a proposed mechanism for glycosidic bond cleavage. Further, the effect of minerals and temperature was investigated. The study provides insight into the fast pyrolysis behavior of hemicellulose and provides a basis for developing models that can predict bio-oil composition resulting from overall biomass fast pyrolysis.

Distinguishing primary and secondary reactions of cellulose pyrolysis.

The objective of this study was to elucidate primary and secondary reactions of cellulose pyrolysis, which was accomplished by comparing results from a micro-pyrolyzer coupled to a GC-MS/FID system and a 100 g/hr bench scale fluidized bed reactor system. The residence time of vapors in the micro-pyrolyzer was only 15-20 ms, which precluded significant secondary reactions. The fluidized bed reactor had a vapor residence time of 1-2 s, which is similar to full-scale pyrolysis systems and is long enough for secondary reactions to occur. Products from the fluidized bed pyrolyzer reactor were analyzed using a combination of micro-GC, GC-MS/FID, LC-MS and IC techniques. Comparison between the products from the two reactor systems revealed that the oligomerization of leglucosan and decomposition of primary products such as 5-hydroxymethyl furfural, anhydro xylopyranose and 2-furaldehyde were the major secondary reactions occurring in the fluidized bed reactor. This study can be used to build more descriptive pyrolysis models that can predict yield of specific compounds.

Direct observation of macropore self-formation in hierarchically structured metal oxides.

The current work presents an unprecedented direct observation of macropore formation in the spontaneous self-assembly process to obtain hierarchical meso/macroporous metal oxides made possible with the help of an unusual titanium alkoxide.

Influence of inorganic salts on the primary pyrolysis products of cellulose.

Processing bio-oil with the help of currently existing petroleum refinery infrastructure has been considered as a promising alternative to produce sustainable fuels in the future. The feasibility of bio-oil production and upgrading processes depend upon its chemical composition which in turn depends on the biomass composition and the process conditions of the fast pyrolysis reactions. The primary goal of this paper was to investigate the effect of mineral salts including mixtures of salts in the form of switchgrass ash on the chemical speciation resulting from primary pyrolysis reactions of cellulose and to gain an insight of the underlying mechanisms. Various concentrations of inorganic salts (NaCl, KCl, MgCl(2), CaCl(2), Ca(OH)(2), Ca(NO(3))(2), CaCO(3) and CaHPO(4)) and switchgrass ash were impregnated on pure cellulose. These samples were pyrolyzed in a micro-pyrolyzer connected to a GC-MS/FID system. Effects of minerals on the formation of (a) low molecular weight species - formic acid, glycolaldehyde and acetol, (b) furan ring derivatives - 2-furaldehyde and 5-hydroxy methyl furfural and (c) anhydro sugar - levoglucosan are reported exclusively. Further, the effect of reaction temperature ranging from 350 to 600 degrees C on the pyrolysis speciation of pure and ash-doped cellulose is also reported. The pyrolysis speciation revealed the competitive nature of the primary reactions. Mineral salts and higher temperatures accelerated the reactions that led to the formation of low molecular weight species from cellulose as compared to those leading to anhydro sugars.

Hydrolysis of oligosaccharides from distillers grains using organic-inorganic hybrid mesoporous silica catalysts.

The use of propylsulfonic acid-functionalized mesoporous silica as a catalyst for the hydrolysis of oligosaccharides released by hydrothermal pretreatment of distiller's grains was examined in batch reactor studies. The effectiveness of the catalyst system for oligosaccharide hydrolysis was found to improve significantly with increased reaction temperature. This higher temperature operation allowed for more selective recovery of glucose, but was detrimental to arabinose recovery since significant degradation occurred. Xylose recovery efficiency improved with increasing temperature, but the higher temperature led to increased degradation. Using a model feed, solubilized proteins were found to deactivate the organic-inorganic hybrid catalyst, but a simple pretreatment with activated silica was found to alleviate the deactivation.

Unleashing biocatalysis/chemical catalysis synergies for efficient biomass conversion.

The goal of incorporating renewable carbon into the fuel and chemical enterprise will most likely be successful when combined systems of biocatalysts and chemical catalysts are exploited. Significant efforts in the biocatalytic release of sugars from biomass are being pursued for subsequent use in fermentation. Two recent papers demonstrate an alternative approach to converting these sugars to a liquid fuel by using chemical catalysts.