Wu, Yuxiao2022-04-132022-04-132022-02https://hdl.handle.net/11299/226940University of Minnesota Ph.D. dissertation. 2022. Major: Material Science and Engineering. Advisor: Paul Dauenhauer. 1 computer file (PDF); 140 pages.Natural and synthetic polymers can be found everywhere in our everyday lives. Polymer materials contribute to crucial roles in sophisticated applications such as electronics, medical devices and implants. They are also found in parts of every trivial thing in modern life such as clothing, food packaging, housing, and transportation. We rely more on synthetic polymers over natural polymers since the prosperity of petrochemical industry after the Second Industrial Revolution. The cheap and abundant fossil fuel allowed the development of a wide array of synthetic polymers in the 20th century. However, environmental concerns associated with using petroleum feedstock as the raw material received more and more attention. Over the past several decades researchers have focused on replacing petroleum feedstock with renewable feedstock to produce sustainable polymers. The abundant biomass is often used as the renewable raw material and one important way to breakdown biomass is through microbial fermentation. The development of genetic engineering allowed successful expansion of the natural metabolic pathways of microorganisms. Many industrial chemicals and novel chemicals were produced from microbial fermentation. The advantage of microbial fermentation is that it is carried out in mild reaction conditions and generates environmentally benign byproducts. However, microbial fermentation lacks the economic viability and utility due to long fermentation time and productivity. A hybrid synthesis process combining microbial fermentation and chemical reaction is a highly efficient approach to produce sustainable polymers. With this in mind, my PhD research has focused on developing hybrid chemical engineering process for the production of novel or existing polymer precursors and implement them for material applications. Using metabolic engineering and simple chemical reaction, I have produced N-acetyldopamine which can be used as a precursor for catechol functionalized polymers. By optimizing the fermentation pathway of mesaconic acid, the yield and productivity have reached an industrially practical level. The hybrid synthesis process to isoprene, the monomer for natural rubber, was established combining this optimized fermentation route with preciously developed one-pot cascade thermal chemical reaction. Finally, I implemented a heterologous pathway to produce citramalic acid. I have worked to establish a C5 diacid platform from microbial fermentation. Combining with a thermocatalytic decarboxylation reaction, an integrated hybrid process for the conversion of glucose to poly(methyl methacrylate) was achieved.enBiosynthesisCatalysisHybridPolymerSustainableThesis or Dissertation