Two decades after the introduction of matrix assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI), soft ionization mass spectrometry represents a powerful toolset for the structural investigation of synthetic polymers. The present review highlights the current state-of-the-art, covering the latest developments of novel techniques, enabling instrumentation as well as the important applications of soft ionization MS from the beginning of 2008. Special attention is paid to the role that soft ionization MS has played in the mechanistic investigation of radical polymerization processes since 2005.

Lignosulfonates are industrial biorefinery products that are characterized by significant variability and heterogeneity in their structural composition. Typically, they exhibit high dispersities in molar mass (molar mass distribution─MMD) and in functionalities (functionality-type distribution─FTD), which crucially affect their material usage. In terms of FTD, state-of-the-art lignin analytics still rely mainly on the determination of functional group contents, which are statistical averages with limited explanatory power. In contrast, our online hydrophobic interaction chromatography–size-exclusion chromatography 2D-LC approach combines the determination of both MMD and FTD in a single measurement to provide a comprehensive picture of the characteristic composition of industrial lignosulfonates─information hitherto inaccessible by state-of-the-art lignin analytics. In this way, the complex inter-relationships between these two important structural parameters can be studied in an unprecedented manner. In this study, we reveal the considerable differences in terms of hydrophobic composition and its dispersity present in a range of different industrial lignosulfonates─data desperately needed in tailoring and refining of lignosulfonate composition for material usage.

The 2-methoxyphenol units (G-units) in lignin are modified by demethylation and oxidation to provide the activated lignin as one part of an advanced biobased two-component (2K) adhesive system, which exhibits promising shear strengths in dry and underwater applications. The activation of lignin is straightforward and generates quinones via demethylation and periodate oxidation. These act as Michael acceptors and react smoothly with multi-thiol-star polymers to yield thiol-catechol connectivities (TCCs). The mussel-inspired material platform acts as a very robust and versatile adhesive, combining low-cost and readily available lignin with multi-thiols to achieve outstanding adhesion strengths of up to 15 MPa in dry application. In particular, the 2K system is compatible with the marine biological environment and shows no acute toxicity to sensitive organisms such as fish eggs. Thus, one possible application of this material could be an adhesive for setting temperature-resistant corals in damaged reefs.