Structural elucidation of isolated and fractionated lignins by means of ultra-high resolving mass spectrometry (LignoMassStructure)

该研究项目的目标是开发ESI-和GALDI-FT-ICR-MS和串联MS程序，用于表征来自不同植物（针叶木，落叶木和一年生植物）和制浆工艺（硫酸盐法，亚硫酸盐法和苏打法制浆）的分离和分馏木质素。与用于木质素表征的经典分析方法（例如，GPC、NMR、Py-GC/MS）。一方面，一般的样品信息是可用这些FT-ICR-MS和-MS/MS方法，如摩尔质量分布。另一方面，通过这些实验也可获得对木质素样品的具体结构见解。为此目的，方法开发和优化实验将进行与从落叶木材（山毛榉）的分级硫酸盐木质素的帮助下。此外，一个异源光谱相关的方法将被应用到联合收割机FT-ICR-MS和-MS/MS的结果与其他分析技术（Py-GC/MS，13 C-，31 P-和2D-HSQC-NMR光谱）的结果，这将有助于获得更多的信息，不同的木质素的结构组成。这些新的结果将显着增加我们的了解的影响，分离过程中的木质素目标结构。特别是固体木质素样品的GALDI-FT-ICR-MS和-MS/MS分析将有助于更详细地表征木质素结构，而与不同样品或样品级分中所含木质素化合物的溶解度无关。在最后一个项目阶段，将通过分析复杂的木质纤维素来证明所开发方法的能力，这将有助于评估所开发的常规方法对其他生物聚合物（纤维素和半纤维素）的适用性。如果该方法应用步骤成功，则有史以来第一次可以在其天然环境中对生物聚合物进行结构表征。因此，该研究项目的结果将对开发更有效和更方便的生物聚合物分离和改性程序产生影响，这将在不久的将来显着有助于生产更高价值的木质素和木质纤维素产品。

The goal of this research project is a development of ESI- and GALDI-FT-ICR-MS and tandem MS routines for a characterization of isolated and fractionated lignins from different plants (coniferous wood, deciduous wood and annual plants) and pulping processes (kraft, sulfite and soda pulping). These routines will massively help to reduce the effort for an analysis of soluble and insoluble lignin samples, in comparison to classical analytical methods for a lignin characterization (e.g., GPC, NMR, Py-GC/MS). On the one hand, general sample information are accessible with these FT-ICR-MS and -MS/MS methods, such as molar mass distribution. On the other hand, also specific structural insights into the lignin samples are obtainable by these experiments. For this purpose, method development and optimization experiments will be performed with the help of a fractionated kraft lignin from deciduous wood (beech). In addition, a hetero spectroscopic correlation approach will be applied to combine the FT-ICR-MS and -MS/MS results with results from other analytical techniques (Py-GC/MS, 13C-, 31P- and 2D-HSQC-NMR spectroscopy), which will help to obtain more information about the structural composition of the different lignins. These novel results will significantly increase our understanding of the influence of an isolation process on the lignin target structure. Especially the GALDI-FT-ICR-MS and -MS/MS analyses of solid lignin samples will be helpful to characterize the lignin structure more detailed, independently from the solubility of the lignin compounds contained in the different samples or sample fractions. In the last project phase, the capabilities of the developed methods will be demonstrated by analyzing a complex lignocellulose, which will help to evaluate the applicability of the developed routines for other biopolymers (cellulose and hemicellulose). If this method application step is successful, for the first time ever, a structural characterization of biopolymers in their native environment is possible. Therefore, the results from this research project will have an impact on the development of more effective and expedient isolation and modification procedures for biopolymers, which will significantly contribute to a production of lignin and lignocellulose based products of higher value in the near future.