Determination of molecular weight parameters of native and, in particular, technical lignins are based on size exclusion chromatography (SEC) approaches. However, no matter which approach is used, either conventional SEC with a refractive index detector and calibration with standards or multi‐angle light scattering (MALS) detection at 488 nm, 633 nm, 658 nm, or 690 nm, all variants can be severely erroneous. The lack of calibration standards with high structural similarity to lignin impairs the quality of the molar masses determined by conventional SEC, and the typical fluorescence of (technical) lignins renders the corresponding MALS data rather questionable. Application of MALS detection at 785 nm by using an infrared laser largely overcomes those problems and allows for a reliable and reproducible determination of the molar mass distributions of all types of lignins, which has been demonstrated in this study for various and structurally different analytes, such as kraft lignins, milled‐wood lignin, lignosulfonates, and biorefinery lignins. The topics of calibration, lignin fluorescence, and lignin UV absorption in connection with MALS detection are critically discussed in detail, and a reliable protocol is presented. Correction factors based on MALS measurements have been determined for commercially available calibration standards, such as pullulan and polystyrene sulfonate, so that now more reliable mass data can be obtained also if no MALS system is available and these conventional calibration standards have to be resorted to.

Technical lignins (waste products obtained from wood pulping or biorefinery processes) have so far required lengthy analysis procedures and different eluents for molar-mass analysis by gel permeation chromatography (GPC). This challenge has become more pressing recently since attempts to utilize lignins have increased, leading to skyrocketing numbers of samples to be analyzed. A new approach, which uses the eluent DMSO/LiBr (0.5 % w/v) and converts lignosulfonate salts into their acidic form before analysis, overcomes these limitations by enabling measurement of all kinds of lignins (kraft, organosolv, soda, lignosulfonates) in the same size-exclusion chromatography (SEC) system without the necessity of prior time-consuming derivatization steps. In combination with ultra-performance liquid chromatography (UPLC), analysis times are shortened to one tenth of classical lignin GPC. The new approach is presented, along with a comparison of GPC and UPLC methods and a critical discussion of the analytical parameters.

In this study, a novel approach for isolation and purification of lignosulfonates from spent sulfite liquor was established.

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A method based on headspace-isotope dilution (HS-ID) GC-MS for the quantitative analysis of methoxyl and ethoxyl groups in any kind of lignin has been developed. The method involves the application of an isotopically labeled internal standard (4-(methoxy-d 3 )-benzoic acid and 4-(ethoxy-d 5 )-benzoic acid), which, together with lignin, undergoes standard hydroiodic acid cleavage of methoxyl and ethoxyl groups, followed by headspace GC-MS analysis of the respective deuterated and non-deuterated iodomethanes and iodoethanes. As also the internal standard is generated in situ during ether cleavage, any variations in the procedure are levelled out. The application of the isotopically labeled internal standard essentially increased the robustness of the overall approach. The accuracy and precision of methoxyl and ethoxyl group quantification in lignins have been assessed, and the data were compared to the classical Zeisel-Vieböck-Schwappach method for methoxyl groups in lignins. The novel approach for methoxyl and ethoxyl group determination showed a more satisfactory precision, accuracy, and also a much higher sample throughput, with approximately 40 samples per day.

The effect of ball milling expressed as the yield of milled wood lignin (MWL) on the structure and molar mass of crude milled wood lignin (MWLc) preparation is studied to better understand the process’ fundamentals and find optimal conditions for MWL isolation (i.e., to obtain the most representative sample with minimal degradation). Softwood (loblolly pine) MWLc preparations with yields of 20–75% have been isolated and characterized based on their molar mass distribution (by Size Exclusion Chromatography (SEC)), hydroxyl groups of different types (31P NMR), methoxyl groups (HS-ID GC-MS), and sugar composition (based on methanolysis). Classical MWL purification is not used to access the whole extracted lignin. The results indicate that lignin degradation during ball milling occurs predominantly in the high molar mass fraction and is less pronounced in the low molar mass fraction. This results in a significant decrease in the Mz and Mw of the extracted MWLc with an increase in the yield of MWLc, but has only a very subtle effect on the lignin structure if the yield of MWLc is kept below about 55%. Therefore, no tedious optimization of process variables is necessary to achieve the required MWLc yield in this range for structural studies of softwood MWL. The sugar composition shows higher amounts of pectin components in MWLs of low yields and higher amounts of glucan and mannan in high-yield MWLs, confirming that lignin extraction starts from the middle lamella in the earlier stages of MWL isolation, followed by lignin extraction from the secondary wall region.

The white-rot fungus Ceriporiopsis subvermispora delignifies plant biomass extensively and selectively and, therefore, has great biotechnological potential. We previously demonstrated that after 7 weeks of fungal growth on wheat straw 70% w/w of lignin was removed and established the underlying degradation mechanisms via selectively extracted diagnostic substructures. In this work, we fractionated the residual (more intact) lignin and comprehensively characterized the obtained isolates to determine the susceptibility of wheat straw lignin’s structural motifs to fungal degradation. Using 13C IS pyrolysis gas chromatography–mass spectrometry (py-GC-MS), heteronuclear single quantum coherence (HSQC) and 31P NMR spectroscopy, and size-exclusion chromatography (SEC) analyses, it was shown that β-O-4′ ethers and the more condensed phenylcoumarans and resinols were equally susceptible to fungal breakdown. Interestingly, for β-O-4′ ether substructures, marked cleavage preferences could be observed: β-O-4′-syringyl substructures were degraded more frequently than their β-O-4′-guaiacyl and β-O-4′-tricin analogues. Furthermore, diastereochemistry (threo > erythro) and γ-acylation (γ-OH > γ-acyl) influenced cleavage susceptibility. These results indicate that electron density of the 4′-O-coupled ring and local steric hindrance are important determinants of oxidative β-O-4′ ether degradation. Our findings provide novel insight into the delignification mechanisms of C. subvermispora and contribute to improving the valorization of lignocellulosic biomass.

Four commercial spruce lignosulfonates representing the most common acidic, neutral, and alkaline sulfite pulping processes and varying significantly in molecular weight characteristics were tested as partial (40 wt %) phenol substitute materials for the manufacture of lignosulfonate‐phenol‐formaldehyde (LPF) resole resins. Similar as recently reported for technical lignins from nonsulfite pulping processes (kraft, soda, organosolv), all lignosulfonates of this study effectuated a faster viscosity gain during resole cooking compared to the lignin‐free reference resin (1000 mPa s after 120 min vs. 250 min to reach 1000 mPa s). Sodium lignosulfonate featuring the lowest weight average molecular weight (Mw 5780 g mol−1) and dispersity (Ð 6.1) turned out to be superior to the other lignosulfonates with regard to curing rate (B‐time; 3:37 min vs. 6:41–9:08 min) and tensile shear strength development under hot pressing (120 °C; TS,max = 5.64 N mm−2 after 8 min) for beech veneer strips glued together with the respective LPF resins. Calcium and magnesium lignosulfonates are less suited with regard to phenol replacement due to the poor performance of the respective LPF adhesives in terms of tensile shear strength (TS,max = 3.29–3.49 N mm−2 after 12 min) most likely caused by considerable amounts of side products formed in the course of formose‐type reactions. Phenolation of the two promising lignosulfonates, that is, sodium and ammonium lignosulfonate, did neither considerably increase the rate of PF network formation during resin cooking and curing nor improve tensile strength development during hot pressing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45893.