Comprehensive characterization of hemicelluloses obtained from Gleditsia sinensis Lam. pods and the application of moderately degraded hemicelluloses in galactomannan film.

The Gleditsia sinensis Lam. pods (GSP) are consistently discarded as waste after saponin extraction due to a lack of industrial or high-value utilization. Herein, the hemicelluloses were extracted from two varieties of GSP and subjected to comprehensive characterization. The molar mass of DMSO-soluble hemicelluloses (53.3-66.0 kDa) was higher compared to that of alkali-soluble ones (24.9-32.6 kDa). The presence of minimal acetyl substitution (3.85-4.49 %) on xylan was unequivocally confirmed. NMR spectroscopic analysis indicated that the hemicelluloses in GSP predominantly consist of a 1,4-ß-ᴅ-Xyl backbone with arabinose substituents at O-3 and 4-O-methyl-α-ᴅ-GlcA substituents at O-2 of the xylose residues. p-Coumaric acid substitution also occurred on the 1,4-ß-ᴅ-Xyl backbone. Hydrothermal treatment significantly reduced the hemicelluloses' relative molar mass and produced 7-10 % xylo-oligosaccharides. Furthermore, the moderately degraded hemicelluloses exhibited significantly enhanced biological activity. Finally, the incorporation of the moderately degraded hemicelluloses imparted the galactomannan film with exceptional antioxidant properties (81.1 % DPPH scavenging activity), while negligibly affecting its transparency. Our study's findings will contribute to a comprehensive understanding of the structural and biochemical properties of hemicellulose in waste G. sinensis pods, thereby facilitating their enhanced utilization in industrial applications.

Efficient production of xylooligosaccharides from Camellia oleifera shells pretreated by pyruvic acid at lower temperature.

XOS production from lignocellulose using organic carboxylic acids and alkyd acids has been widely reported. However, it still faces harsh challenges such as high energy consumption, high cost, and low purity. Pyruvic acid (PYA), a carbonyl acid with carbonyl and carboxyl groups, was used to produce XOS due to its stronger catalytic activity. In this work, XOS was efficiently prepared from COS in an autoclave under the condition of 0.21 M PYA-121 °C-35 min. The total yield of XOS reached 68.72 % without producing any toxic by-products, including furfural (FF) and 5-hydroxymethylfurfural (5-HMF). The yield of xylobiose (X2), xylotriose (X3), xylotetraose (X4), and xylopentaose (X5) were 20.58 %, 12.47 %, 15.74 %, and 10.05 %, respectively. Meanwhile, 89.05 % of lignin was retained in the solid residue, which provides a crucial functional group for synthesizing layered carbon materials (SRG-a). It achieves excellent electromagnetic shielding (EMS) performance through graphitization, reaching -30 dB at a thickness of 2.0 mm. The use of a PYA catalyst in the production of XOS has proven to be an efficient method due to lower temperature, lower acid consumption, and straightforward operation.

Structural characterization of lignin from the green pretreatments for co-producing xylo-oligosaccharides and glucose: Toward full biomass utilization.

Three green non-enzymatic catalysis pretreatments (NECPs) including autohydrolysis, subcritical CO2-assisted seawater autohydrolysis, and inorganic salt catalysis were utilized to simultaneously produce xylo-oligosaccharides (XOS), glucose, and cellulolytic enzyme lignin (CEL) from sugarcane bagasse (SCB). The yield of XOS in all three NECPs was over 50 % with a competitive glucose yield of enzymatic hydrolysis. And the effects of different pretreatments on the chemical structure and composition of CEL samples were also investigated. The pretreatments significantly increased the thermal stability, yield, and purity of the CEL samples. Moreover, the net yield of lignin was 58.3 % with lignin purity was 98.9 % in the autohydrolysis system. Furthermore, there was a decrease in the molecular weight of CEL samples as the pretreatment intensity increased. And the original lignin structural units sustained less damage during the NECPs, due to the cleavage of the ß-O-4 bonds dominating lignin degradation. Meanwhile, these pretreatments increased the phenolic-OH in CEL samples, making the lignin more reactive, and enhancing its subsequent modification and utilization. Collectively, the described techniques have demonstrated practical significance for the coproduction of XOS and glucose, and lignin, providing a promising strategy for full utilization of biomass.

Fabrication of multi-functional biodegradable liquid mulch utilizing xyloglucan derived from tamarind waste for agricultural application.

Biodegradable liquid mulch is considered a promising alternative to plastic mulch for sustainable agriculture. This work proposed a xyloglucan-based liquid mulch with multi-function using a combination of chemical modification and blending methods. The esterification product of tamarind xyloglucan (TXG) from forestry wastes was synthesized with benzoic anhydride (BA). The effect of esterification modification was investigated, and BA-TXG was utilized as a film-forming and sand-fixation agent. The rheological properties, thermal stability, and hydrophobicity were improved following esterification. Additionally, waterborne polyurethane and urea were incorporated into the mulch to enhance its mechanical strength (23.28 MPa, 80.71 %), and homogeneity, as well as improve its nutritive properties. The xyloglucan-based liquid mulch has excellent UV protection, a high haze value (approximately 90 %), and retains water at a rate of 80.45 %. SEM and immersion experiment showed the effect of xyloglucan-based liquid mulch on sustainable sand-fixation. Moreover, the liquid mulch treatment demonstrated an impressive germination rate of 83.8 % and degradation rate of 51.59 % (60 days). The modified polysaccharide film increases stability and slows down the degradation rate. Tamarind xyloglucan-based liquid mulch exhibits powerful and diverse optical properties as well as sand fixation functions, indicating their great potential in sustainable agriculture as an alternative to plastic mulch.

Structural variations of lignin and lignin-carbohydrate complexes from the fruit shells of Camellia oleifera during ripening.

Camellia oleifera fruit shell (CFS), a waste lignocellulosic biomass resulting from Camellia oleifera oil production industry, is abundantly available in Southern China. Herein, to understand the structural variations of CFS lignins and lignin-carbohydrate complexes (LCC) during ripening, the native lignin and LCC fractions from CFS (harvested every seven days from October 1 to 30, 2022) were isolated and characterized systematically. The molecular weights of both MWL and DEL fractions steadily increased during ripening. CFS lignins contained abundance of ß-O-4' linkages (maximum of 58.6 per 100Ar in DEL-2), and had low S/G ratios (S/G < 0.6). Moreover, the amounts of ß-O-4' linkages in MWL, DEL, and LCC-AcOH fractions increased first and then decreased during ripening. The main lignin-carbohydrate linkages in the LCC-AcOH fractions were benzyl-ether (7.0-9.4 per 100Ar) and phenyl-glycoside (4.5-5.2 per 100Ar) bonds. Based on the quantitative results, the potential structural diagrams of lignins from different ripening stages of CFS were proposed. Additionally, the LCC-AcOH fractions exhibited pronounced antioxidant capacity and were promising as natural antioxidants. The properties and functions of lignin in plant cell walls, as well as its further appreciation, are crucial for the design and selection of feasible pretreatment strategies for the lignocellulosic materials.

Structural characterization of lignin-carbohydrate complexes from Chinese quince fruits extracted after enzymatic hydrolysis pretreatment.

Chinese quince fruit (CQF) contains abundant pectin; however, the pectin cannot be efficiently separated by conventional approaches because of strong lignin-carbohydrate complexes (LCC). In this study, to elucidate the structural characteristics of the original LCC formed by lignin and pectin in CQF, single and multiple enzymatic hydrolysis pretreatments were innovatively performed, and the resulting LCC preparations were comprehensively characterized using a series of techniques. The enzymatic hydrolysis pretreatments significantly increase the LCC yield, releasing LCC fractions with low molecular weights (Mw = 4660-8288 Da). LCC-4, isolated by pretreatment with cellulase plus xylanase, had the highest galacturonic acid content (15.5 %), followed by LCC-2 (isolated by xylanase pretreatment) of 14.0 %. In CQF, lignin develops lignin-carbohydrate (LC) bonds with pectin to form LCC, with phenyl-glycoside bond being the dominant linkage. Although the pectinase pretreatment reduced the pectin content, signals of the LC linkages in the 2D-HSQC spectra were enhanced. LCC-4 could be considered as the most representative of the original LCC in CQF due to its high pectin content and multiple LCC signals in the 2D-HSQC spectrum. The structural understanding of the original LCC in CQF will lay a foundation for designing appropriate methods for extracting pectin from CQF.

Coproduction of xylooligosaccharides, glucose, and less-condensed lignin from sugarcane bagasse using syringic acid pretreatment.

Current strategies for the production of xylooligosaccharides (XOS) from biomass through non-enzymatic catalysis often led to a certain degree of lignin condensation, which severely restrains subsequent enzyme hydrolysis of cellulose. Herein, syringic acid (SA) pretreatment was investigated to coproduce XOS, glucose, and less-condensed lignin from sugarcane bagasse. SA acted as a catalyst and lignin condensation inhibitor during the pretreatment. The highest XOS yield of 58.7% (27.7% xylobiose and 24.7% xylotriose) was obtained at 180 °C - 20 min - 9% SA, and the corresponding xylose/XOS ratio was only 0.42. Compared with the pretreatment at 180 °C - 20 min - 0% SA, the addition of 9% SA increased the glucose yield from 85.7% to 92.4% and decreased the degree of lignin condensation from 0.55 to 0.42. Moreover, 26.7% of SA could be easily recovered. This work presents a pretreatment strategy in which the efficient production of XOS and the suppression of lignin condensation are achieved simultaneously.

Production of xylooligosaccharides from Camellia oleifera Abel fruit shell using a shell-based solid acid catalyst.

This study aimed to produce xylooligosaccharides (XOS) from Camellia oleifera Abel fruit shell (CFS) using a shell-based solid acid derived from CFS (CFS-BSA). CFS-BSA preparation was optimized by incomplete carbonization at 450 °C for 1 h, followed by sulfonation at 130 °C for 8 h to yield a -SO3H functional group concentration of 1.04 mmol/g. When CFS-BSA was used to hydrolyze CFS with a 1:5 ratio of CFS-BSA to CFS at 170 °C for 20 min, a maximum XOS yield (X2-X5) of 51.41 % was achieved, which was notably higher than when using subcritical H2O solely. CFS-BSA can be recycled and reused at least six times by sieving without a substantial loss in its catalytic activity. CFS-BSA can also be used to produce XOS from other lignocellulosic materials such as corncob (41.04 %), sugarcane bagasse (45.03 %), corn stalk (45.89 %), birchwood (46.05 %), and poplar (40.10 %).

Sequential aqueous acetone fractionation and characterization of Brauns native lignin separated from Chinese quince fruit.

Lignin, especially Brauns native lignin (BNL), from Chinese quince (Chaenomeles sinensis) fruit represents a potential source of natural antioxidants. However, the highly inhomogeneous structure and the carbohydrate impurity reduce the antioxidant properties of BNL. Accordingly, a sequential aqueous acetone fractionation was used to prepare pure lignin fractions with homogeneous molecular structures; these fractions showed strong antioxidant properties. Analytical results showed that the yields of F50% and F60% exceeded 20% (i.e., 20.6% and 24.1%, respectively). The sugar impurities in BNL were mainly retained in the F30% and F40% fractions. For all fractions, molecular weight increased as the acetone concentration increased. The results from 2D HSQC NMR and 31P NMR indicated that the number of lignin linkages (ß-O-4', ß-ß' and ß-5') and functional groups (S-OH, G-OH, H-OH, and COOH) of these fractions varied with their molecular weights. Antioxidant assays showed that F40%, F50% and F60% had higher antioxidant properties than BNL. Overall, the study provides a simple, environmentally friendly fractionation method to prepare lignin with various structural features and strong antioxidant properties from Chinese quince fruit. These lignin fractions have promising application in some fields with high value, such as antioxidants production, biomaterials, packaging materials, and drug delivery and so on.

Structural features and antioxidant activities of Chinese quince (Chaenomeles sinensis) fruits lignin during auto-catalyzed ethanol organosolv pretreatment.

Chinese quince fruits (Chaenomeles sinensis) have an abundance of lignins with antioxidant activities. To facilitate the utilization of Chinese quince fruits, lignin was isolated from it by auto-catalyzed ethanol organosolv pretreatment. The effects of three processing conditions (temperature, time, and ethanol concentration) on yield, structural features and antioxidant activities of the auto-catalyzed ethanol organosolv lignin samples were assessed individually. Results showed the pretreatment temperature was the most significant factor; it affected the molecular weight, S/G ratio, number of ß-O-4' linkages, thermal stability, and antioxidant activities of lignin samples. According to the GPC analyses, the molecular weight of lignin samples had a negative correlation with pretreatment temperature. 2D-HSQC NMR and Py-GC/MS results revealed that the S/G ratios of lignin samples increased with temperature, while total phenolic hydroxyl content of lignin samples decreased. The structural characterization clearly indicated that the various pretreatment conditions affected the structures of organosolv lignin, which further resulted in differences in the antioxidant activities of the lignin samples. These results can be helpful for controlling and optimizing delignification during auto-catalyzed ethanol organosolv pretreatment, and they provide theoretical support for the potential applications of Chinese quince fruits lignin as a natural antioxidant in the food industry.

Effect of drying pretreatment methods on structure and properties of pectins extracted from Chinese quince fruit.

Pectin was extracted from the sun-dried, lyophilized, and subcritical dimethyl ether (DME) dewatered fruits as well as fresh fruits, giving rise to fractions SP, LP, DP, and FP, respectively. The structure and properties of the pectin samples were investigated. Among all the pectin samples, LP had the highest yield (10.49%), the highest molar mass (Mw 65,120 g/mol), and the highest water holding capacity, and was the most thermally stable. In addition, LP exhibited the highest DPPH scavenging activity and reducing power. DP had the highest degree of esterification (72.95%), the lowest molar mass (Mw 45,860 g/mol), and the highest oil holding capacity. The four pectin samples had different surface morphology. At the concentration of 2.5% (w/w) in water, all four pectins presented pseudo-plastic behavior. The study provides theoretical support for the potential application of Chinese quince pectin in food field.