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.
It is important to be aware that biopesticides are still pesticides and fall under the same regulations as their synthetic counterparts. Although manufacturers are still reluctant to commit to such alternatives due to difficulties with approval and registration, biopesticides could be alternatives for traditional plant protection products, either as a base for the synthesis of new products or integrated with traditional plant protection products. In addition, biopesticides have to be used only as indicated on the label, which provides critical information about how to safely handle and use plant protection products.
The chemical composition of the lipophilic extracts of bark and core, of the Miscanthus x giganteus stalk, was studied by gas chromatography-mass spectrometry (GC-MS). Aromatic compounds, sterols, and fatty acids, followed by long-chain fatty alcohols, were the major families of components present in the M. x giganteus stalk. Aromatic compounds are more abundant in the M. x giganteus bark (521 mg/kg of bark), with vanillic acid, vanillin, and p-hydroxybenzaldehyde as the major compounds of this family. In the M. x giganteus core, sterols represent about 949 mg/kg of dry core with beta-sitosterol, 7-oxo-beta-sitosterol, stigmasterol, and campesterol as the major components. The detection of small amounts of esters in the GC-MS analysis with short columns explains the small increase in the abundance of the identified families after alkaline hydrolysis. The high content of valuable sterols and aromatic compounds in M. x giganteus and, particularly, in the core, which is considered a residue in most applications, can open new perspectives for the integrated upgrading of this grass within the biorefinery perspective.
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