Biosynthesized halogenated tryptophan derivatives

A new E. coli-based system uses metabolic engineering and co-cultures to produce various halogenated tryptophan molecules from glucose, providing an environmentally friendly alternative for creating diverse compounds used in pharmaceuticals and other industries.

Background

Halogenated molecules are critical to various industries, including pharma­ceuticals, agrochemicals, and materials science, due to their enhanced bio­logical activities and stability. The precise incorporation of halogen atoms into organic compounds can significantly improve their efficacy, selectivity, and metabolic stability, making them valuable for the development of advanced drugs and specialized materials.

As the demand for such tailored compounds grows, there is an increasing need for sustainable and efficient methods to produce a diverse array of halo­genated derivatives. Biological synthesis, leveraging enzymatic processes, offers a promising alternative to traditional chemical methods by providing greater specificity while reducing environmental impact. However, current approaches to synthesizing halogenated molecules face significant challenges.

Traditional chemical synthesis often relies on toxic reagents and harsh conditions, leading to poor atom economy and difficulties in achieving regio- and stereo-selectivity. These methods can also generate substantial waste, making them less environmentally friendly. Existing biosynthetic techniques may also suffer from limited enzyme efficiency, narrow substrate scope, and restricted halogenation sites, constraining the diversity and yield of the desired halogenated products. Additionally, metabolic bottlenecks in host organisms can impede the scalable production of these valuable compounds, highlighting the need for more advanced and versatile biosynthetic platforms.

Technology description

UT researchers developed a technology for the de novo biosynthesis of various halogenated tryptophan-derived molecules in E. coli, utilizing glucose as the starting material. This system integrates metabolic engineering with a modular co-culture approach to optimize production efficiency and molecular diversity. Key features include the deletion of tnaA and trpR genes to prevent tryptophan degradation and repression, the introduction of feedback-resistant mutations in critical biosynthetic genes, and the overexpression of enzymes involved in tryptophan synthesis.

Additionally, the platform employs specific halogenases alongside a thermo­stable flavin reductase to achieve precise halogenation of tryptophan at multiple positions. By segregating the production and conversion processes into distinct E. coli strains, the system successfully synthesizes 26 distinct halogenated molecules, including novel beta-carbolines and prodrug precursors, offering a sustainable alternative to traditional chemical methods.

This technology stands out due to its innovative combination of metabolic engineering and modular co-culture strategies, enabling the efficient produc­tion of a wide range of halogenated compounds that are challenging to synthesize chemically. The precise regioselectivity of halogenase enzymes ensures high specificity in halogenation, while the use of feedback-resistant mutations and overexpressed biosynthetic pathways maximizes precursor availability. The thermostable flavin reductase enhances the efficiency of the halogenation process, and the spatial separation of pro­duction and conversion in different strains minimizes metabolic burden and increases overall yield. This approach not only enhances the diversity and scalability of bio-based halogenated molecule production but also promotes environ­mentally friendly practices, making it highly valuable for pharmaceuticals, agrochemicals, and materials science applications.

Benefits

  • Reduces the use of toxic chemicals by providing a greener alternative to traditional chemical synthesis.
  • Enhances production efficiency and diversity through metabolic engineering and a modular co-culture approach.
  • Enables the synthesis of 26 distinct halogenated molecules, including novel beta-carbolines and prodrug precursors.
  • Achieves high regio- and stereo-selectivity in halogenation, improving product specificity.
  • Offers improved atom economy, making the production process more sustainable.
  • Facilitates applications across various industries, including pharmaceuticals, agrochemicals, and materials.
  • Increases production yields of halogenated tryptophan derivatives, enhancing scalability and commercial viability.

Commercial applications

  • Pharmaceutical drug synthesis
  • Prodrug precursor manufacturing
  • Agrochemical development
  • Specialty chemical production
  • Material science applications

Patents

U.S. Provisional filed 12 Sept 2024

Publication link

https://www.nature.com/articles/s41467-023-40242-9

Patent Information: