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Precursor-Dependent Routing of Aromatic Amino Acids Determines Lignin Structure in Grasses by Sensitivity-Enhanced Solid-State NMR
Lignin biosynthesis in grasses exhibits unique metabolic flexibility, yet the precursor-specific routing of carbon into lignin polymers remains poorly resolved in planta. Here, we combine 13 C-isotope labeling with solid-state NMR under sensitivity-enhancement by dynamic nuclear polarization (DNP), to directly track phenylalanine- and tyrosine-derived carbon incorporation into the lignin polymer in Brachypodium distachyon. Precursor-specific 13 C labeling reveals that phenylalanine is the dominant contributor to canonical guaiacyl and syringyl lignins, whereas tyrosine preferentially enriches hydroxyphenyl lignin and hydroxycinnamates, including ferulates characteristic of grass cell walls. Two-dimensional 13 C− 13 C correlation NMR resolves distinct lignin moieties arising from each precursor. Disruption of pcoumarate 3-hydroxylase (C3H) selectively impairs phenylalanine-derived lignification, while tyrosine-derived lignin remains comparatively unchanged, maintaining polymer assembly through alternative metabolic routes. These findings show precursordependent control of lignin composition and reveal tyrosine-mediated lignification as a compensatory pathway in grasses. This work also establishes precursor-resolved solid-state NMR and DNP as a powerful framework for dissecting lignin biosynthesis and metabolic plasticity in plant cell walls.
Understanding Electrochemical Alcohol Hydrogenolysis Enabled by Carbonyl Reduction in Lignocellulosic Biomass-Derived Aromatic Oxygenates
Molecules derived from lignocellulosic biomass are oxygenates with multiple oxygen-containing functional groups, such as hydroxyl and carbonyl groups. Therefore, the ability to selectively reduce a specific oxygenate group is essential for the reductive upgrading of such molecules. Previous studies on electrochemical biomass conversion have shown that alcohol hydrogenolysis, which involves cleavage of the σ(C–O alcohol ) bond, is extremely challenging for furfural and 5-hydroxymethylfurfural (HMF) derivatives, including furfuryl alcohol, 5-methylfurfuryl alcohol (MFA), and 2,5-bis(hydroxymethyl)furan (BHMF). In contrast, HMF itself undergoes alcohol hydrogenolysis relatively easily in acidic aqueous media. Considering that the only structural difference between HMF and BHMF or MFA is the presence of a carbonyl group, this observation raises the question of whether the carbonyl group in HMF facilitates alcohol hydrogenolysis. In this study, we designed systematic experiments to provide a coherent explanation of when and how a carbonyl group enables hydrogenolysis of a copresent alcohol group. Specifically, we show that alcohol hydrogenolysis in HMF proceeds via reduction of the carbonyl group to a ketyl radical, followed by a spin-center shift (SCS) through extended π conjugation. We also elucidate the effect of pH on the selectivity between carbonyl hydrogenation and alcohol hydrogenolysis, both of which share the ketyl radical intermediate. This mechanistic understanding enhances our ability to predict and control alcohol hydrogenolysis in the reductive upgrading of biomass-derived oxygenates.
Tandem Reactions of CO2 Reduction and Ethane Aromatization
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Suppressing vanadium crossover using sulfonated aromatic ion exchange membranes for high performance flow batteries
Novel ion exchange membrane with just the right width of selective aqueous ionic domain (<0.6 nm) and unique functionalities show extraordinary ion selectivity. These unique ion transport properties of our membrane is reflected in a remarkable flow battery performance.
Electrostatics does not dictate the slip-stacked arrangement of aromatic π–π interactions
According to the Hunter–Sanders model, geometries in π–π systems arise from competition between quadrupolar electrostatics (favoring an edge-to-face geometry) and London dispersion (favoring stacking), but this model misrepresents the molecular physics.
Expeditious synthesis of aromatic-free piperidinium-functionalized polyethylene as alkaline anion exchange membranes
Piperidinium-functionalized polyethylene-based alkaline anion exchange membranes that show high hydroxide conductivities and good alkaline stabilities are easily prepared using photocatalytic hydroamination reactions.
Catalyst choice impacts aromatic monomer yields and selectivity in hydrogen-free reductive catalytic fractionation
Pd/C and Pt/C show high activity for hydrogen-free reductive catalytic fractionation compared to Ru/C and Ni/C.
A skeletal randomization strategy for high-performance quinoidal-aromatic polymers
A simple and effective skeletal randomization strategy is proposed to finely tune solution-state aggregation towards simultaneously improving the solubility and crystallinity of conjugated polymers, leading to a markedly boosted hole mobility.
Reactivity in Friedel–Crafts aromatic benzylation: the role of the electrophilic reactant
Density functional theory is employed in understanding the reactivity in the TiCl 4 catalyzed Friedel–Crafts benzylation of benzene with substituted benzyl chlorides in nitromethane solvent.
Achieving high productivity of 2-pyrone-4,6-dicarboxylic acid from aqueous aromatic streams with Novosphingobium aromaticivorans
Enhancing the production of biochemicals from lignocellulosic biomass is one potential way to decrease society's dependence on fossil fuels.
One-pot single-step copolymerization of aromatic trifluorovinyl ethers toward perfluorocyclobutyl (PFCB) segmented copolymers
A segmented PFCB aryl ether copolymer was synthesized directly from two aryl TFVE monomers having different reactivities and the blocky copolymer structure was confirmed by 19 F NMR spectroscopic data.
Biochemical and structural characterization of an aromatic ring–hydroxylating dioxygenase for terephthalic acid catabolism
Significance More than 400 million tons of plastic waste is produced each year, the overwhelming majority of which ends up in landfills. Bioconversion strategies aimed at plastics have emerged as important components of enabling a circular economy for synthetic plastics, especially those that exhibit chemically similar linkages to those found in nature, such as polyesters. The enzyme system described in this work is essential for mineralization of the xenobiotic components of poly(ethylene terephthalate) (PET) in the biosphere. Our description of its structure and substrate preferences lays the groundwork for in vivo or ex vivo engineering of this system for PET upcycling.
Valence and patterning of aromatic residues determine the phase behavior of prion-like domains
Abstract not provided
Evolving a New Electron Transfer Pathway for Nitrogen Fixation Uncovers an Electron Bifurcating-Like Enzyme Involved in Anaerobic Aromatic Compound Degradation
There is increasing evidence that protein electron carriers like Fd evolved to form specific partnerships with select electron donors and acceptors to keep native electron transfer pathways insulated from one another. This makes it challenging to integrate a Fd-dependent pathway such as biological nitrogen fixation into non-nitrogen-fixing organisms and provide the high-energy reducing power needed to fix nitrogen.