Native Lignin Structure of Miscanthus x giganteus and Its Changes during Acetic and Formic Acid Fractionation

Abstract

Milled wood lignin (MWL) and acetic and formic acid lignin (AL and FL) from Miscanthus x giganteus bark were produced, respectively, before and after organosolv fractionations under optimal conditions, in terms of organic and hydrochloric acid concentrations, liquid/wood ratio, and reaction time. In order to study the M. x giganteus native lignin structure and its modifications during the fractionation process, the lignins were studied by two-dimensional heteronuclear single quantum coherence (2D-(HSQC)), (13)C- and (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR), size-exclusion chromatography (SEC) both before and after thioacidolysis, and elemental analysis. In addition, chemical composition analysis was performed on ash, Klason lignin, and carbohydrate content. The analyses demonstrated that M. x giganteus native lignin (MWL) is highly acylated at the C(gamma) of the lignin side chain (46%), possibly with p-coumarate and/or acetate groups. This is newsworthy since several earlier studies showed that acylation at the gamma-carbon commonly occurs in C(3) and CAM grasses, whereas M. x giganteus is a C(4) grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of beta-O-4' linkages (up to 93% of all linkages). AL and FL lose part of these linkages during organosolv fractionation (up to 21 and 32%, respectively). The p-coumarate groups resist fractionation processes and are still present in high quantities in AL and FL. During the fractionation process, lignin is acetylated (acetic acid process) and condensed, with the G units condensing more than S units. M. x giganteus MWL contains a high content of carbohydrates (22.8%), suggesting that it is a lignin-carbohydrate complex (LCC). AL and FL showed low carbohydrate contents because of the breaking down of the LCC structures. AL and FL have high molecular weights and low polydispersities, and are high in phenolic content, qualities that make these suitable for different applications. These results suggest that refinement of M. x giganteus via organosolv processes could potentially turn this grass into a valuable source of both fiber and lignin.

Isolation and Structural Characterization of Lignin from Cardoon (Cynara cardunculus L.) Stalks

“…The same12 % value was also obtained for γ-acylated cinnamyl alcohol endgroups (I') by integration of their signals. This is a rather low value when compared to those obtained in other plants such as sisal, elephant grass, or Miscanthus that presented, respectively, 68, 39-55, and 46 % of acylation [22,33,34]. Lignin acylation in cardoon stalks occurred exclusively at the Cγ position, as also reported for other plants [35].…”

Miscanthus x giganteus as a Source Of Biobased Products Through Organosolv Fractionation: A Mini Review

“…Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of -O-4' linkages (up to 93% of all linkages) [17]. Also contains a very low proportion of condensed linkages such as spirodienone ( -1') (detected in a quantity lower than 0.5%), phenylcoumaran ( -5') and resinol ( -') [17]. It is believed that the high acylation at C could be the reason for the low abundance of the double tetrahydrofuran ring from resinol, which requires free hydroxyls in C to be formed [19].…”

“…This is remarkable since several earlier studies showed that acylation at thecarbon commonly occurs in C3-and CAM-grasses [19], whereas M. x giganteus is a C4 grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of -O-4' linkages (up to 93% of all linkages) [17]. Also contains a very low proportion of condensed linkages such as spirodienone ( -1') (detected in a quantity lower than 0.5%), phenylcoumaran ( -5') and resinol ( -') [17].…”

“…A number of studies on the structural characterization of lignin from different herbaceous crops have been reported in the literature, but the first study on the determination of phenolic hydroxyl group content of milled wood lignin from Miscanthus sinensis was published by Faix [16]. Recently, more complete studies in the characterization of Miscanthus x giganteus MWL were reported [17,18], showing that it is highly acylated at the C of the side chain (46%), possibly with pcoumarate and/or acetate groups [17]. This is remarkable since several earlier studies showed that acylation at thecarbon commonly occurs in C3-and CAM-grasses [19], whereas M. x giganteus is a C4 grass.…”

“…5), reaching precipitation rates near 90% of the initial lignin. Therefore, for study, all lignins were precipitated using a volumetric ratio water/liquor = 6 [17].…”