Lignin is considered a promising renewable source of valuable chemical compounds and a feedstock for the production of various materials. Its suitability for certain directions of processing is determined by the chemical structure of its macromolecules. Its formation depends on botanical origin, isolation procedure and other factors. Due to the complexity of the chemical composition, revealing the structural differences between lignins of various origins is a challenging task and requires the use of the most informative methods for obtaining and processing data. In the present study, a combination of two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy and multivariate analysis of heteronuclear single quantum coherence (HSQC) spectra is proposed. Principal component analysis and hierarchical cluster analysis techniques demonstrated the possibility to effectively classify lignins at the level of belonging to classes and families of plants, and in some cases individual species, with an error rate for data classification of 2.3%. The reverse transformation of loading plots into the corresponding HSQC loading spectra allowed for structural information to be obtained about the latent components of lignins and their structural fragments (biomarkers) responsible for certain differences. As a result of the analysis of 34 coniferous, deciduous, and herbaceous lignins, 10 groups of key substructures were established. In addition to syringyl, guaiacyl, and p-hydroxyphenyl monomeric units, they include various terminal substructures: dihydroconiferyl alcohol, balanopholin, cinnamic acids, and tricin. It was shown that, in some cases, the substructures formed during the partial destruction of biopolymer macromolecules also have a significant effect on the classification of lignins of various origins.

ABS plastic is an inexpensive material with attractive physical and chemical properties. Unfortunately, it is susceptible to degradation under UV radiation, so it limits the use of this material outdoors. In this paper, we demonstrate a low-cost approach to reduce the photodegradation of ABS plastic by using additives of kraft lignin and dioxane lignin as UV absorbers. Lignin is an abundant plant polymer, which is a waste product of the pulp and paper industry. Non-regular structure of lignin hampers its use in industry. However, there is possible use of lignin as an addition to enhance the properties of resulting materials. In this study, we obtained composites of ABS and lignin with the hot extrusion method. Adding up to 15% of lignin to ABS plastic does not have a significant negative impact on tensile properties. We irradiated the resulting composites with UV and studied the UV effects on their mechanical properties and chemical structure. Oxidative degradation was characterized by FTIR and 2D NMR methods. The results showed that small lignin additions reduced the photodegradation of ABS. The previously undescribed product of the degradation of the obtained composites was detected with the use of the set of 2D NMR spectra of the composites. We proposed a scheme for the formation of this photodegradation product based on the obtained data.

This article proposes an approach for acquiring HSQC (Heteronuclear Single Quantum Coherence) spectra using a high-resolution probehead originally designed for solutions. The method is suitable for studying organic substances with relatively low melting points, such as copolymers, composites, waxes, resins, and similar materials. The procedure involves preparing a melt of the substance directly inside the NMR (Nuclear Magnetic Resonance) sample tube prior to analysis. A comparison of HSQC spectra obtained from both the molten state and a solution of the same substance demonstrates that representative spectra can be acquired, enabling detailed analysis of their fine structure. The method has been successfully tested on a range of materials, including: paraffin, wax, honey, vanillin, polycaprolactone, a copolymer of lactide with phenol and maleic anhydride, composites of polycaprolactone and vanillin. This approach enables the identification of impurities in polymers and biological samples without requiring expensive deuterated solvents.