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. 2016 Mar 14;55(12):3925-30.
doi: 10.1002/anie.201509864. Epub 2016 Feb 10.

Triazine-Based Sequence-Defined Polymers with Side-Chain Diversity and Backbone-Backbone Interaction Motifs

Jay W Grate  1 , Kai-For Mo  2 , Michael D Daily  2
Affiliations

Triazine-Based Sequence-Defined Polymers with Side-Chain Diversity and Backbone-Backbone Interaction Motifs

Jay W Grate et al. Angew Chem Int Ed Engl. .

Abstract

Sequence control in polymers, well-known in nature, encodes structure and functionality. Here we introduce a new architecture, based on the nucleophilic aromatic substitution chemistry of cyanuric chloride, that creates a new class of sequence-defined polymers dubbed TZPs. Proof of concept is demonstrated with two synthesized hexamers, having neutral and ionizable side chains. Molecular dynamics simulations show backbone-backbone interactions, including H-bonding motifs and pi-pi interactions. This architecture is arguably biomimetic while differing from sequence-defined polymers having peptide bonds. The synthetic methodology supports the structural diversity of side chains known in peptides, as well as backbone-backbone hydrogen-bonding motifs, and will thus enable new macromolecules and materials with useful functions.

Keywords: biomimetics; macromolecules; sequence-defined polymers; simulations; solid-phase synthesis.

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Figures

Scheme 1
Scheme 1
Triazine‐based polymers.
Scheme 2
Scheme 2
Submonomer solid‐phase synthesis of a triazine‐based polymer.
Figure 1
Figure 1
HPLC chromatogram of crude and pure TZP 3.
Figure 2
Figure 2
High‐resolution mass spectrum and isotopic pattern of TZP 3. The expanded spectrum shows the adduct [M+H]+.
Figure 3
Figure 3
1H NMR spectra (500 MHz) of TZPs 3 (upper) and 4 (bottom) in deuterated methanol.
Figure 4
Figure 4
Tandem MS spectra of the [M+H]+ adduct of TZPs 3 (upper) and 4 (bottom). Fragments from breaking triazine rings(T) are indicated by ring number and left(L) or right(R) fragments. See the Supporting Information for details.
Figure 5
Figure 5
MD simulations of a) two tetramers and b) two trimers interacting by hydrogen bonding and pi–pi interactions. Side chains are S‐ethyl, and nonpolar hydrogen atoms are not shown.
Figure 6
Figure 6
Backbone–backbone hydrogen‐bonding motifs found in molecular dynamics simulations of triazine‐based polymers. Paired hydrogen bonds in DNA and peptide beta sheets are shown for comparison.
See this image and copyright information in PMC

References

    1. None
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