Precision polymers containing main-chain-amino acids: ADMET polymerization and crystallization

Abstract

New PE-type precision oligomers displaying different amino acids (chiral/achiral, polar/non-polar) placed at every 19th carbon atom are presented.

Secondary Structures in Synthetic Poly(Amino Acids): Homo‐ and Copolymers of Poly(Aib), Poly(Glu), and Poly(Asp)

“…Synthesis of the hybrid molecules and their biological assembly processes within the CRC TRR 102 @ Halle/Leipzig. [ 48–50,52,54–56,58–61,63,66,67,143 ] Poly(amino acids) are prepared by ring‐opening polymerization of the respective N ‐carboxy anhydrides, followed by end group modification via the initiator/quencher strategies. Subsequent arrangement into longer chains is accomplished by acyclic diene metathesis (ADMET)‐polymerization, followed by hydrogenation of the double bonds, if desired.…”

Polypeptide‐PEG Conjugates via Ring Opening Polymerization of l‐Alanine N‐Carboxyanhydride

“…The monomer of NCA Alanine ( 2a ) ( Scheme a) was prepared according to literature [ 48 ] verifying the structure of the NCA monomer ( 2a ) by 1 H and 13 C‐NMR (see Figure S1, Supporting Information, for 1 H‐NMR spectra and Figure S2, Supporting Information, for 13 C‐NMR spectra). Subsequently, the primary amine initiator ( 3b ) (Scheme 1b) was synthesized according to the previously published procedure [ 13 ] from ( 1b ) (Scheme 1b) in a two‐step process, firstly by amidation of acyl chloride to prepare the corresponding carboxiamide ( 2b ) (Scheme 1b) (see Figure S3, Supporting Information, for 1 H‐NMR spectra), followed by reduction of the amide to the primary amine to obtain 10‐undecene‐1‐amine ( 3b ) (Scheme 1b). The pure product 3b was obtained in a yield of 52% and its structure was verified by 1 H‐NMR (see Figure S4, Supporting Information).…”

“…The monomer of NCA Alanine (2a) (Scheme 1a) was prepared according to literature [48] verifying the structure of the NCA monomer (2a) by 1 H and 13 C-NMR (see Figure S1, Supporting Information, for 1 H-NMR spectra and Figure S2, Supporting Information, for 13 C-NMR spectra). Subsequently, the primary amine initiator (3b) (Scheme 1b) was synthesized according to the previously published procedure [13] from (1b) (Scheme 1b) in a two-step process, firstly by amidation of acyl chloride to prepare the corresponding carboxiamide (2b) (Scheme 1b) (see Figure S3, Supporting Information, for 1 H-NMR spectra), followed by reduction of the amide to the primary amine to obtain 10-undecene-1-amine (3b) (Scheme 1b). The pure product 3b was obtained in a yield of 52% and its structure was verified by 1 H-NMR (see Figure S4, Supporting Information).…”

“…Amphiphilic polypeptide-polymer hybrids have been of interest for biomedical and nonbiological applications [1,2] as materials [3][4][5][6] to achieve biocompatibility, stable 3D structures and responsiveness to external stimuli [7,8] by taking advantage of the versatility of folding and self-assembly of their polypeptide elements. [9][10][11][12][13][14] Specific interactions of the amino acids inside the polypeptide with solvents, [15][16][17][18] together with inter-and intramolecular hydrogen bonding, [19][20][21] hydrophobic, [21,22] and van der Waals forces [21] can induce the formation of secondary structures such as 𝛼-helices [23] or 𝛽-sheets, [24] further ordering the poly(peptides) inside these materials.…”

Tuning layered superstructures in precision polymers

“…The freedom to elegantly engineer molecules with accurately controlled sequences has opened up an untapped reservoir of application relevant materials. Biomimetic approaches towards engineering in-vivo biocompatible materials incorporating various other regularly spaced groups along a flexible aliphatic chain have received considerable interest 13,14 . According to a recent study, precision polyethylenes containing regularly spaced acidic groups can be used for efficient ion transport 5 .…”