An official website of the United States government
Abstract The selective introduction of amine groups within deconstruction products of lignin could provide an avenue for valorizing waste biomass while achieving a green synthesis of industrially relevant building blocks from sustainable sources. Here, we built and characterized enzyme cascades that create aldehydes and subsequently primary amines from diverse lignin‐derived carboxylic acids using a carboxylic acid reductase (CAR) and an ω‐transaminase (TA). Unlike previous studies that have paired CAR and TA enzymes, here we examine multiple homologs of each of these enzymes and a broader set of candidate substrates. In addition, we compare the performance of these systems in cell‐free and resting whole‐cell biocatalysis formats using the conversion of vanillate to vanillyl amine as model chemistry. We also demonstrate that resting whole cells can be recycled for multiple batch reactions. We used the knowledge gained from this study to produce several amines from carboxylic acid precursors using one‐pot biocatalytic reactions, several of which we report for the first time. These results expand our knowledge of these industrially relevant enzyme families to new substrates and contexts for environmentally friendly and potentially low‐cost synthesis of diverse aryl aldehydes and amines.
more »
« less
Aqueous Solutions of Peptides and Trialkylamines Lead to Unexpected Peptide Modification
When trialkylamines are added to buffered solutions of peptides, unexpected adducts can be formed. These adducts correspond to Schiff base products. The source of the reaction is the unexpected presence of aldehydes in amines. The aldehydes can be detected in a few ways. Most importantly, they can lead to unanticipated results in proteomics experiments. Their undesirable effects can be minimized through the addition of other amines.
more »
« less
- Award ID(s):
- 1904749
- PAR ID:
- 10329047
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 26
- Issue:
- 21
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 6481
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)Hydrogen bonding plays a critical role in maintaining order and structure in complex biological and synthetic systems. N -heterocyclic carbenes (NHCs) represent one of the most versatile tools in the synthetic chemistry toolbox, yet their potential as neutral carbon hydrogen bond acceptors remains underexplored. This report investigates this capability in a strategic manner, wherein carbene-based hydrogen bonding can be assessed by use of ditopic NH -containing molecules. N–H bonds are unique as there are three established reaction modes with carbenes: non-traditional hydrogen bonding adducts (X–H⋯:C), salts arising from proton transfer ([H–C] + [X] − ), or amines from insertion of the carbene into the N–H bond. Yet, there are no established rules to predict product distributions or the strength of these associations. Here we seek to correlate the hydrogen bond strength of symmetric and asymmetric ditopic secondary amines with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene ( IPr , a representative NHC). In symmetric and asymmetric ditopic amine adducts both the solid-state (hydrogen bond lengths, NHC interior angles) and solution-state ( 1 H Δ δ of NH signals, 13 C signals of carbenic carbon) can be related to the p K a of the parent amine.more » « less
-
Naphthoquinone (1,4-NQ) and its derivatives (NQs, juglone, plumbagin, 2-methoxy-1,4-NQ, and menadione) have a variety of therapeutic applications, many of which are attributed to redox cycling and the production of reactive oxygen species (ROS). We previously demonstrated that NQs also oxidize hydrogen sulfide (H2S) to reactive sulfur species (RSS), potentially conveying identical benefits. Here we use RSS-specific fluorophores, mass spectroscopy, EPR and UV-Vis spectrometry, and oxygen-sensitive optodes to examine the effects of thiols and thiol-NQ adducts on H2S-NQ reactions. In the presence of glutathione (GSH) and cysteine (Cys), 1,4-NQ oxidizes H2S to both inorganic and organic hydroper-/hydropolysulfides (R2Sn, R=H, Cys, GSH; n = 2–4) and organic sulfoxides (GSnOH, n = 1, 2). These reactions reduce NQs and consume oxygen via a semiquinone intermediate. NQs are also reduced as they form adducts with GSH, Cys, protein thiols, and amines. Thiol, but not amine, adducts may increase or decrease H2S oxidation in reactions that are both NQ- and thiol-specific. Amine adducts also inhibit the formation of thiol adducts. These results suggest that NQs may react with endogenous thiols, including GSH, Cys, and protein Cys, and that these adducts may affect both thiol reactions as well as RSS production from H2S.more » « less
-
We report sequential ruthenium(0)-catalysis for the synthesis of sterically-hindered amines via direct C–H arylation of simple imines and imine hydrosilylation. The method involves direct C–H arylation under neutral conditions with organoboranes enabled by ruthenium(0) catalysis. The catalytic hydrosilylation was performed in a one-pot fashion using Et 3 SiH. The reaction is compatible with a broad range of electronically- and sterically-varied imines, enabling rapid production of valuable biaryl amines in good to excellent yields. The method constitutes a two-step, one-pot procedure to synthesize sterically-hindered amines from aldehydes. The utility of this atom-economic strategy is demonstrated in one-pot, three-component coupling, direct in situ aldehyde arylation and the use of transfer hydrogenation.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/molecules26216481
