Chemo- und biokatalytische Synthesestrategien zur Darstellung und funktionellen Charakterisierung Aminosäure-basierter Tenside aus biogenen Rohstoffen

• Main Author: Jolmes, Tristan
• Format: Doctoral or Postdoctoral Thesis
• Language: German
• Published: Hannover : Institutionelles Repositorium der Leibniz Universität Hannover 2023
• Subjects: amino acid-surfactants; sustainable synthesis; enzyme catalysis; contains research data; Aminosäure-Tenside; nachhaltige Synthese; Enzymkatalyse; enthält Forschungsdaten; ddc:540; Antarc*; Antarctica
• Online Access: https://www.repo.uni-hannover.de/handle/123456789/15861; https://doi.org/10.15488/15737

The current trend for greener products and processes has an increasing significance for the chemical industry and plays a major role in surfactant synthesis which are produced and released into the environment in large scale. To match this trend, this work follows two distinct strategies: Firstly, the development and subsequent optimization of greener synthesis routes for already established surfactants and secondly the development, characterisation, and evaluation of novel structures. Usually, amino acids are acylated following the Schotten-Bauman-procedure via chlorinated carboxylic acids, which need to be synthesized by harmful and dangerous chlorination agents in the first hand. Initially, alternative routes were evaluated in hindsight of their applicability for the green synthesis of acyl-amino acids. Chemical coupling with propyl-phosphonic anhydride (T3P) and enzymatic acylation with novel aminoacylase from Paraburkholderia monticola (PmAcy) were found to be potentially viable candidates. The application of T3P allows synthesis of acyl-amino acids in good yields without further need for protective groups. The necessity for organic bases and the ability to easily produce tailor-made peptides qualifies the route for the application in the production of speciality chemicals and pharmaceutical active peptides. The novel enzyme PmAcy accepts a variety of basic and hydrophobic amino acids as well as fatty acids in varying chain lengths. The application in a buffer-free system and a potential recycling strategy were demonstrated. The sustainable production of already established antimicrobial agent N-lauroyl-arginine ethyl ester (LAE) was demonstrated in a two-step enzymatic cascade with PmAcy and immobilized Pseudozyma antarctica lipase. Successful development and synthesis of novel, completely bio-based surfactant structures was done in a two-step approach. Myrcene or conjugated linoleic acid were coupled to cyclic anhydrides maleic anhydride and citraconic anhydrides in a microwave-assisted reaction set-up. ...