Influence of polymer molar mass and mixture stoichiometry on polyelectrolyte complexes of poly(l-arginine) and Poly(l-glutamic acid)

DOI: 10.1016/j.polymer.2022.125497

Authors: Valeria Castelletto (University of Reading) , Lucas De Mello (University of Reading) , Foteini Arfara (University of Athens) , Hermis Iatrou (University of Athens) , Jani Seitsonen (Aalto University) , Ian W. Hamley (University of Reading)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Polymer , VOL 3

State: Published (Approved)
Published: November 2022
Diamond Proposal Number(s): 29895

Abstract: Poly(l-arginine) (PARG) and poly(l-glutamic acid) (PLGA) homopolypeptides were custom synthesized by precision N-carboxyanhydride ring-opening polymerization methods with two molar masses, matched for pairs of cationic and anionic polypeptides (degrees of polymerization n = 100 and n = 500). The conformations of the homopolypeptides were probed using circular dichroism (CD) and FTIR spectroscopy which showed the presence of mainly polyproline II (PPII) conformation. Small-angle X-ray scattering (SAXS) showed concentration-dependent polyelectrolyte peaks and form factor with high q scaling due to the excluded volume behaviour of the wormlike chains. We then examined polyelectrolyte complexation in mixtures of pairs of PARG and PLGA polypeptides with matched molar masses. Precipitation was generally observed and the structures of precipitates, supernatant and resuspended precipitates were investigated using CD, SAXS and cryo-TEM. These revealed that, contrary to prior suggestions in the literature, the precipitates contain mostly polypeptides in a PPII-like conformation, and there is only a minimal β-sheet content (which is enhanced upon drying the sample during preparation for certain measurements). The precipitates have a fractal-like structure as revealed by cryo-TEM and SAXS. Our findings on the structure of polypeptide complex precipitates contribute to the understanding of phase separation of polyelectrolyte complexes and coacervation and may shed light on the formation of inter-cellular bodies of proteins and peptides such as Lewy and other inclusion bodies.

Subject Areas: Chemistry, Biology and Bio-materials


Instruments: B21-High Throughput SAXS

Other Facilities: SWING at SOLEIL

Added On: 16/11/2022 10:47

Discipline Tags:

Biochemistry Chemistry Polymer Science Life Sciences & Biotech

Technical Tags:

Scattering Small Angle X-ray Scattering (SAXS)