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Kim, Kwang Ho

Publications and source records attributed to Kim, Kwang Ho.

17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Impacts of Hydrogen Bond Donor Structures in Phenolic Aldehyde Deep Eutectic Solvents on Pretreatment Efficiency

As a green solvent for biomass processing, deep eutectic solvents (DESs) have shown effectiveness in biomass processing. Here, in this study, phenolic aldehydes with different numbers of methoxy groups, including 4-hydroxybenzaldehyde (HBA, no methoxy), vanillin (VA, monomethoxy), and syringaldehyde (SA, dimethoxy) were employed to synthesize DESs with choline chloride (ChCl). The presence of methoxy groups in the hydrogen bond donor structure affected DES properties, as well as biomass pretreatment performance. The high thermal stability of phenolic aldehyde DESs was shown with over 225 °C onset temperature. The hydrogen bond donor with one aldehyde and one hydroxyl group at the para position without a methoxy group (ChCl-HBA) showed the highest xylan removal and delignification, reaching 59.3 and 88.0%, respectively, leading to the highest enzymatic hydrolysis yield. Sonication after pretreatment further enhanced the hydrolysis yields, achieving 83.3% glucan conversion and 50.1% xylan conversion. In the lignin-rich fraction, the recovered lignin showed a low weight–average molecular weight under 2100 g/mol with a relatively uniform molecular weight dispersity below 1.5. This study provides insights into how the chemical structure of hydrogen bond donors in DESs affects biomass processing and paves the way for designing effective lignin-derived DES in future biorefinery processes.

09 BIOMASS FUELS↗
DOE OSTI2023

Investigation of the effects of ternary deep eutectic solvent composition on pretreatment of sorghum stover

Biomass‐derived deep eutectic solvents (DESs) have been introduced as promising pretreatment and fractionation solvents because of their mild processing conditions, easy synthesis, and green solvent components from biomass. In recent DES studies, solvent‐based third constituents like water, ethanol, and others improve the processibility of typical binary DESs. However, the impacts of these components are not well understood. Here, two solvent‐based constituents, including water and ethylene glycol, were applied to 3,4‐dihydroxybenzoic acid (DHBA)‐based DES system for improving the conversion efficiency of cellulose‐rich fraction and the properties of lignin fraction. Chemical composition, enzymatic digestibility, degree of polymerization of cellulose and physicochemical properties of lignin were used to evaluate the impact of each third constituent on biomass processing. Ternary ChCl‐DHBA DESs exhibited better performances in delignification, fermentable sugar production, and preservation of β‐O‐4 ether linkage in lignin compared with binary ChCl‐DHBA DES.

09 BIOMASS FUELS↗
DOE OSTI2022

A new approach to zip–lignin: 3,4–dihydroxybenzoate is compatible with lignification

Renewed interests in the development of bioenergy, biochemicals, and biomaterials have elicited new strategies for engineering the lignin of biomass feedstock plants. Furthermore, this study shows, for the first time, that 3,4-dihydroxybenzoate (DHB) is compatible with the radical coupling reactions that assemble polymeric lignin in plants. We introduced a bacterial 3-dehydroshikimate dehydratase into hybrid poplar (Populus alba × grandidentata) to divert carbon flux away from the shikimate pathway, which lies upstream of lignin biosynthesis. Transgenic poplar wood had up to 33% less lignin with p-hydroxyphenyl units comprising as much as 10% of the lignin. Mild alkaline hydrolysis of transgenic wood released fewer ester-linked p-hydroxybenzoate groups than control trees, and revealed the novel incorporation of cell-wall-bound DHB, as well as glycosides of 3,4-dihydroxybenzoic acid (DHBA). Two-dimensional nuclear magnetic resonance (2D-NMR) analysis uncovered DHBA-derived benzodioxane structures suggesting that DHB moieties were integrated into the lignin polymer backbone. In addition, up to 40% more glucose was released from transgenic wood following ionic liquid pretreatment and enzymatic hydrolysis. This work highlights the potential of diverting carbon flux from the shikimate pathway for lignin engineering and describes a new type of ‘zip-lignin’ derived from the incorporation of DHB into poplar lignin.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Ferric chloride aided peracetic acid pretreatment for effective utilization of sugarcane bagasse

The synergetic impacts of ferric chloride aided peracetic acid (FPA) pretreatment were investigated to enhance the total biomass utilization through effective cellulose conversion and high-quality lignin production. The sugarcane bagasse pretreatment with 2% peracetic acid (PAA) and 0.1 mol/L ferric chloride (FeCl 3 ) effectively removed 57.3% of lignin and 72.2% of xylan while preserving ~ 97% of cellulose from sugarcane bagasse under mild temperature (90 °C). The FPA pretreated sugarcane bagasse was effectively hydrolyzed with a glucose yield of 313.0 mg/g-biomass, which was 4.5 times higher than the yield of untreated biomass (69.75 mg/g-biomass) and 1.6 and 3.6 times higher than that of individual PAA and FeCl 3 pretreated sugarcane bagasse, respectively. The regenerated lignin (FPA lignin) showed great potential for further valorization by preserving the major interunit linkage (up to 86% of β-O-4) without significant carbohydrate contamination and lignin condensation due to its mild reaction conditions. In this paper, the combination of PAA and FeCl 3 synergistically enhanced the pretreatment efficiency on sugarcane bagasse and resulted in high fermentable sugar and high-quality lignin production.

09 BIOMASS FUELS↗
DOE OSTI2021

Engineered Sorghum Bagasse Enables a Sustainable Biorefinery with p-Hydroxybenzoic Acid-Based Deep Eutectic Solvent

Integrating multidisciplinary research in plant genetic engineering and renewable deep eutectic solvents (DESs) can facilitate a sustainable and economic biorefinery. In this work, we leveraged a plant genetic engineering approach to specifically incorporate C6C1 monomers into the lignin structure. By expressing the bacterial ubiC gene in sorghum, p-hydroxybenzoic acid (PB)-rich lignin was incorporated into the plant cell wall while this monomer was completely absent in the lignin of the wild-type (WT) biomass. A DES was synthesized with choline chloride (ChCl) and PB and applied to the pretreatment of the PB-rich mutant biomass for a sustainable biorefinery. The release of fermentable sugars was significantly enhanced (~190 % increase) compared to untreated biomass by the DES pretreatment. In particular, the glucose released from the pretreated mutant biomass was up to 12 % higher than that from the pretreated WT biomass. Lignin was effectively removed from the biomass with the preservation of more than half of the β-Ο-4 linkages without condensed aromatic structures. Hydrogenolysis of the fractionated lignin was conducted to demonstrate the potential of phenolic compound production. In addition, a simple hydrothermal treatment could selectively extract PB from the same engineered lignin, showing a possible circular biorefinery. These results suggest that the combination of PB-based DES and engineered PB-rich biomass is a promising strategy to achieve a sustainable closed-loop biorefinery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2020

Enhancing Enzyme-Mediated Hydrolysis of Mechanical Pulps by Deacetylation and Delignification

Alkaline induced deacetylation of the hemicellulose combined with subsequent mechanical refining enhanced the enzyme-mediated hydrolysis of pretreated corn stover. The addition of either NaOH (80 °C) or mild KOH (25 °C) to corn stover prior to mechanical refining led to greater than 80% deacetylation with the NaOH treatment also solubilizing low-molecular-weight lignin that was enriched in $β$-O-4 linkages with more than 25% and 13% of the total and surface lignin removed, respectively. Furthermore, the influence of deacetylation and delignification were further enhanced when NaOH was supplemented with 3% Na 2 SO 3 , resulting in 100% deacetylation, 34% delignification, and a >20% increase in the hydrolysis yield of the substrate xylan. A milder KOH treatment resulted in the retention of more than 95% of the lignin within the cellulose rich, water-insoluble fraction with no apparent change in the surface lignin. However, both methods resulted in enhanced xylan hydrolysis when treated with xylanases, suggesting that deacetylation had enhanced accessibility to the xylan present in the pretreated of corn stover. It was apparent that cellulose accessibility was also enhanced by partial delignification, as NaOH treatment resulted in a 65% and 43% increase in the Water Retention Value and Directed Orange dye adsorption, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Influence of hydrocracking and ionic liquid pretreatments on composition and properties of Arabidopsis thaliana wild type and CAD mutant lignins

Lignin is the primary contributor to the high cost of biofuel-production from lignocellulosic biomass. Here, in order to study lignin removal and the release of aromatic monomers, we applied hydrocracking and ionic liquid pretreatments on Arabidopsis thaliana biomass from both wild type (WT) and a mutant (CAD cxd) defective in two cinnamyl alcohol dehydrogenase genes involved in the lignin biosynthetic pathway. For Arabidopsis WT, our results highlight that pretreatments reduce average molecular weight of lignin by about 65% and decrease the content of β-O-4 linkages between lignin monomers. For Arabidopsis CAD mutant, an opposite effect is evidenced. Fewer differences were observed on depolymerization and molecular structure of lignin, which indicates that (8-O-4), (8-5), and (8-8) linkages observed in CAD mutant make lignin more resilient to pretreatment than wild-type lignin. Finally, our study shows the potential of hydrocracking pretreatment technology for extracting valuable aldehyde monomers such as vanillin and syringaldehyde from biomass.

09 BIOMASS FUELS↗