Controlling lignin solubility and hydrogenolysis selectivity by acetal-mediated functionalization

Komarova, Anastasia O.; Luterbacher, Jeremy S.

doi:10.1039/d1gc02575a

Cited by 21 publications

(19 citation statements)

References 44 publications

(42 reference statements)

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“…As shown in Figure , the assignment of major cross-signals in the spectra of lignin is based on previous publications. , 2D-HSQC NMR analysis confirmed the formation of the six-membered 1,3-dioxane structure in FAL-T80–90t100–120C80–90 samples. The formation of the six-membered 1,3-dioxane structures in FAL-T80–90t100–120C80–90 was confirmed by the signal at δ C /δ H 92.5/4.9 ppm in the side-chain region. , This indicated that the formic acid reacted with lignin’s α,γ-diol group during the pretreatment. Therefore, the addition of formic acid successfully blocked the reactive benzylic positions during the pretreatment, which effectively prevented the irreversible condensation of lignin.…”

Section: Resultssupporting

confidence: 65%

“…As shown in Figure 3, the assignment of major cross-signals in the spectra of lignin is based on previous publications. 35,36 2D-HSQC NMR analysis confirmed the formation of the sixmembered 1,3-dioxane structure in FAL-T80−90t100− 120C80−90 samples. The formation of the six-membered 1,3-dioxane structures in FAL-T80−90t100−120C80−90 was confirmed by the signal at δ C /δ H 92.5/4.9 ppm in the sidechain region.…”

Section: Methodsmentioning

confidence: 74%

“…The formation of the six-membered 1,3-dioxane structures in FAL-T80−90t100−120C80−90 was confirmed by the signal at δ C /δ H 92.5/4.9 ppm in the sidechain region. 26,36 This indicated that the formic acid reacted with lignin's α,γ-diol group during the pretreatment. Therefore, the addition of formic acid successfully blocked the reactive benzylic positions during the pretreatment, which effectively prevented the irreversible condensation of lignin.…”

Section: Methodsmentioning

confidence: 99%

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Highly Efficient Fractionation of Cornstalk into Noncondensed Lignin, Xylose, and Cellulose in Formic Acid

Xie

Fan

et al. 2022

J. Agric. Food Chem.

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Traditional pretreatment of lignocellulose is usually conducted under higher acidic and high temperature conditions, which leads to both the degradation of sugar and the condensation of lignin, hindering the subsequent conversion. An effective approach to fractionate lignocellulose into 93.9% of noncondensed lignin, 99.4% of cellulose, 17.8% of xylose, and 66.7% of xylooligosaccharides under mild conditions was developed using the formic acid solution at 80 °C for 100 min. The β-O-4 bond content of lignin fractionated with formic acid (54.6 per 100 C9 units) was higher than dioxasolv lignin (48.4 per 100 C9 units), indicating that formic acid pretreatment well protected the ether bonds in lignin. Therefore, the hydrogenolysis of fractionated lignin contributed to 28.0% of aromatic monomer yield, which was comparable to dioxasolv lignin. As cellulose possesses a large amount of porosity because lignin was separated from lignocellulose, the hydrolysis of fractionated cellulose by molten salt hydrates gave a 96.4% of glucose yield.

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Section: Resultssupporting

confidence: 65%

Section: Methodsmentioning

confidence: 74%

Section: Methodsmentioning

confidence: 99%

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Highly Efficient Fractionation of Cornstalk into Noncondensed Lignin, Xylose, and Cellulose in Formic Acid

Xie

Fan

et al. 2022

J. Agric. Food Chem.

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“…S.3.1). [15,29,30] We performed 8 extractions with terephthalic aldehyde (TALD) to glyoxylic acid (GA) ratios ranging from 0.1 to 6.01. Two additional control experiments were performed where lignin was extracted only in presence of GA or TALD.…”

Section: Lignin Extraction and Characterizationmentioning

confidence: 99%

Controlled dual functionalization of lignin generates unique properties in gelatin-based hydrogels

Bertella

Rana

Karami

et al. 2022

Preprint

Self Cite

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Uncontrolled side reactions during lignin fractionation lead to the loss of its chemical functionalities and the uncontrolled formation of unwanted structures. Because of these structural issues, functionalization steps are usually performed on residual active sites of isolated lignin in order to improve reactivity and/or miscibility towards other materials. Even with these additional steps, potential applications—especially high-performance applications—are generally substantially curtailed. In this work, we use aldehyde assisted fractionation (AAF) on this process with two multifunctional aldehydes to introduce multiple functionalities (aldehydes and carboxylic acids) on the lignin in a controlled way and in a single step from lignocellulosic biomass. We show that the quantity of the various functionalities can be easily monitored and tuned in order to impart different properties to the lignin in terms of reactivity and solubility. These bi-functional lignins were then employed in the fabrication of novel cross-linked gelatin-based hydrogels for soft tissue engineering. The resulting hydrogels showed enhanced and controllable mechanical (rheology, compressive and tensile), adhesive, temperature-resistant and self-healing properties but only when a bi-functional lignin was used. This work demonstrates the importance and potential of controlled multi-functionalization of lignin, opening the way for its use in high performance materials.

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“…The choice of aldehyde determines the structure of the extracted lignin, and consequently its solubility and properties. 25 The AAF technology enables the simultaneous isolation of highquality lignin from biomass and its controlled functionalization. 26 To extract the lignin utilized in this work, glyoxylic acid (GA) has been used as the protection group during AAF.…”

Section: ■ Introductionmentioning

confidence: 99%

Ductile, High-Lignin-Content Thermoset Films and Coatings

Boarino,

Charmillot,

Figueirêdo

et al. 2023

ACS Sustainable Chem. Eng.

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In the context of transitioning toward a more sustainable use of natural resources, the application of lignin to substitute commonly utilized petroleum-based plastics can play a key role. Although lignin is highly available at low cost and presents interesting properties, such as antioxidant and UV barrier activities, its application is limited by its low reactivity, which is a consequence of harsh conditions normally used to extract lignin from biomass. In this work, the use of glyoxylic acid lignin (GA lignin), rich in carboxylic acid groups and hence highly reactive toward epoxy cross-linkers, is presented. GA lignin, which is directly extracted from biomass via a one-step aldehyde-assisted fractionation process, allowed the preparation of thermoset films and coatings via a simple reaction with sustainable poly(ethylene glycol) diglycidyl ether and glycerol diglycidyl ether cross-linkers. This allows one to prepare freestanding films containing up to 70 wt % lignin with tunable mechanical properties and covalently surface-attached coatings containing up to 90 wt % lignin with high solvent resistance. Both films and coatings display antioxidant properties and combine excellent UV barrier activity with high visible transparency, which is attractive for applications in sustainable food packaging.

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Controlling lignin solubility and hydrogenolysis selectivity by acetal-mediated functionalization

Abstract: Existing lignocellulosic biomass fractionation processes produce lignin with random, interunit C–C bonds that inhibit its depolymerization and constrain its use. Here, we exploit the aldehyde stabilization of lignin to tailor...

Cited by 21 publications

References 44 publications

Highly Efficient Fractionation of Cornstalk into Noncondensed Lignin, Xylose, and Cellulose in Formic Acid

Highly Efficient Fractionation of Cornstalk into Noncondensed Lignin, Xylose, and Cellulose in Formic Acid

Controlled dual functionalization of lignin generates unique properties in gelatin-based hydrogels

Ductile, High-Lignin-Content Thermoset Films and Coatings

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