The ratio of monomeric units is one of the main characteristics of lignin, which affects the possibilities and strategies for further processing. Pyrolytic and thermal desorption decomposition of lignins followed by mass detection of macromolecule fragments are the most common methods for determining the amount of lignin structural units. Two methods of thermal decomposition of lignin were studied: thermal desorption–GC/MS (TD–GC/MS) and pyrolysis–GC/MS (Py–GC/MS). It was noted that, when using different thermal decomposition modes, the composition of the products changes, which affects the accuracy of determining the amount of lignin structural fragments. This article investigated the influence of the sample weight, the thermal decomposition temperature, and the duration of the process in various modes on the quantitation of the lignin structural units. The optimal process conditions were established. It was shown that the DS–Py–GC/MS with cryofocusing, a sample weight of 0.2–0.4 mg, and heating from 50 to 400 °C at a rate of 120 °C/min are preferable. The HSQC NMR was used as a comparison method to obtain the content of the S/G/H units. The results showed the applicability of the proposed approaches to hardwood lignins close to native.

In this article, we represented the review of literature data about the study of lignin as one of the most abundant biopolymers. The review is based on the articles published in the most quoted world publishing. It is noted that already nowadays the lignin is considered as a powerful renewable source of valuable organic raw materials, also it’s pointed that potential possibilities of lignin valorization are much wider than those are used in present times. The special attention is paid to the structure and molecular organization of birch lignin, which wood is actively utilized in chemical industry, meanwhile the hardwood lignins are less studied in literature than softwood lignins. The authors touched the most basic methods of research of such complex and irregular polymer as lignin, methods’ advantages, disadvantages and perspectives are analyzed. It is noted that nowadays the most effective methods of lignin structure units study are pyrolisys gas chromatography and nuclear magnetic resonance. The article describes various ways of lignins isolation from the wood, and influence of the isolation way on the structure of isolated substance. Also, the structural features of birch lignin and its differences from other species are shown.

NMR spectroscopy is one of the effective methods for the study of plant raw materials, which makes it possible to identify differences in the structure and functional composition of lignins of various types of plant biomass. However, there are a number of limitations in the use of this method – in particular, the registration of NMR spectra at some nuclei (13C, 31P, etc.) usually requires considerable amount of time. This article proposes an approach to reduce the recording time of 31P NMR spectra by a factor of 17 without losing the quality of the result. With the help of this method and with the use of optimized experimental parameters, the functional group analysis of lignins of some softwood and hardwood species and herbaceous plants distributed in the European North of the Russian Federation was carried out. The types of structural units and their characteristic interstructural relationships per 100 phenylpropane units were determined by HSQC NMR. Differences in the functional composition and features of the structural organization of lignins were identified depending on the family to which the plant belongs. On the basis of the obtained array of experimental data the strategies of processing of specific types of plant raw materials were proposed. For example, lignins of the Birch and Beech families showed the largest number of β-aryl ether fragments with a free hydroxyl group in the α-position, which indicates the greater reactivity of these lignins. Accordingly, representatives of these families are priority raw materials in the development of lignin processing methods. At the same time, the structure of lignins of representatives of the Beech family proved to be the most resistant to hydrolytic degradation, which is important for lignin-directed bioprocessing concepts. For citation: Sypalova Yu.A., Shestakov S.L., Kozhevnikov A.Yu. Functional Composition and Structural Features of Higher Plant Lignins. Lesnoy Zhurnal = Russian Forestry Journal, 2023, no. 5, pp. 164–183. (In Russ.). https://doi.org/10.37482/0536-1036-2023-5-164-183

Lignin is one of the most abundant biopolymers. Information about the functional composition and structure of various lignins may be useful in the study of biosynthesis processes in plants. The subject of the article is the determination of ³¹P NMR spectroscopy possibilities to identify lignins obtained from various plant forms. To obtain spectra on ³¹P nuclei, a modification of the studied samples was applied by phosphitylating their OH-groups with a special reagent. We obtained qualitative and quantitative analysis of samples of softwood and hardwood lignins and herbaceous plants. According to the NMR spectra we noted the differences in composition and structure of the studied lignins. We confirmed that the structure of lignins of softwood and hardwood wood mainly contain guaiacilpropane and syringylpropane structural units, respectively. We found that lignins of herbaceous plants contain all types of OH-groups characteristic for lignins, including p-hydroxyphenyl groups. It was observed that samples of herbaceous plants lignins contain fragments of flavonoid structures in most cases. The ³¹P NMR spectrum of quercetin, as the flavonoids representative, was registered and also modeled using the ACDLabs software package to confirm the presence of flavone structures in the macromolecules of the herbaceous lignins.

Improving the quality of cellulose semi-finished products for subsequent chemical processing in combination with the “green” concept is an important technical challenge. The article investigated a number of organic solvents as a delignifying agent. It has been shown that DMSO usage is the most efficient organosolv way to obtain cellulose from birch wood (B. pendula). The influence of the concentration of the organic solvent in the cooking liquid, the concentration of the acid catalyst, the duration and temperature of the process has been studied. The conditions for maximum process desirability at which the highest yield of cellulosic semi-finished product (CSP) and degree of delignification were as follows: 2 h treatment time at 156 °C, DMSO/water 75–95% solvent system with solid to liquid ratio of 1:10. At a concentration of DMSO in the cooking liquor of 85–90%, the degree of wood delignification was about 95%. The mechanical properties of the experimental DMSO pulp were similar to those of kraft pulp. DMSO lignin was characterized by Pyr-GC/MS. More than 65% of monomer fragments of phenolic compounds were S-unit derivatives. The results show that organosolv delignification with DMSO/Water can be proposed as an eco-friendly alternative process to the kraft pulping.