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Updated: Jun 23, 2025

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
Duplex-forming oligocarbamates with tunable nonbonding sites
R Kenton Weigel1, Christopher A Alabi1
1Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University Ithaca New York USA caa238@cornell.edu.
Sequence-defined oligocarbamates (SeDOCs) enable precise control over synthetic assembly. Their hybridization is cooperative and sequence-dependent, offering a new handle for designing functional materials.
Area of Science:
- Polymer Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Biopolymers like proteins and nucleic acids use monomer sequence for self-assembly and function.
- Synthetic polymers lack this sequence-defined control, limiting their applications.
- Existing methods using biopolymers for synthetic assembly are not scalable or robust for harsh conditions.
Purpose of the Study:
- To develop sequence-defined oligocarbamates (SeDOCs) for controlled synthetic assembly.
- To investigate the role of monomer sequence in controlling hybridization and assembly.
- To explore SeDOCs as a platform for creating functional materials in diverse environments.
Main Methods:
- Synthesis of monovalent, divalent, and trivalent SeDOCs with thymine (T) and diaminotriazine (D) pendant groups.
- Characterization of self-assembly using diffusion ordered spectroscopy (DOSY).
- Quantification of binding interactions via 1H-NMR titration and isothermal titration calorimetry (ITC).
Main Results:
- SeDOCs assemble into duplexes via complementary hydrogen bonds.
- Monovalent SeDOC binding is entropically driven and sequence-independent.
- Multivalent SeDOC hybridization is cooperative, with sequence-dependent enthalpy and entropy changes.
- Sequence-dependent thermodynamic changes minimize overall binding free energy.
Conclusions:
- SeDOCs provide a versatile platform for sequence-controlled supramolecular assembly.
- Monomer sequence critically influences the thermodynamics of multivalent hybridization.
- This platform offers a new strategy for designing synthetic materials with tunable properties for various applications.
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