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At least 91 records · Page 5

iNovo479: Metabolic Modeling Provides a Roadmap to Optimize Bioproduct Yield from Deconstructed Lignin Aromatics by Novosphingobium aromaticivorans

Lignin is an abundant renewable source of aromatics and precursors for the production of other organic chemicals. However, lignin is a heterogeneous polymer, so the mixture of aromatics released during its depolymerization can make its conversion to chemicals challenging. Microbes are a potential solution to this challenge, as some can catabolize multiple aromatic substrates into one product. Novosphingobium aromaticivorans has this ability, and its use as a bacterial chassis for lignin valorization could be improved by the ability to predict product yields based on thermodynamic and metabolic inputs. In this work, we built a genome-scale metabolic model of N. aromaticivorans, iNovo479, to guide the engineering of strains for aromatic conversion into products. iNovo479 predicted product yields from single or multiple aromatics, and the impact of combinations of aromatic and non-aromatic substrates on product yields. We show that enzyme reactions from other organisms can be added to iNovo479 to predict the feasibility and profitability of producing additional products by engineered strains. Thus, we conclude that iNovo479 can help guide the design of bacteria to convert lignin aromatics into valuable chemicals.

59 BASIC BIOLOGICAL SCIENCES↗

Renewable Aromatics from Syngas

This study focuses on developing a catalytic process for the aromatization of mixed olefin (comprised of C 2 -C 6 ) over various metal doped zeolites towards the formation of large aromatics (preferably C 8 -C 16 ) compliance to the sustainable aviation fuel (SAF). Experiments were carried out using model olefin feedstocks containing either ethylene (C 2 ) or mixture of C 2 and C 3+ olefins. Both the catalyst composition and process parameters were evaluated in detail to identify their impact on the formation large aromatics. We specifically focus on the aromatization of ethylene as the model reaction and evaluated the impact of C 2+ olefins and paraffins that may present in the real feedstock. In all the reaction condition, aromatization of ethylene was used as the baseline to evaluate the effect of larger olefins or paraffins. Our results show that at this reaction condition paraffins remained either inert or show positive impact on the formation of large aromatics. While C 2 and C 3 olefins are highly reactive towards aromatization during reaction condition, large olefins are less reactive and thus, strategy was developed to oligomerize these large olefins (C 4+ ) alongside the aromatization of smaller olefins (C 2 /C 3 ).

10 SYNTHETIC FUELS↗

Fluorescent aromatic sensors and their methods of use

Aromatic molecules that can be used as sensors are described. The aromatic sensors include a polycyclic aromatic hydrocarbon core with a five-membered imide rings fused to the core and at least two pendant aryl groups. The aromatic sensor molecules can detect target analytes or molecular strain as a result of changes in their fluorescence, in many cases with on-off behavior. Aromatic molecules that fluoresce at various frequencies can be prepared by altering the structure of the aromatic core or the substituents attached to it. The aromatic molecules can be used as sensors for various applications such as, for example, the detection of dangerous chemicals, biomedical diagnosis, and the detection of damage or strain in composite materials. Methods of preparing aromatic sensor molecules are also described.

Meador, Michael A.↗

Kinetic modeling of anaerobic degradation of plant-derived aromatic mixtures by Rhodopseudomonas palustris

Abstract Rhodopseudomonas palustris is a model microorganism for studying the anaerobic metabolism of aromatic compounds. While it is well documented which aromatics can serve as sole organic carbon sources, co-metabolism of other aromatics is poorly understood. This study used kinetic modeling to analyze the simultaneous degradation of aromatic compounds present in corn stover hydrolysates and model the co-metabolism of aromatics not known to support growth of R. palustris as sole organic substrates. The simulation predicted that p -coumaroyl amide and feruloyl amide were hydrolyzed to p -coumaric acid and ferulic acid, respectively, and further transformed via p -coumaroyl-CoA and feruloyl-CoA. The modeling also suggested that metabolism of p -hydroxyphenyl aromatics was slowed by substrate inhibition, whereas the transformation of guaiacyl aromatics was inhibited by their p -hydroxyphenyl counterparts. It also predicted that substrate channeling may occur during degradation of p -coumaroyl-CoA and feruloyl-CoA, resulting in no detectable accumulation of p -hydroxybenzaldehyde and vanillin, during the transformation of these CoA ligated compounds to p- hydroxybenzoic acid and vanillic acid, respectively. While the simulation correctly represented the known transformation of p -hydroxybenzoic acid via the benzoyl-CoA pathway, it also suggested co-metabolism of vanillic acid and syringic acid, which are known not to serve as photoheterotrophic growth substrate for R. palustris .

59 BASIC BIOLOGICAL SCIENCES↗

Unique methionine-aromatic interactions govern the calmodulin redox sensor

Highlights: • Calmodulin’s open and closed states are stabilized by unique, redox sensitive methionine-aromatic interactions. • Methionine-aromatic interactions govern key conformational transitions in calmodulin through coupling with EF hand motion. • Methionine oxidation likely tunes target specificity by altering the strength of key methionine-aromatic interactions. Calmodulin contains multiple redox sensitive methionines whose oxidation alters the regulation of numerous targets. Molecular dynamics simulations were used to define the molecular principles that govern how calmodulin is structurally poised to detect and respond to methionine oxidation. We found that calmodulin's open and closed states were preferentially stabilized by unique, redox sensitive, methionine-aromatic interactions. Key methionine-aromatic interactions were coupled to reorientation of EF hand helices. Methionine to glutamine substitutions designed to mimic methionine oxidation strongly altered conformational transitions by modulating the strength of methionine-aromatic interactions. Together, these results suggest a broadly applicable redox sensing mechanism though which methionine oxidation by cellular oxidants alters the strength of methionine-aromatic interactions critical for functional protein dynamics.

60 APPLIED LIFE SCIENCES↗

Catalytic conversion of rubber wastes to produce aromatic hydrocarbons over USY zeolites: Effect of SiO 2 /Al 2 O 3 mole ratio

Catalytic conversion of rubber wastes to produce an alternative fuel resource is a promising approach to dispose of solid wastes and address environmental issues. In this study, catalytic fast pyrolysis (CFP) of rubber wastes over acidic zeolites was conducted, and the effect of SiO 2 /Al 2 O 3 mole ratio of USY zeolites on the formation of aromatic hydrocarbons was explored. Experimental results indicated that alkenes and aromatic hydrocarbons were the main pyrolytic products obtained from fast pyrolysis of rubber wastes, and the pyrolysis temperature played a vital role in the formation of aromatics with the highest concentration achieved at 750 °C. Furthermore, catalyst types also affected the catalytic degradation of rubber wastes since limonene was completely decomposed in the presence of zeolites. Compared to SAPO-34, zeolites with higher external surface area, stronger Brønsted acid sites, and larger pore size, including USY, HY, and Hβ, were more effective in the production of aromatic hydrocarbons with the highest content obtained from USY catalyzed run. Given the observed effect of SiO 2 /Al 2 O 3 mole ratio of USY zeolites on the formation of aromatic hydrocarbons during the CFP of rubber wastes, USY with low SiO 2 /Al 2 O 3 ratio of 5.3 was more beneficial to the generation of aromatic hydrocarbons, while that with higher SiO 2 /Al 2 O 3 mole ratio (11.5) facilitated the formation of alkenes. Simultaneously, the product distribution of aromatic hydrocarbons obtained from CFP of rubber wastes over USY zeolites was dominated by xylenes, alkylbenzenes, and toluene, and USY with SiO 2 /Al 2 O 3 mole ratio of 5.3 was more active in the production of toluene and xylenes.

30 DIRECT ENERGY CONVERSION↗

MarK, a Novosphingobium aromaticivorans kinase required for catabolism of multiple aromatic monomers

The aromatic compounds used in a variety of industrial products are currently obtained from nonrenewable petroleum sources. Alternatively, the plant polymer lignin is an abundant renewable source of aromatics, and its depolymerization generates a variety of products that can include acetovanillone, a vanillin derivative containing an acetyl side chain. The Alphaproteobacterium Novosphingobium aromaticivorans DSM12444 can metabolize several chemically modified aromatics in deconstructed lignin, but not acetovanillone. In this work, adaptive laboratory evolution identified a single amino acid change in the previously uncharacterized gene product Saro_1862 that is necessary and sufficient for N. aromaticivorans growth with acetovanillone as a sole growth substrate, as well as other aromatic monomers not metabolized by wild-type cells. We show that a glutamate (E) to lysine (K) substitution at amino acid residue 16 of Saro_1862 results in a ~1600-fold increase in the rate of ATP-dependent acetovanillone phosphorylation. We also find that recombinant Saro_1862 E16K phosphorylates several other aromatic compounds in vitro , defining the first reported catalytic activity for the widespread UPF0261 protein domain contained in Saro_1862. Thus, we propose naming Saro_1862 MarK, for multiple aromatic kinase. A 1.57 Å crystal structure of MarK E16K predicts that the E16K substitution lies in a potential ATP binding site, suggesting how this amino acid change increased catalytic activity. A search for homologs of MarK and other proteins required for acetovanillone degradation predicts that this pathway for aromatic metabolism exists throughout the bacterial phylogeny.

Novosphingobium↗

Critical Enzyme Reactions in Aromatic Catabolism for Microbial Lignin Conversion

The application of microbes to valorize aromatic compounds derived from the abundant plant biopolymer lignin is a rapidly developing area of research that may ultimately enable viable conversion of this recalcitrant and heterogeneous resource to valuable bio-based chemical products. Starting from the three canonical lignin building blocks, which differ in the extent of aromatic ring methoxylation, several common classes of enzymatic reaction occur in the upper pathways of aromatic catabolism to prepare aromatic compounds for assimilation into central carbon metabolism, including aromatic O-demethylation, hydroxylation and decarboxylation. These critical enzymatic steps can often be rate-limiting for efficient biological funnelling of aromatic compounds. Here we review the known enzymatic mechanisms for these reactions that are relevant for aerobic aromatic catabolism of lignin-related monomers, highlighting opportunities at the intersection of biochemistry, enzyme engineering and metabolic engineering for applications in the expanding field of microbial lignin valorization.

aromatic catabolism↗

Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds

In this tutorial review, we provide an overview of heterogeneous Diels–Alder catalysis for the production of lignocellulosic biomass-derived aromatic compounds. Diels–Alder reactions afford an extremely selective and efficient route for carbon–carbon cycloadditions to produce intermediates that can readily undergo subsequent dehydration or dehydrogenation reactions for aromatization. As a result, catalysis of Diels–Alder reactions with biomass-derived dienes and dienophiles has seen a growth of interest in recent years; however, significant opportunities remain to (i) tailor heterogeneous catalyst materials for tandem Diels–Alder and aromatization reactions, and (ii) utilize biomass-derived dienes and dienophiles to access both conventional and novel aromatic monomers. As such, this review discusses the mechanistic aspects of Diels–Alder reactions from both an experimental and computational perspective, as well as the synergy of Brønsted–Lewis acid catalysts to facilitate tandem Diels–Alder and aromatization reactions. Heterogeneous catalyst design strategies for Diels–Alder reactions are reviewed for two exemplary solid acid catalysts, zeolites and polyoxometalates, and recent efforts for targeting direct replacement aromatic monomers from biomass are summarized. In conclusion, we point out important research directions for progressing Diels–Alder catalysis to target novel, aromatic monomers with chemical functionality that enables new properties compared to monomers that are readily accessible from petroleum.

09 BIOMASS FUELS↗

Using MALDI-FTICR-MS Imaging to Track Low-Molecular-Weight Aromatic Derivatives of Fungal Decayed Wood

Low-molecular-weight (LMW) aromatics are crucial in meditating fungal processes for plant biomass decomposition. Some LMW compounds are employed as electron donors for oxidative degradation in brown rot (BR), an efficient wood-degrading strategy in fungi that selectively degrades carbohydrates but leaves modified lignins. Previous understandings of LMW aromatics were primarily based on “bulk extraction”, an approach that cannot fully reflect their real-time functions during BR. Here, we applied an optimized molecular imaging method that combines matrix-assisted laser desorption ionization (MALDI) with Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) to directly measure the temporal profiles of BR aromatics as Rhodonia placenta decayed a wood wafer. We found that some phenolics were pre-existing in wood, while some (e.g., catechin-methyl ether and dihydroxy-dimethoxyflavan) were generated immediately after fungal activity. These pinpointed aromatics might be recruited to drive early BR oxidative mechanisms by generating Fenton reagents, Fe2+ and H2O2. As BR progressed, ligninolytic products were accumulated and then modified into various aromatic derivatives, confirming that R. placenta depolymerizes lignin. Together, this work confirms aromatic patterns that have been implicated in BR fungi, and it demonstrates the use of MALDI-FTICR-MS imaging as a new approach to monitor the temporal changes of LMW aromatics during wood degradation.

59 BASIC BIOLOGICAL SCIENCES↗

The C-H stretching features at 3.2-3.5 μm of polycyclic aromatic hydrocarbons with aliphatic sidegroups

The so-called “unidentified” infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 μm aromatic C–H stretching feature is often accompanied by a weaker feature at 3.4 μm. The latter is generally thought to result from the C–H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of the 3.3 μm aromatic C–H feature to that of the 3.4 μm aliphatic C–H feature allows one to estimate the aliphatic fraction of the UIE carriers, provided that the intrinsic oscillator strengths of the 3.3 μm aromatic C–H stretch (A{sub 3.3}) and the 3.4 μm aliphatic C–H stretch (A{sub 3.4}) are known. While previous studies on the aliphatic fraction of the UIE carriers were mostly based on the A{sub 3.4}/A{sub 3.3} ratios derived from the mono-methyl derivatives of small PAH molecules, in this work we employ density functional theory to compute the infrared vibrational spectra of PAH molecules with a wide range of sidegroups including ethyl, propyl, butyl, and several unsaturated alkyl chains, as well as all the isomers of dimethyl-substituted pyrene. We find that, except for PAHs with unsaturated alkyl chains, the corresponding A{sub 3.4}/A{sub 3.3} ratios are close to that of mono-methyl PAHs. This confirms the predominantly aromatic nature of the UIE carriers previously inferred from the A{sub 3.4}/A{sub 3.3} ratio derived from mono-methyl PAHs.

79 ASTRONOMY AND ASTROPHYSICS↗

Direct aromatization of CO 2 via combined CO 2 hydrogenation and zeolite-based acid catalysis

Aromatics, including benzene, toluene, and xylenes (BTX), are essential chemical building blocks and are widely used as solvents, fuel additives, and polymers. With the recent development in CO 2 capture technologies and the progress made in producing H 2 using renewable energy, direct hydrogenation of CO 2 to aromatics via heterogeneous catalysis has emerged as a promising pathway to accomplish the production of aromatics with simultaneous utilization of waste CO 2 . In this review, we focus on recent advances in the nascent field of direct CO 2 aromatization, whereby tandem catalysts composed of CO 2 hydrogenation and aromatization functionalities are designed and deployed. We review two categories of tandem catalysts: catalysts integrating Fe-based/H-ZSM-5 components following RWGS (reverse water-gas shift of CO 2 to CO)-FT (Fischer-Tropsch synthesis of lower olefins)-aromatization pathways, and catalysts combining metal oxide/H-ZSM-5 domains following CO 2 to methanolaromatization pathways. The key parameters that determine the catalytic performance, such as the composition and structure of the Fe-based or metal oxide-based CO 2 conversion catalysts, the properties of H-ZSM-5, and the synergy between the two components, are analyzed to provide insights for the design of efficient tandem catalysts for CO 2 aromatization. In parallel, thermodynamic analyses, mechanistic studies, and density functional theory (DFT) computations for the relevant reaction routes and pathways are discussed to offer improved understanding of CO 2 activation, reaction intermediates, and product formation. In closing, the challenges and prospects for these tandem reactions are addressed to provide suggested paths forward for future research.

10 SYNTHETIC FUELS↗

Rapid estimation of concentration of aromatic classes in middistillate fuels by high-performance liquid chromatography

An high performance liquid chromatography (HPLC) method to estimate four aromatic classes in middistillate fuels is presented. Average refractive indices are used in a correlation to obtain the concentrations of each of the aromatic classes from HPLC data. The aromatic class concentrations can be obtained in about 15 min when the concentration of the aromatic group is known. Seven fuels with a wide range of compositions were used to test the method. Relative errors in the concentration of the two major aromatic classes were not over 10 percent. Absolute errors of the minor classes were all less than 0.3 percent. The data show that errors in group-type analyses using sulfuric acid derived standards are greater for fuels containing high concentrations of polycyclic aromatics. Corrections are based on the change in refractive index of the aromatic fraction which can occur when sulfuric acid and the fuel react. These corrections improved both the precision and the accuracy of the group-type results.

Otterson, D. A.↗

Thermal Stability Results of a Fischer-Tropsch Fuel With Various Blends of Aromatic Solution

Fischer-Tropsch (F-T) jet fuel composition differs from petroleum-based, conventional commercial jet fuel because of differences in feedstock and production methodology. F-T fuel typically has a lower aromatic and sulfur content and consists primarily of iso and normal paraffins. The ASTM D3241 specification for Jet Fuel Thermal Oxidation Test (JFTOT) break point testing method was used to test the breakpoint of a baseline commercial grade F-T jet fuel, and various blends of this F-T fuel with an aromatic solution. The goal of this research is to determine the effect of aromatic content on the thermal stability of F-T fuel. The testing completed in this report was supported by the NASA Fundamental Aeronautics Subsonic Fixed Wing Project. Two different aromatic content fuels from Rentech, as well as these fuels with added aromatic blend were analyzed for thermal stability using the JFTOT method. Preliminary results indicate a reduction in thermal stability occurs upon increasing the aromatic content to 10% by adding an aromatic blend to the neat fuel. These results do not specify a failure based on pressure drop, but only on tube color. It is unclear whether tube color correlates to more deposition on the tube surface or not. Further research is necessary in order to determine if these failures are true failures based on tube color. Research using ellipsometry to determine tube deposit thickness rather than color will be continued in follow-up of this study.

Lindsey, Jennifer↗

Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester

Acylation is an effective C-C bond-forming reaction to condense acetic acid and lignin-derived aromatic compounds into acetophenones, valuable precursors to fuels and chemicals. However, acetic acid is intrinsically an ineffective acylating agent. Here, we report that its acylation activity can be greatly enhanced by forming intermediate aromatic esters directly derived from acetic acid and phenolic compounds. Additionally, the acylation reaction was studied in the liquid phase over acid zeolites and was found to happen in two steps: 1 formation of an acylium ion and 2) C-C bond formation between the acylium ion and the aromatic substrate. Each of these steps may be rate-limiting, depending on the type of acylating agent and the aromatic substrate. Oxygen-containing substituents, such as -OH and -OCH 3 , can activate aromatic substrates for step 2, with -OH> -OCH 3 , whereas alkyl substituent -R cannot. At the same time, aromatic esters can rearrange to acetophenones by both an intramolecular pathway and, preferentially, an intermolecular one.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sequential oxidation-depolymerization strategies for lignin conversion to low molecular weight aromatic chemicals

Lignin is the largest source of bio-derived aromatic chemicals, and oxidative conversion of this polymeric material can generate valuable oxygenated aromatic compounds. Oxidative depolymerization of lignosulfonate feedstocks under alkaline conditions is used commercially for vanillin production. Recent studies have led to other oxidation methods that access different aromatic products from lignin in good yields. A particularly effective strategy that accesses some of the highest yields of aromatic monomers to date features a two-step process in which the oxidation of specific alcohol groups in lignin is followed by an oxidative, reductive, or redoxneutral step that cleaves the polymer into aromatic monomers and oligomers. Studies of model compounds have provided crucial mechanistic insights and contributed to the development of effective lignin depolymerization methods. Furthermore, this review provides a general overview of lignin depolymerization methods, followed by a survey of oxidation-depolymerization methods that access oxygenated aromatic monomers in good yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrothermal synthesis of core-shell ZSM-5/SAPO-34 composite zeolites and catalytic performance in methanol-to-aromatics reaction

A series of core-shell ZSM-5/SAPO-34 composite catalysts with different molar ratios were synthesized using hydrothermal method, and their catalytic performance was tested for the conversion of methanol-to-aromatics. The catalysts were characterized by means of XRD, SEM, NH{sub 3}-TPD and N{sub 2} adsorption-desorption analysis. The results showed that pristine SAPO-34 showed much lower selectivity to aromatics due to its narrow cage structure and lower acid sites. However, with increasing ZSM-5/SAPO-34M ratio, composite zeolite showed higher selectivity to aromatics. As the molar ratio was up to two, the selectivity to aromatics was even higher than that of pristine ZSM-5, indicating that core-shell composite zeolites with hierarchical structure and moderate acid sites were favored for methanol to aromatics. Meanwhile the optimum reaction condition for high yield of aromatics is determined to be 450 °C and 1.5 h{sup −1}(WHSV).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Mass Growth Processes to Polycyclic Aromatic Hydrocarbons through Radical–Radical Reactions Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) represent critical building blocks in molecular mass growth processes to carbonaceous nanoparticles, referred to as interstellar and circumstellar grains along with soot particles in astrophysical environments and combustion systems, respectively. Recent advancements on elucidating elementary steps to PAHs have utilized reactions of aromatic radicals, resonantly stabilized free radicals, and aliphatic radicals with closed shell hydrocarbons. However, the role of radical–radical reactions (RRRs) leading to PAHs has remained largely unexplored on the molecular level due to preceding experimental challenges in producing sufficiently high number densities of radical reactants for isomer-selective detection of products from bimolecular and termolecular reactions. This Account offers the latest developments in our knowledge on the mechanisms and pathways to PAHs via RRRs probed in a chemical microreactor at temperatures as high as 1600 K. Product preservation in a molecular beam coupled with synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and photoelectron photoion coincidence spectroscopy enabled isomer-selective detection of PAHs of up to three rings by their photoionization efficiency curves, which were fit with a linear combination of reference curves for identification. Experiments were combined with computational fluid dynamics modeling of the physicochemical processes in the microreactor, as well as high-level electronic structure calculations to reveal the reaction pathways of each system. Six distinct reaction mechanisms were discovered in this work: propargyl addition─benzannulation (PABA), methyl addition─ring expansion (MARE), cyclopentadienyl addition─naphthylization (CPAN), fulvenallenyl addition─cyclization─aromatization (FACA), benzyl addition─aromatization (BAA), and phenyl addition─pentacyclization (PAP). By systematically varying the number of carbon atoms in the radical reactants, molecular mass growth processes involving reactions between radicals with odd numbers of carbon atoms access aromatics carrying one, two, or three six-membered rings, whereas reactions between even- and odd-carbon-numbered radicals produce aromatics combining five- and six-membered rings. Our investigations reveal unconventional cycloadditions on excited state triplet surfaces, additions of radicals to low spin density carbon-centered radicals, spiroaromatic and fulvene-type intermediates, and highly strained bicyclic reaction intermediates, challenging current perceptions of PAH molecular mass growth processes. All of the listed mechanisms, except for FACA, feature endoergic reactions or barriers which lie above the separated reactants and therefore might be central to circumstellar environments of carbon-rich stars and planetary nebulae as their descendants, but they play no role in the gas phase of cold molecular clouds where temperatures as low as 10 K dominate. Altogether, this work provides detailed reaction mechanisms of PAH growth processes, advancing our knowledge of the chemistry of carbonaceous matter in the universe.

Addition reactions↗