Research Field 3

Freudenberg, J., et al. Macromolecules 2019,52 (12), 4534-4544,DOI: https://doi.org/10.1021/acs.macromol.9b00684.

The synthesis of multisegmented polymers containing repetitive oligo-(^BnAsp_n, ^BnGlu_n) sequences separated by methylene units and their secondary structure formation in solution and in the solid state are reported. Combining ring-opening polymerization (ROP) of N-carboxyanhydrides with postfunctionalization of the respective N-terminus yields the oligo-( ^BnAsp₃, ^BnAsp₁₀, ^BnGlu₃, and ^BnGlu₁₀) sequences bearing terminal vinyl groups on either side of the polymer chain by preparative gel permeation chromatography generate polymers of a precise degree of polymerization (n = 3, 10; m = 1–136). β-sheet conformation is identified as the thermodynamically more stable conformation, as supported by our experiments in the solid state and in solution. Reproduced with permission. Copyright 2019©, American Chemical Society.

Evgrafova, Z., et al. Physical Chemistry Chemical Physics 2019,21 (37), 20999-21006,DOI: http://dx.doi.org/10.1039/C9CP02683E.

A substantial number of diseases leading to loss of neurologic functions such as Morbus Alzheimer, Morbus Parkinson, or Chorea Huntington are related to the fibrillation of particular amyloidogenic peptides. We investigated amyloid-beta 1–40 peptide (Aβ_1–40) fibrillation in mixture with thermoresponsive poly(oligo(ethylene glycol)macrylates), in which the polymer’s hydrophobicity is tuned by variation of the number of ethylene glycol-units in the side chain (m = 1–9), the end groups (B = butoxy; C = carboxy; D = dodecyl; P = pyridyldisulfide). The polymers were prepared via RAFT-polymerization. Less hydrophilic polymers (m = 1–2) were able to both decrease and elongate the lag (tlag) and characteristic times (tchar) of Aβ_1–40 fibril formation in dependence of their end groups, molecular mass and hydrophilicity. Reproduced with permission from the PCCP Owner Societies.

Evgrafova, Z., et al. ChemPhysChem2019,20 (2), 236-240,DOI: https://doi.org/10.1002/cphc.201800867.

Covalent conjugates between a synthetic polymer and a peptide hormone were used to probe the molecular extension of these macromolecules. NMR spectroscopy of ¹⁵N labeled parathyroid hormone (PTH) was employed to visualize the shroud-like polymer conformation of the conjugated chimeras. Reproduced by permission. Copyright © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Canalp, M., et al. RCS Advances2019,9 (38), 21707-21714,DOI: http://dx.doi.org/10.1039/C9RA03099A.

Narrow-dispersed, end group-telechelic, oligomeric-(l-lysine(carboxybenzyl (Z)/trifluoroacetyl (TFA)))ns (n = 3–33) were prepared as a model system for studying assembly and secondary structure formation. Fibril formation of oligomeric-(L-lysine(Z/TFA))_ns with shorter chain lengths (n = 7 and n = 3) were chosen to investigate the effect of the number of repeating units’ role on the self-assembly of the oligomers in TFE. Reproduced by permission of The Royal Society of Chemistry.

Deike, S., et al. Macromolecules 2017,50 (7), 2637-2644,DOI: http://dx.doi.org/10.1021/acs.macromol.7b00343.

Chiral and achiral β-turn mimetic polymer conjugates were synthesized, based on chiral helical poly(n-hexyl isocyanate)s (PHICs), and allowing to tune the distance between the PHIC-helix and the chiral center from 7 to 14 Å.. Circular dichroism (CD) spectra confirmed chirality induction from the chiral β-turn mimetic structure to the polymer backbone of the achiral PHIC over five chemical bonds via postpolymerization modification, and revealed a distance-dependent effect for the transmission of stereochemical information. Reproduced with permission. Copyright 2017©, American Chemical Society.