Electrochemical conversion of biomass-derived intermediate compounds to high-value products has emerged as a promising approach in the field of biorefinery. Biomass upgrading allows for the production of chemicals from non-fossil-based carbon sources and capitalization on electricity as a green energy input. Amino acids, as products of biomass upgrading, have received relatively little attention. Pharmaceutical and food industries will benefit from an alternative strategy for the production of amino acids that does not rely on inefficient fermentation processes. The use of renewable biomass resources as starting materials makes this proposed strategy more desirable. Herein, we report an electrochemical approach for the selective oxidation of biomass-derived α-hydroxyl acids to α-keto acids, followed by electrochemical reductive amination to yield amino acids as the final products. Such a strategy takes advantage of both reactions at the anode and cathode and produces amino acids under ambient conditions with high energy efficiency. A flow electrolyzer was also successfully employed for the conversion of α-hydroxyl acids to amino acids, highlighting its great potential for large-scale application.
more »
« less
Anaerobic Conversion of Proteinogenic Amino Acids When Methanogenesis Is Inhibited: Carboxylic Acid Production from Single Amino Acids
Proteins are an abundant biopolymer in organic waste feedstocks for biorefining. When degraded, amino acids are released, but their fate in non-methanogenic microbiomes is not well understood. The ability of a microbiome obtained from an anaerobic digester to produce volatile fatty acids from the twenty proteinogenic amino acids was tested using batch experiments. Batch tests were conducted using an initial concentration of each amino acid of 9000 mg COD L−1 along with 9000 mg COD L−1 acetate. Butyrate production was observed from lysine, glutamate, and serine fermentation. Lesser amounts of propionate, iso-butyrate, and iso-valerate were also observed from individual amino acids. Based on 16S rRNA gene amplicon sequencing, Anaerostignum, Intestimonas, Aminipila, and Oscillibacter all likely play a role in the conversion of amino acids to butyrate. The specific roles of other abundant taxa, including Coprothermobacter, Fervidobacterium, Desulfovibrio, and Wolinella, remain unknown, but these genera should be studied for their role in fermentation of amino acids and proteins to VFAs.
more »
« less
- Award ID(s):
- 2143446
- PAR ID:
- 10506914
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Fermentation
- Volume:
- 10
- Issue:
- 5
- ISSN:
- 2311-5637
- Page Range / eLocation ID:
- 237
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
ABSTRACT The diets of animals are essential to support development, and protein is key. Accumulation of stored nutrients can support developmental events such as molting and initiation of reproduction. Agricultural studies have addressed how dietary protein quality affects growth, but few studies have addressed the effects of dietary protein quality on developmental transitions. Studies on how dietary quality may affect protein storage and development are possible in arthropods, which store proteins in the hemolymph. We hypothesized that diets with a composition of amino acids that matches the precursor of egg yolk protein (vitellogenin, Vg) will be high quality and support both egg production and accumulation of storage proteins. Grasshoppers were fed one of two isonitrogenous solutions of amino acids daily: Vg-balanced (matched to Vg) or Unbalanced (same total moles of amino acids, but not matched to egg yolk). We measured reproduction and storage protein levels in serial hemolymph samples from individuals. The Vg-balanced group had greater reproduction and greater cumulative levels of storage proteins than did the Unbalanced group. This occurred even though amino acids fed to the Vg-balanced group were not a better match to storage protein than were the amino acids fed to the Unbalanced group. Further, oviposition timing was best explained by a combination of diet, age at the maximum level of storage protein hexamerin-270 and accumulation of hexamerin-90. Our study tightens the link between storage proteins and commitment to reproduction, and shows that dietary protein quality is vital for protein storage and reproduction.more » « less
-
Synthesis and Characterization of Amino Acid Decyl Esters as Early Membranes for the Origins of LifeUnderstanding how membrane forming amphiphiles are synthesized and aggregate in prebiotic settings is required for understanding the origins of life on Earth 4 billion years ago. Amino acids decyl esters were prepared by dehydration of decanol and amino acid as a model for a plausible prebiotic reaction at two temperatures. Fifteen amino acids were tested with a range of side chain chemistries to understand the role of amino acid identity on synthesis and membrane formation. Products were analyzed using LC-MS as well as microscopy. All amino acids tested produced decyl esters, and some of the products formed membranes when rehydrated in ultrapure water. One of the most abundant prebiotic amino acids, alanine, was remarkably easy to get to generate abundant, uniform membranes, indicating that this could be a selection mechanism for both amino acids and their amphiphilic derivatives.more » « less
-
Abstract Beta-hydroxy non-standard amino acids (β-OH-nsAAs) have utility as small molecule drugs, precursors for beta-lactone antibiotics, and building blocks for polypeptides. While the L-threonine transaldolase (TTA), ObiH, is a promising enzyme for β-OH-nsAA biosynthesis, little is known about other natural TTA sequences. We ascertained the specificity of the TTA enzyme class more comprehensively by characterizing 12 candidate TTA gene products across a wide range (20-80%) of sequence identities. We found that addition of a solubility tag substantially enhanced the soluble protein expression level within this difficult-to-express enzyme family. Using an optimized coupled enzyme assay, we identified six TTAs, including one with less than 30% sequence identity to ObiH that exhibits broader substrate scope, two-fold higher L-Threonine (L-Thr) affinity, and five-fold faster initial reaction rates under conditions tested. We harnessed these TTAs for first-time bioproduction of β-OH-nsAAs with handles for bio-orthogonal conjugation from supplemented precursors during aerobic fermentation of engineeredEscherichia coli, where we observed that higher affinity of the TTA for L-Thr increased titer. Overall, our work reveals an unexpectedly high level of sequence diversity and broad substrate specificity in an enzyme family whose members play key roles in the biosynthesis of therapeutic natural products that could benefit from chemical diversification.more » « less
-
Phosphorylated amino acids are involved in many cell regulatory networks; proteins containing these post-translational modifications are widely studied both experimentally and computationally. Simulations are used to investigate a wide range of structural and dynamic properties of biomolecules, such as ligand binding, enzyme-reaction mechanisms, and protein folding. However, the development of force field parameters for the simulation of proteins containing phosphorylated amino acids using the Amber program has not kept pace with the development of parameters for standard amino acids, and it is challenging to model these modified amino acids with accuracy comparable to proteins containing only standard amino acids. In particular, the popular ff14SB and ff19SB models do not contain parameters for phosphorylated amino acids. Here, the dihedral parameters for the side chains of the most common phosphorylated amino acids are trained against reference data from QM calculations adopting the ff14SB approach, followed by validation against experimental data. Library files and corresponding parameter files are provided, with versions that are compatible with both ff14SB and ff19SB.more » « less
An official website of the United States government

