Structural Changes in Milled Wood Lignin (MWL) of Chinese Quince (Chaenomeles sinensis) Fruit Subjected to Subcritical Water Treatment.

Subcritical water treatment has received considerable attention due to its cost effectiveness and environmentally friendly properties. In this investigation, Chinese quince fruits were submitted to subcritical water treatment (130, 150, and 170 °C), and the influence of treatments on the structure of milled wood lignin (MWL) was evaluated. Structural properties of these lignin samples (UL, L130, L150, and L170) were investigated by high-performance anion exchange chromatography (HPAEC), FT-IR, gel permeation chromatography (GPC), TGA, pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), 2D-Heteronculear Single Quantum Coherence (HSQC) -NMR, and 31P-NMR. The carbohydrate analysis showed that xylose in the samples increased significantly with higher temperature, and according to molecular weight and thermal analysis, the MWLs of the pretreated residues have higher thermal stability with increased molecular weight. The spectra of 2D-NMR and 31P-NMR demonstrated that the chemical linkages in the MWLs were mainly ß-O-4' ether bonds, ß-5' and ß-ß', and the units were principally G- S- H- type with small amounts of ferulic acids; these results are consistent with the results of Py-GC/MS analysis. It is believed that understanding the structural changes in MWL caused by subcritical water treatment will contribute to understanding the mechanism of subcritical water extraction, which in turn will provide a theoretical basis for developing the technology of subcritical water extraction.

Structural characterization of Chinese quince fruit lignin pretreated with enzymatic hydrolysis.

Lignin is an increasingly valuable raw material for industrial, pharmaceutical and the food industries; natural antioxidants are also being used more and more widely. The Chinese quince fruits have an abundance of lignins with antioxidant properties; however, the lignins cannot be isolated by the methods conventionally used on other sources (e.g., wood, straw). In this investigation, multi-enzymatic hydrolytic pretreatments were used to isolate lignins from Chinese quince fruit, and the structures of these multi-enzyme mixture lignin (EML) fractions were then analyzed and compared with conventional cellulolytic enzyme lignin (CEL). EML fractions are structurally similar to CEL fractions except for an increased S/G ratio, greater number of ß-O-4 linkages, higher average molecular weight and decreased thermal stability. The EML-2 fraction in particular seemed most representative of the lignins isolated, and it exhibited the highest antioxidant activity in comparison with CEL and other EML fractions.

Structural elucidation of lignin-carbohydrate complexes (LCCs) from Chinese quince (Chaenomeles sinensis) fruit.

The lignin-carbohydrate complexes (LCCs) of the mesocarp (MS) and near the endocarp (NE) of Chinese quince (Chaenomeles sinensis) fruits were analyzed using three different methods of fractioning: milled wood lignin (MWL), LCC extracted from crude MWL with acetic acid (LCC-AcOH), and Bjorkman LCC. The MWL and LCC fractions were characterized by carbohydrate composition analysis, SEC, FT-IR, Py-GC/MS, thermal analysis and 2D HSQC NMR. Notably, large amounts of arabinose and galactose remained in the Björkman LCC fractions suggesting a chemical bond between the lignin and pectin. MWL and LCC-AcOH fractions showed better thermal stability than the Björkman LCC fractions. The structure of MS lignin was similar to that of NE lignin; however, fractions from the different fractionation methods revealed differences. The MWL fractions were rich in benzyl ether and γ-ester linkages, while the Björkman LCC fractions contained phenyl glycoside and γ-ester linkages, and the LCC-AcOH fractions contained phenyl glycoside and benzyl ether linkages. These findings are helpful in understanding the nature of lignin and LCC in Chinese quince fruits and provide a theoretical support for their potential application.