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DOE OSTI2024

Quantification of Native Lignin Structural Features with Gel–Phase 2D–HSQC 0 Reveals Lignin Structural Changes During Extraction

Our ability to study and valorize the lignin fraction of biomass is hampered by the fundamental and still unmet challenge of precisely quantifying native lignin's structural features. Here, we developed a rapid elevated-temperature 1 H– 13 C Heteronuclear Single-Quantum Coherence Zero (HSQC 0 ) NMR method that enables this precise quantification of native lignin structural characteristics even with whole plant cell wall (WPCW) NMR spectroscopy, overcoming fast spin relaxation in the gel phase. We also formulated a Gaussian fitting algorithm to perform automatic and reliable spectral integration. By combining HSQC 0 measurements with yield measurements following depolymerisation, we can confirm the combinatorial nature of radical coupling reactions during biosynthesis leading to a random sequential organization of linkages within a largely linear lignin chain. Such analyses illustrate how this analytical method can greatly facilitate the study of native lignin structure, which can then be used for fundamental studies or to understand lignin depolymerization methods like reductive catalytic fractionation or aldehyde-assisted fractionation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Quantification of Native Lignin Structural Features with Gel–Phase 2D–HSQC 0 Reveals Lignin Structural Changes During Extraction

09 BIOMASS FUELS↗

DOE OSTI2020

2D HSQC Chemical Shifts of Impurities from Biomass Pretreatment

Two dimensional (2D) heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) is a powerful analytical method which can be used to elucidate the structure of biomass. During processing, biomass is typically subjected to some form of chemical treatment which can be performed with a variety of compounds. The presence of these compounds, even in trace amounts, has the potential to contaminate the sample and lead to misinterpretation of the HSQC spectra. Here we report the chemical shifts of 29 compounds commonly used in biomass processing which have the potential to contaminate the biomass samples and lead to the misinterpretation of peaks associated with biomass (Populus trichocarpa ) pretreated via autohydrolysis. The identification of these chemical shifts could serve as a valuable tool in preventing errors in characterizing biomass via HSQC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Nanolignin-based high internal phase emulsions for efficient protection of curcumin against UV degradation

As an emulsifier, lignin exhibits excellent UV resistance on drug-loaded emulsion systems for drug delivery. However, due to the structural variation and complexity of lignins from various origins, their UV shielding performance varies with the techniques for lignin extraction, which impacts properties and the protection efficiency of lignin-based HIPEs (high internal phase emulsions). In this work, lignin nanoparticles, prepared from three lignin preparations of Eucalyptus, were used in HIPEs delivery systems to protect curcumin from degradation by UV radiation. Structures of the lignin preparations were characterized using 2D HSQC (heteronuclear single-quantum coherence) NMR (nuclear magnetic resonance), 31 P NMR, and GPC (gel permeation chromatography). The residual curcumin level after 36h UV exposure in the nanolignin-based HIPEs was over 72%, much higher than that (< 10% after 24 h UV exposure) in the oil phase without lignin, indicating that the nanolignin-based HIPEs with enhanced UV shielding ability protect curcumin better. Of the three lignin preparations, AL (alkali lignin), with the lowest molecular weight, highest contents of phenolic hydroxyl and carboxyl groups, and highest S/G ratio, displayed the best anti-UV radiation ability and the most uniform nanoparticle size.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Examining the Reactions of Ethanolamine’s Thermal Degradation Compounds in Carbon Capture through 1 H NMR and 13 C NMR

In amine scrubbing carbon capture, concerns about amine solvent degradation include whether it can affect the ability of the solvent to capture CO 2 . This study examines the interactions between the three most reported monoethanolamine (MEA) thermal degradation compounds namely, oxazolidine-2-one (OZD), N-(2-hydroxyethyl)-ethylenediamine (HEEDA), and N-(2- hydroxyethyl)-imidazoline-2-one (HEIA) with CO 2 in the presence and absence of MEA. We compared 1 H NMR, 13 C NMR, and heteronuclear single-quantum coherence (HSQC) NMR for neat OZD, HEEDA, and HEIA samples with CO 2 -loaded samples to observe changes in protonation and unique carbamate species formation. We found that OZD and HEIA did not directly react with CO 2 or undergo proton shifting based on our comparison of the neat OZD and HEIA samples with CO 2 -loaded spectra. However, we observed that the OZD can protonate when sparged with CO 2 in the presence of MEA, which suggests that the OZD acts as an intermediate. The NMR spectra for HEEDA indicated that HEEDA directly reacts with CO 2 at both amino groups and can protonate. In the presence of MEA, HEEDA and MEA can act like a solvent blend, resulting in multiple carbamates forming within the solvent. The neat HEIA spectrum, compared with CO 2 -loaded HEIA spectra, revealed similar results as OZD, where it does not react with CO 2 or protonate directly. However, HEIA does not protonate in the presence of MEA. These degradation compound reactions can increase the number of general equilibrium reactions during carbon capture and impact the model MEA solvent. This work helps provide a more complete picture of the reactions as the solvent degrades. Although this study examines CO 2 effects on thermal degradation products for MEA, other amines such as piperazine or 1- amino-3-propanol will degrade, and the degradation may speciate similarly with CO 2 . Furthermore, this study can impact and improve process models by assessing the degradation compounds’ reactions with CO 2 and potentially incorporating them into the model based on a neat solvent.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2019

Enhanced Softwood Cellulose Accessibility by H 3 PO 4 Pretreatment: High Sugar Yield without Compromising Lignin Integrity

Softwood lignocellulose is a potential feedstock for the production of biofuels and bioproducts. However, the highly cross-linked nature of softwood lignocellulose restricts enzyme access to its sugars. Thus, harsh pretreatment conditions (180–280 °C) and/or high enzyme loading are required to unlock sugars. These requirements negatively affect the economic viability of softwoods in biorefineries. Here we show that H 3 PO 4 pretreatment of pine and Douglas fir under a mild reaction temperature (50 °C) and atmospheric pressure enabled a high (~80%) glucan digestibility with low enzyme loading (5 filter paper units (FPU)/g glucan). The dissolution and regeneration of softwoods disrupted the hydrogen bonding between cellulose chains, thereby increasing the cellulose accessibility to cellulase (CAC) values by ~38-fold (from ~0.4 to 15 m 2 /g biomass). Examination of H 3 PO 4 -pretreated softwoods by cross-polarization/magic angle spin (CP/MAS), 13 C- nuclear magnetic resonance (NMR), and Fourier-transform infrared spectroscopy (FTIR) revealed that breaking of the orderly hydrogen bonding of crystalline cellulose caused the increase in CAC (higher than 11 m 2 /g biomass), which, in turn, was responsible for the high glucan digestibility of pretreated softwoods. The H 3 PO 4 pretreatment process was feedstock independent. Finally, 2D 13 C– 1 H heteronuclear single quantum coherence (HSQC) NMR showed that the lignin was depolymerized but not condensed; thus, the lignin can be available for producing high-value products.

09 BIOMASS FUELS↗

DOE OSTI2022

Trajectory Ensemble Methods Provide Single-Molecule Statistics for Quantum Dynamical Systems

The emergence of experiments capable of probing quantum dynamics at the single-molecule level requires the development of new theoretical tools capable of simulating and analyzing these dynamics beyond an ensemble-averaged description. In this article, we present an efficient method for sampling and simulating the dynamics of the individual quantum systems that make up an ensemble and apply it to study the nonequilibrium dynamics of the ubiquitous spin-boson model. We generate an ensemble of single-system trajectories, and we analyze this trajectory ensemble using tools from classical statistical mechanics. Our results demonstrate that the dynamics of quantum coherence is highly heterogeneous at the single-system level due to variations in the initial bath configuration, which significantly affects the transient exchange of coherence between the system and its bath. Here, we observe that single systems tend to retain coherence over time scales longer than that of the ensemble. We also compute a novel thermodynamic entanglement entropy that quantifies a thermodynamic driving force favoring system–bath entanglement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Multiplex Detection of Multiple-Quantum/Single-Quantum NMR Correlation Spectra

High-ordered multiple-quantum coherences have been used to gauge the size of coupled networks of nuclear spins but are seldom used in modern high-resolution solid-state NMR spectroscopy due to the low resolution of earlier techniques. Herein, we extend this work to the third dimension by designing an MQ spin counting experiment with full chemical resolution of the nuclei involved in the coherences. The technique uses multiplex processing to simultaneously acquire MQ/1Q correlation 2D spectra, with all even-ordered values of M, in the same amount of time it would take to acquire the 2Q/1Q spectrum alone. Further, we apply this multiplexed MQ/1Q correlation method to probe site clustering on functionalized silica surfaces and find the first evidence of clusters involving three or more functionalities. When applied to a supported zirconium metallocene, the observation of a 6Q coherence between six cyclopentadienyl proton nuclei confirms the colocation of two cyclopentadienyl ligands on a single metal center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Mechanism of Molecular Polariton Decoherence in the Collective Light–Matter Couplings Regime

Molecular polaritons, the hybridization of electronic states in molecules with photonic excitation inside a cavity, play an important role in fundamental quantum science and technology. Understanding the decoherence mechanism of molecular polaritons is among the most significant fundamental questions. We theoretically demonstrate that hybridizing many molecular excitons in a cavity protects the overall quantum coherence from phononinduced decoherence. The polariton coherence time can be prolonged up to 100 fs with a realistic collective Rabi splitting and quality factor at room temperature, compared to the typical electronic coherence time which is around 15 fs. Our numerically exact simulations and analytic theory suggest that the dominant decoherence mechanism is the population transfer from the upper polariton state to the dark state manifold. Increasing the collective coupling strength will increase the energy gap between these two sets of states and thus prolong the coherence lifetime. We further derived valuable scaling relations that directly indicate how polariton coherence depends on the number of molecules, Rabi splittings, and light–matter detunings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Analysis of the Amorphous and Interphase Influence of Comononomer Loading on Polymer Properties toward Forwarding Bioadvantaged Copolyamides

In this paper we present an approach for selectively modifying the properties of semicrystalline polymers by introducing “bioadvantaged” counits. With this approach, the unique functionality of biomass can be leveraged to tailor the properties of the amorphous phase of semicrystalline polymers with minimal impact on crystallinity and thermomechanical properties. As a model case, PA 6,6 copolyamides were produced using the bioadvantaged monomer trans-3-hexenedioic acid (t3HDA). The analogous structure of t3HDA to adipic acid, a PA 6,6 monomer, allows for seamless integration. Screening over the entire composition range identified the t3HDA loading (20 mol%) beyond which properties deviate appreciably from Nylon 6,6. Once identified, copolyamides of suitable compositions were upgraded to commercial quality and fully characterized to assess the influence of counit loading and polymer structure on thermal and mechanical properties. Samples were characterized using gel permeation chromatography (GPC), proton nuclear magnetic resonance spectroscopy (1H NMR), heteronuclear single quantum coherence spectroscopy (HSQC), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), tensile testing, flexural testing, and water absorption testing. t3HDA units were shown to hydrate during the harsh polycondensation to 3-hydroxyhexanedioic acid (3HHDA) and fully incorporate into the polymer backbone. Loading levels up to 20% were shown to have comparable thermal and mechanical properties in the dry state, yet moisture absorption—a known method for improving the toughness, yield strain, and elongation of polyamides—was enhanced by over 100% at 20% loading. This case study on bioadvantaged copolymers elucidates the governing structure-function principles that can be leveraged to forward value-added renewable polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Above the Energy Gap Law: Heavy Chalcogenide Substitution in NIR II-Emissive Diradicaloid Qubits

Near-infrared (NIR, 700–1700 nm)- and telecom (∼1260–1625 nm)-emissive molecules are good candidates for biological imaging and quantum sensing applications, respectively; however, bright low energy emission is rare due to exponentially increasing nonradiative decay rates in these regions, a phenomenon known as the energy gap law. Recent literature has emphasized the importance of minimizing skeletal modes to prevent increased nonradiative decay rates, but most organic lumiphores in these regions utilize large, conjugated scaffolds containing many C═C modes. Here we report a compact, telecom-emissive scaffold, tetrathiafulvalene-2,3,6,7-tetraselenate, or TTFts, that displays remarkable air, water, and acid stability, exhibits record quantum yields and brightness values, and retains quantum coherence under ambient conditions. These properties are enabled through methodical selenium substitution, which bathochromically shifts emission while shifting skeletal vibrations to lower energies. This new scaffold validates heavy heteroatom substitution strategies and establishes a new class of bright telecom emitters and robust qubits.

biological imaging↗

DOE OSTI2020

Investigation of a Lignin-Based Deep Eutectic Solvent Using p -Hydroxybenzoic Acid for Efficient Woody Biomass Conversion

Deep eutectic solvents (DESs) are effective solvents for biomass conversion and have been proposed as alternatives to ionic liquids (ILs). In this paper, we first report an effective pretreatment of woody biomass using a novel hardwood lignin-based DES prepared from p -hydroxybenzoic acid (PB) and choline chloride (ChCl), which are used as the hydrogen bond donor and acceptor, respectively. The impacts of the ChCl-PB DES on structural properties and enzymatic hydrolysis of poplar wood were comprehensively evaluated. The performance of ChCl-PB DES was also compared with two other DESs with p -coumaric acid (PCA) and 4-hydroxybenzaldehyde (PHA) as the hydrogen bond donors, which have been successfully applied to herbaceous biomass conversion in previous studies. The results showed that hemicellulose and lignin were effectively fractionated during the proposed ChCl-PB DES pretreatment under a relatively mild temperature. The ChCl-PB DES pretreatment resulted in up to 69% of delignification, and the pretreated poplar residues had over 90% of glucose yield by a 72 h-enzymatic hydrolysis. Transformation of poplar biomass during the DES pretreatment was evaluated by gel permeation chromatography (GPC), two-dimensional heteronuclear single quantum coherence (2D-HSQC), and 31 P nuclear magnetic resonance (NMR) spectroscopies. The recovered lignin showed relatively high purity, narrow molecular weight distribution (PDI < 1.6), and relatively low molecular weight (~1400 g/mol for M w ). A sustainable process was achieved by recycling DES as well as the utilization of PB, which is a producible aromatic compound from hardwood lignin, for the proposed DES formation in the system. This study indicates that the proposed novel DES with a hardwood lignin-based PB compound is a promising pretreatment solvent to achieve an economically feasible biomass conversion process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Effective Biomass Fractionation through Oxygen-Enhanced Alkaline–Oxidative Pretreatment

The high recalcitrance of plant cell walls is an obstacle for effective chemical or biological conversion into renewable chemicals and transportation fuels. Here, we investigated the utilization of both oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) as co-oxidants during alkaline-oxidative pretreatment to improve biomass fractionation and increase enzymatic digestibility. The oxidative pretreatment of hybrid poplar was studied over a variety of conditions. Employing O 2 in addition to H 2 O 2 as a co-oxidant during the two-stage alkaline pre-extraction/copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in a substantial improvement in delignification relative to using H 2 O 2 alone during the second-stage Cu-AHP pretreatment, leading to high overall sugar yields even at H 2 O 2 loadings as low as 2% (w/w of original biomass). The presence of H 2 O 2 , however, was both critical and synergistic. Performing analogous reactions in the absence of H 2 O 2 resulted in approximately 25% less delignification and a 30% decrease in sugar yields. Here, the lignin isolated from this dual oxidant second stage had high aliphatic hydroxyl group content and reactivity to isocyanate, indicating that it is a promising substrate for the production of polyurethanes. To test the suitability of the isolated lignin as a source of aromatic monomers, the lignin was subjected to a sequential Bobbitt’s salt oxidation followed by formic-acid catalyzed depolymerization process. Monomer yields of approximately 17% (w/w) were obtained, and the difference in yields was not significant between lignin isolated from our Cu-AHP process with and without O 2 as a co-oxidant. Thus, the addition of O 2 did not lead to significant lignin crosslinking, a result consistent with the two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR spectra of the isolated lignin.

09 BIOMASS FUELS↗

DOE OSTI2021

Revealing the Surface Structure of CdSe Nanocrystals by Dynamic Nuclear Polarization-Enhanced 77 Se and 113 Cd Solid-State NMR Spectroscopy

Dynamic nuclear polarization (DNP) solid-state NMR (SSNMR) spectroscopy was used to obtain detailed surface structures of zinc blende CdSe nanocrystals (NCs) with plate or spheroidal morphologies which are capped by carboxylic acid ligands. 1D 113 Cd and 77 Se cross-polarization magic angle spinning (CPMAS) NMR spectra revealed distinct signals from Cd and Se atoms on the surface of the NCs, and those residing in bulk-like environments, below the surface. 113 Cd cross-polarization magic-angle-turning (CP-MAT) experiments identified CdSe 3 O, CdSe 2 O 2 , and CdSeO 3 Cd coordination environments on the surface of the NCs, where the oxygen atoms are presumably from coordinated carboxylate ligands. The sensitivity gain from DNP enabled natural isotopic abundance 2D homonuclear 113 Cd– 113 Cd and 77 Se– 77 Se and heteronuclear 113 Cd– 77 Se scalar correlation solid-state NMR experiments which revealed the connectivity of the Cd and Se atoms. Importantly, 77 Se{ 113 Cd} scalar heteronuclear multiple quantum coherence ( J -HMQC) experiments were used to selectively measure one-bond 77 Se– 113 Cd scalar coupling constants ( 1 J ( 77 Se, 113 Cd)). With knowledge of 1 J ( 77 Se, 113 Cd), heteronuclear 77 Se{ 113 Cd} spin echo ( J -resolved) NMR experiments were used to determine the number of Cd atoms bonded to Se atoms and vice versa. Furthermore, the J -resolved experiments directly confirmed that major Cd and Se surface species have CdSe 2 O 2 and SeCd 4 stoichiometries, respectively. Considering the crystal structure of zinc blende CdSe and the similarity of the solid-state NMR data for the platelets and spheroids, we conclude that the surface of the spheroidal CdSe NCs is primarily composed of {100} facets. The methods outlined here will generally be applicable to obtain detailed surface structures of various main group semiconductor nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

An epitaxial graphene platform for zero-energy edge state nanoelectronics

Graphene’s original promise to succeed silicon faltered due to pervasive edge disorder in lithographically patterned deposited graphene and the lack of a new electronics paradigm. Here we demonstrate that the annealed edges in conventionally patterned graphene epitaxially grown on a silicon carbide substrate (epigraphene) are stabilized by the substrate and support a protected edge state. The edge state has a mean free path that is greater than 50 microns, 5000 times greater than the bulk states and involves a theoretically unexpected Majorana-like zero-energy non-degenerate quasiparticle that does not produce a Hall voltage. In seamless integrated structures, the edge state forms a zero-energy one-dimensional ballistic network with essentially dissipationless nodes at ribbon–ribbon junctions. Seamless device structures offer a variety of switching possibilities including quantum coherent devices at low temperatures. This makes epigraphene a technologically viable graphene nanoelectronics platform that has the potential to succeed silicon nanoelectronics.

42 ENGINEERING↗

DOE OSTI2022

Chern Fermi pocket, topological pair density wave, and charge-4e and charge-6e superconductivity in kagomé superconductors

Abstract The recent discovery of novel charge density wave (CDW) and pair density wave (PDW) in kagomé lattice superconductors A V 3 Sb 5 ( A = K, Rb, Cs) hints at unexpected time-reversal symmetry breaking correlated and topological states whose physical origin and broader implications are not understood. Here, we make conceptual advances toward a mechanism behind the striking observations and new predictions for novel macroscopic phase coherent quantum states. We show that the metallic CDW state with circulating loop currents is a doped orbital Chern insulator near van Hove filling. The emergent Chern Fermi pockets (CFPs) carry concentrated Berry curvature and orbital magnetic moment. We find that the pairing of electrons on the CFPs leads to a superconducting state with an emergent vortex-antivortex lattice and the formation of a complex triple- Q PDW. A plethora of correlated and topological states emerge, including a never-before-encountered chiral topological PDW superconductor, a loop-current pseudogap phase, and vestigial charge-4 e and charge-6 e superconductivity in staged melting of the vortex-antivortex lattice and hexatic liquid crystal. Our findings reveal previously unknown nature of the superconducting state of a current-carrying Chern metal, with broad implications for correlated and topological materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Trapping light in air with membrane metasurfaces for vibrational strong coupling

Optical metasurfaces can manipulate electromagnetic waves in unprecedented ways at ultra-thin engineered interfaces. Specifically, in the mid-infrared (mid-IR) region, metasurfaces have enabled numerous biochemical sensing, spectroscopy, and vibrational strong coupling (VSC) applications via enhanced light-matter interactions in resonant cavities. However, mid-IR metasurfaces are usually fabricated on solid supporting substrates, which degrade resonance quality factors (Q) and hinder efficient sample access to the near-field electromagnetic hotspots. Besides, typical IR-transparent substrate materials with low refractive indices, such as CaF 2 , NaCl, KBr, and ZnSe, are usually either water-soluble, expensive, or not compatible with low-cost mass manufacturing processes. Here, we present novel free-standing Si-membrane mid-IR metasurfaces with strong light-trapping capabilities in accessible air voids. We employ the Brillouin zone folding technique to excite tunable, high-Q quasi-bound states in the continuum (qBIC) resonances with our highest measured Q-factor of 722. Leveraging the strong field localizations in accessible air cavities, we demonstrate VSC with multiple quantities of PMMA molecules and the qBIC modes at various detuning frequencies. Our new approach of fabricating mid-IR metasurfaces into semiconductor membranes enables scalable manufacturing of mid-IR photonic devices and provides exciting opportunities for quantum-coherent light-matter interactions, biochemical sensing, and polaritonic chemistry. The authors introduce a mid-IR metasurface fabricated by decorating a free-standing Si-membrane with air holes. The enhanced light-matter interactions in such air cavities enable vibrational strong coupling and advanced biochemical sensing.

infrared spectroscopy↗

DOE OSTI2021

Strikingly high amount of tricin-lignin observed from vanilla (Vanilla planifolia) aerial roots

Lignin has attracted tremendous interest as a renewable resource for biofuels, biomaterials, and chemicals especially in the era of bio-based refineries. The structural studies of lignin play an essential role in both understanding the nature and biosynthesis of these polymers and optimizing their valorization values. In this study, we have investigated the structures of lignin from different tissues—aerial roots, nodes, internodes, and seeds, from vanilla (Vanilla planifolia) by using gel permeation chromatography (GPC), heteronuclear single-quantum coherence (HSQC) nuclear magnetic resonance (NMR), and 31P NMR. An unusual tricin-lignin was observed in the aerial roots of vanilla with an strikingly high level of tricin unit, whereas the lignin from the nodes and internodes displayed traditional S/G type lignin with only 4–10% tricin abundance. The aerial roots lignin is primarily composed of β-O-4' alkyl-aryl ether substructures (96% of linkages) in comparison to 65 and 73% in the nodes and internodes lignin, respectively. Additionally, thioacidolysis quantification results showed that lignin from aerial roots has 29.1 mg g -1 tricin, about 3- to 5-fold higher than the lignins isolated from nodes (10.1 mg g -1 ) and internodes (6.9 mg g -1 ). This communication of a particularly high level of tricin-lignin in vanilla plant has important impacts including: (1) the presence of the high amount of tricin as part of lignin from aerial roots could play a vital role for the valorization of lignin, even tricin itself, as a feedstock for value-added chemicals and commodities; and (2) it could open new ways to scientists to design and engineer the structure of tricin-lignin, or lignin in general, to confer plants with new or improved properties due to the plasticity of lignification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗