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Natural products, particularly ribosomally synthesized and post-translationally modified peptides (RiPPs), can be synthesized into diverse libraries using natural biosynthetic machinery. This approach enables the creation of millions of novel compounds through genetic engineering and understanding of biosynthetic pathways.

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Area of Science:

  • Biochemistry
  • Synthetic Biology
  • Natural Product Chemistry

Background:

  • Natural products are crucial therapeutic agents and drug leads due to their complex structures.
  • Enzymes in natural product biosynthesis pathways offer potential for generating novel compounds and libraries.
  • Challenges exist in rationally synthesizing small molecules with novel structures and maximizing chemical diversity.

Purpose of the Study:

  • To describe recent advances in synthesizing natural product-like libraries using natural biosynthetic machinery.
  • To focus on the pat and tru biosynthetic pathways for cyanobactin class natural products.
  • To explore principles of diversity-generating biosynthesis.

Main Methods:

  • Utilized the pat and tru biosynthetic pathways from cyanobacterial symbionts.
  • Leveraged the ribosomal synthesis and post-translational modification of peptides (RiPPs).
  • Applied recombinant technologies and genetic engineering tools.

Main Results:

  • Enabled synthesis of rationally designed small molecules and libraries with over 1 million estimated derivatives.
  • Demonstrated compatibility of RiPPs with recombinant technologies for synthesizing natural products and derivatives.
  • Identified three principles of diversity-generating biosynthesis: substrate evolution, recognition sequence-enzyme pairing, and inverse metabolic flux.

Conclusions:

  • The principles identified may enable the design of novel derivatives through biosynthetic engineering.
  • Shuffling recognition sequences and enzymes can create new hybrid products.
  • Understanding biosynthetic pathway regulation, including inverse metabolic flux, can optimize in vivo synthesis of new compounds.