Thioacidolysis of Spruce Lignin: GC-MS Analysis of the Main Dimers Recovered After Raney Nickel Desulphuration

Lapierre, Catherine; Pollet, Brigitte; Monties, Bernard; Rolando, Christian

doi:10.1515/hfsg.1991.45.1.61

Cited by 152 publications

(175 citation statements)

References 21 publications

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“…A ␤ -5 dimer also was found in small amounts. Similar dimer analyses and typical mass fragments of thioacidolysis monomers and dimers have been described previously (Lapierre et al, 1991;Rolando et al, 1992).…”

Section: Thioacidolysis Degradation Products Of the Dhpssupporting

confidence: 70%

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Polymerization of Monolignols by Redox Shuttle–Mediated Enzymatic Oxidation

et al. 2002

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Lignin is one of the most abundant biopolymers, and it has a complex racemic structure. It may be formed by a radical polymerization initiated by redox enzymes, but much remains unknown about the process, such as how molecules as large as enzymes can generate the compact structure of the lignified plant cell wall. We have synthesized lignin oligomers according to a new concept, in which peroxidase is never in direct contact with the lignin monomers coniferaldehyde and coniferyl alcohol. Instead, manganese oxalate worked as a diffusible redox shuttle, first being oxidized from Mn(II) to Mn(III) by a peroxidase and then being reduced to Mn(II) by a simultaneous oxidation of the lignin monomers to radicals that formed covalent linkages of the lignin type. Furthermore, a high molecular mass polymer was generated by oxidation of coniferyl alcohol by Mn(III) acetate in a dioxane and water mixture. This polymer was very similar to natural spruce wood lignin, according to its NMR spectrum. The possible involvement of a redox shuttle/peroxidase system in lignin biosynthesis is discussed.

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Section: Thioacidolysis Degradation Products Of the Dhpssupporting

confidence: 70%

“…By incorporating a second step consisting of desulfuration over Raney nickel (a metal catalyst), thioethyl groups are removed, which makes it possible to identify oligomers using gas chromatography-mass spectrometry after acetylation and/or silylation of the products (Lapierre et al, 1991).…”

Section: Thioacidolysis Degradation Products Of the Dhpsmentioning

confidence: 99%

Polymerization of Monolignols by Redox Shuttle–Mediated Enzymatic Oxidation

et al. 2002

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“…In order to determine the S-G ratio, thioacidolysis was carried out according to Lange et al (1995), and the reaction products were analyzed by gas chromatography-mass spectrometry (Lapierre et al, 1991) using a Shimadzu GCMS-QP Plus 2010, equipped with a moving needle-type injector and a flame ionization mass detector. Silylated samples were injected onto a polydimethylsiloxane capillary column (DB5; 30 m, 0.32 mm i.d., film thickness of 0.25 pm; J&W Scientific), and helium was the gas carrier, using a temperature program from 160°C to 260°C at 2°C min 21 .…”

Section: Lignin Determinationsmentioning

confidence: 99%

Lignification in Sugarcane: Biochemical Characterization, Gene Discovery, and Expression Analysis in Two Genotypes Contrasting for Lignin Content

et al. 2013

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Sugarcane (Saccharum spp.) is currently one of the most efficient crops in the production of first-generation biofuels. However, the bagasse represents an additional abundant lignocellulosic resource that has the potential to increase the ethanol production per plant. To achieve a more efficient conversion of bagasse into ethanol, a better understanding of the main factors affecting biomass recalcitrance is needed. Because several studies have shown a negative effect of lignin on saccharification yield, the characterization of lignin biosynthesis, structure, and deposition in sugarcane is an important goal. Here, we present, to our knowledge, the first systematic study of lignin deposition during sugarcane stem development, using histological, biochemical, and transcriptional data derived from two sugarcane genotypes with contrasting lignin contents. Lignin amount and composition were determined in rind (outer) and pith (inner) tissues throughout stem development. In addition, the phenolic metabolome was analyzed by ultra-highperformance liquid chromatography-mass spectrometry, which allowed the identification of 35 compounds related to the phenylpropanoid pathway and monolignol biosynthesis. Furthermore, the Sugarcane EST Database was extensively surveyed to identify lignin biosynthetic gene homologs, and the expression of all identified genes during stem development was determined by quantitative reverse transcription-polymerase chain reaction. Our data provide, to our knowledge, the first in-depth characterization of lignin biosynthesis in sugarcane and form the baseline for the rational metabolic engineering of sugarcane feedstock for bioenergy purposes.

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“…Chemical analyses: Thioacidolysis and subsequent Raney nickel desulfurization were performed according to the protocols of Lapierre et al (1991) and Rolando et al (1992) with slight modifications. Approx.…”

Section: Tof-sims Analysismentioning

confidence: 99%

“…The structures of the main compounds and mass spectral data are summarized in Figure 6 and Table 1, respectively. The peak assignments of the main G-G, G-S, and S-S dimers are based on the MS data under consideration of the RT values available in the literature (Lapierre et al 1991;Saito and Fukushima 2005a;Rencoret et al 2008Rencoret et al , 2011Zheng et al 2014b). …”

Section: Tof-sims Analysismentioning

confidence: 99%

Lignification of ray parenchyma cells (RPCs) in the xylem of Phellodendron amurense Rupr.: quantitative and structural investigation by TOF-SIMS and thioacidolysis of laser microdissection cuts of RPCs

Zheng¹,

Aoki

Matsushita

et al. 2015

Holzforschung

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Lignification of ray parenchyma cells (RPCs) in the sapwood (sW), transition zone (TZ), and heartwood (hW) of Phellodendron amurense Rupr. has been investigated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) and thioacidolysis. The results of TOF-SIMS indicate that the relative ion intensity of lignin in RPCs increased from sW to hW, while there was almost no difference in the case of axial wood fibers. The ratio of syringyl (S) to guaiacyl (G) lignin units (S/G value) in RPCs was higher than that in wood fibers. Samples containing more RPCs were prepared by laser microdissection (LMD) and analyzed by thioacidolysis, including also the subsequent Raney nickel desulfurization, and the resulting monomers and dimers were quantitatively analyzed by GC/MS. The monomer analysis shows that lignin content and S/G values in RPCs rich samples increased from sW towards hW. The dimer analysis reveals that the S-S dimers are dominant in all types of samples. The results of TOF-SIMS and thioacidolysis of LMD samples are interpreted that the lignification of RPCs progresses from the sW towards the hW and that the chemical structure of lignin in RPCs is different from that in axial elements.

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Thioacidolysis of Spruce Lignin: GC-MS Analysis of the Main Dimers Recovered After Raney Nickel Desulphuration

Cited by 152 publications

References 21 publications

Polymerization of Monolignols by Redox Shuttle–Mediated Enzymatic Oxidation

Polymerization of Monolignols by Redox Shuttle–Mediated Enzymatic Oxidation

Lignification in Sugarcane: Biochemical Characterization, Gene Discovery, and Expression Analysis in Two Genotypes Contrasting for Lignin Content

Lignification of ray parenchyma cells (RPCs) in the xylem of Phellodendron amurense Rupr.: quantitative and structural investigation by TOF-SIMS and thioacidolysis of laser microdissection cuts of RPCs

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