Analysis of Fruit Lignin Content, Composition, and Linkage Types in Pear Cultivars and Related Species.

Lignin content, composition, and linkage types were investigated in pear fruit cultivars and related species. Lignin content increased during early stages and then decreased toward ripening in the core and flesh of "Gold Nijisseiki" and "Alexandrine Douillard". The lignin content was highest at harvest in Chinese quince. Only trace amounts of lignin were detected in apple flesh. The lignin content was low in Japanese pears "Ohshu", "Hosui", and "Kosui", and the noncondensed lignin index was high in flesh. The lignin type was guaiacyl-syringyl (GS) in these pears and related species. The S/G ratio at harvest varied widely (0.75-2.64) and increased during early stages and remained constant toward harvest in "Gold Nijisseiki" and "Alexandrine Douillard". "Gold Nijisseiki" and "Alexandrine Douillard" were determined to be G- and S-lignin-rich types, respectively. ß-Aryl ether, phenylcoumaran, and resinol interunit linkage types were detected among monolignol bonds, and ß-Aryl ether units were the main linkages in the pear.

Two-dimensional NMR analysis of Angiopteris evecta rhizome and improved extraction method for angiopteroside.

INTRODUCTION: The rhizome of Angiopteris evecta is of academic interest in Kalimantan, Indonesia, from an ethnobotanical perspective. Angiopteroside is a substance of pharmaceutical importance that is found in the rhizome of A. evecta. OBJECTIVE: The aims of this research are to improve the extraction method for angiopteroside from the rhizome, compared to that in a previous report, and to determine the yield of angiopteroside from the rhizome of A. evecta, as well as to obtain precise data for extractives from the rhizome of A. evecta by using two-dimensional NMR spectroscopy and liquid chromatography-mass spectrometry (LC-MS). METHODOLOGY: We investigated the chemical constituents of the whole rhizome by means of two-dimensional NMR (heteronuclear single quantum coherence or HSQC) spectroscopy, neutral sugar analysis using the alditol acetate method, and lignin analysis using alkaline nitrobenzene oxidation and Klason lignin methods. LC-MS revealed the purity of the angiopteroside. Antimicrobial assays were also performed for the purified angiopteroside by using a broth microdilution method. RESULTS: Angiopteroside was isolated by Soxhlet extraction with aqueous acetone followed by preparative thin-layer chromatography (eluent: 20% methanol/dichloromethane). LC-MS revealed that angiopteroside can be found in the rhizome of A. evecta in 9.9% yield, which is an extremely high yield for a plant extractive. CONCLUSION: HSQC analysis is a powerful tool for surveying compounds in plant materials, such as the whole rhizome of A. evecta. Soxhlet extraction with aqueous acetone is an effective method for extracting glycosides from plant materials.

Distribution of coniferin in differentiating normal and compression woods using MALDI mass spectrometric imaging coupled with osmium tetroxide vapor treatment.

Matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI) was employed to detect monolignol glucosides in differentiating normal and compression woods of two Japanese softwoods, Chamaecyparis obtusa and Cryptomeria japonica Comparison of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry collision-induced dissociation fragmentation analysis and structural time-of-flight (MALDI-TOF CID-FAST) spectra between coniferin and differentiating xylem also confirmed the presence of coniferin in differentiating xylem. However, as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and MALDI-TOF CID-FAST spectra of sucrose were similar to those of coniferin, it was difficult to distinguish the distribution of coniferin and sucrose using MALDI-MSI and collision-induced dissociation measurement only. To solve this problem, osmium tetroxide vapor was applied to sections of differentiating xylem. This vapor treatment caused peak shifts corresponding to the introduction of two hydroxyl groups to the C=C double bond in coniferin. The treatment did not cause a peak shift for sucrose, and therefore was effective in distinguishing coniferin and sucrose. Thus, it was found that MALDI-MSI combined with osmium tetroxide vapor treatment is a useful method to detect coniferin in differentiating xylem.