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

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1]
  1. Centre for Interfacial Reaction Engineering (CIRE) and School of Chemical, Biological and Materials Engineering, University of Oklahoma, 100 E. Boyd Norman OK 73019 USA
Publication Date:
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1400839
Grant/Contract Number:
Grant DESC0004600
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 13; Related Information: CHORUS Timestamp: 2017-10-20 15:32:26; Journal ID: ISSN 1864-5631
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Duong, Nhung N., Wang, Bin, Sooknoi, Tawan, Crossley, Steven P., and Resasco, Daniel E. Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester. Germany: N. p., 2017. Web. doi:10.1002/cssc.201700394.
Duong, Nhung N., Wang, Bin, Sooknoi, Tawan, Crossley, Steven P., & Resasco, Daniel E. Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester. Germany. doi:10.1002/cssc.201700394.
Duong, Nhung N., Wang, Bin, Sooknoi, Tawan, Crossley, Steven P., and Resasco, Daniel E. 2017. "Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester". Germany. doi:10.1002/cssc.201700394.
@article{osti_1400839,
title = {Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester},
author = {Duong, Nhung N. and Wang, Bin and Sooknoi, Tawan and Crossley, Steven P. and Resasco, Daniel E.},
abstractNote = {},
doi = {10.1002/cssc.201700394},
journal = {ChemSusChem},
number = 13,
volume = 10,
place = {Germany},
year = 2017,
month = 6
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 5, 2018
Publisher's Accepted Manuscript

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  • The conversion of biomass-derived sugars and aromatic molecules to cis,cis-muconic acid (referred to hereafter as muconic acid or muconate) has been of recent interest owing to its facile conversion to adipic acid, an important commodity chemical. Metabolic routes to produce muconate from both sugars and many lignin-derived aromatic compounds require the use of a decarboxylase to convert protocatechuate (PCA, 3,4-dihydroxybenzoate) to catechol (1,2-dihydroxybenzene), two central aromatic intermediates in this pathway. Several studies have identified the PCA decarboxylase as a metabolic bottleneck, causing an accumulation of PCA that subsequently reduces muconate production. A recent study showed that activity of the PCAmore » decarboxylase is enhanced by co-expression of two genetically associated proteins, one of which likely produces a flavin-derived cofactor utilized by the decarboxylase. Using entirely genome-integrated gene expression, we have engineered Pseudomonas putida KT2440-derived strains to produce muconate from either aromatic molecules or sugars and demonstrate in both cases that co-expression of these decarboxylase associated proteins reduces PCA accumulation and enhances muconate production relative to strains expressing the PCA decarboxylase alone. In bioreactor experiments, co-expression increased the specific productivity (mg/g cells/h) of muconate from the aromatic lignin monomer p-coumarate by 50% and resulted in a titer of >15 g/L. In strains engineered to produce muconate from glucose, co-expression more than tripled the titer, yield, productivity, and specific productivity, with the best strain producing 4.92+/-0.48 g/L muconate. Furthermore, this study demonstrates that overcoming the PCA decarboxylase bottleneck can increase muconate yields from biomass-derived sugars and aromatic molecules in industrially relevant strains and cultivation conditions.« less
  • The structures of the rotamers about the C-O bonds of formic acid, methyl formate, acetic acid, and methyl acetate were calculated by using the 6-31G* basis set and complete geometrical relaxation. Large basis sets (6-311+G**) and correction for electron correlation were needed in order to obtain calculated barriers that were in good agreement with the available experimental data. The factors that control the geometry at a carbonyl group are considered, and it is shown that an analysis in terms of bond path angles leads to a direct connection with electronegativity. The nature of the interaction between an amino group andmore » a carbonyl, as in an amide, is examined and shown not to involve charge transfer from the nitrogen to the carbonyl oxygen, but rather it involves charge transfer between carbon and nitrogen. The origin of the rotational barrier in esters and of the difference in energy between the E and Z conformers is discussed.« less
  • Treatment with the methyl ester of 3-indoleacetic acid reduced considerably the high initial decay rate in potato tubers and tomatoes treated with gamma radiation to preserve the storage life. (C.H.)
  • Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by ..gamma.. radiation at a temperature of 25/sup 0/C, a dose rate of 1 x 10/sup 6/ rad/hr, and FVA/..cap alpha..-olefin and MFVA/..cap alpha..-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with ..cap alpha..-olefin to form waxlike copolymers. The copolymerization rates of both FVA andmore » MFVA with ..cap alpha..-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene were nearly 1/2 over a wide range of the monomer compositions. The Mayo-Lewis method gave negative r/sub 1/ (FVA) and r/sub 1/(MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model.« less