Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation.

Area of Science:

• Polymer Chemistry
• Organic Synthesis
• Materials Science

Background:

• Sequence-defined polymers are crucial for applications like biomimetics, self-assembly, catalysis, and information storage.
• Precisely controlling polymer primary structure is key to unlocking complex chemical functionalities.

Purpose of the Study:

• To develop efficient solution-phase and solid-phase synthesis methods for discrete oligourethanes.
• To establish a self-immolative sequencing strategy for rapid and robust characterization of oligourethanes and polymers.

Main Methods:

• Synthesized discrete oligourethanes using both solution-phase and high-yielding solid-phase techniques.
• Utilized the inherent reactivity of the terminal alcohol group to initiate a controlled, iterative
• unzipping
• self-immolation process.
• Monitored the self-immolation reaction using liquid chromatography-mass spectrometry (LC/MS) and applied an algorithm for sequence determination.

Main Results:

• Achieved high-yielding syntheses of discrete oligourethanes.
• Demonstrated a novel self-immolative sequencing method that rapidly characterizes oligomers without MS/MS.
• Successfully identified each released monomer as a 2-oxazolidinone during the unzipping process.
• The applied algorithm accurately deduced the oligourethane sequence from LC/MS data.

Conclusions:

• The developed self-immolative sequencing method provides rapid and robust characterization of oligourethanes and related polymers.
• This approach effectively reads molecular information encoded in the polymer sequence, enabling the characterization of complex structures.
• The methodology offers a powerful tool for analyzing sequence-defined polymers, advancing their application in diverse fields.