Effect of polyelectrolyte structure on protein-polyelectrolyte coacervates: coacervates of bovine serum albumin with poly(diallyldimethylammonium chloride) versus chitosan.
Electrostatic interactions between synthetic polyelectrolytes and proteins can lead to the formation of dense, macroion-rich liquid phases, with equilibrium microheterogeneities on length scales up to hundreds of nanometers. The effects of pH and ionic strength on the rheological and optical properties of these coacervates indicate microstructures sensitive to protein-polyelectrolyte interactions. We report here on the properties of coacervates obtained for bovine serum albumin (BSA) with the biopolyelectrolyte chitosan and find remarkable differences relative to coacervates obtained for BSA with poly(diallyldimethylammonium chloride) (PDADMAC). Coacervation with chitosan occurs more readily than with PDADMAC. Viscosities of coacervates obtained with chitosan are more than an order of magnitude larger and, unlike those with PDADMAC, show temperature and shear rate dependence. For the coacervates with chitosan, a fast relaxation time in dynamic light scattering, attributable to relatively unrestricted protein diffusion in both systems, is diminished in intensity by a factor of 3-4, and the consequent dominance by slow modes is accompanied by a more heterogeneous array of slow apparent diffusivities. In place of a small-angle neutron scattering Guinier region in the vicinity of 0.004 A-1, a 10-fold increase in scattering intensity is observed at lower q. Taken together, these results confirm the presence of dense domains on length scales of hundreds of nanometers to micrometers, which in coacervates prepared with chitosan are less solidlike, more interconnected, and occupy a larger volume fraction. The differences in properties are thus correlated with differences in mesophase structure.
Kayitmazer
A Basak
AB
Department of Chemistry, University of Massachusetts-Amherst, 710 North Pleasant Street, Amherst, MA 01003, USA. kayitmazer@northwestern.edu
Strand
Sabina P
SP
Tribet
Christophe
C
Jaeger
Werner
W
Dubin
Paul L
PL
D000818:Animals; D002417:Cattle; D048271:Chitosan / Q000737:chemistry*; D020285:Cryoelectron Microscopy; D004058:Diffusion; D004573:Electrolytes; D006863:Hydrogen-Ion Concentration; D046529:Microscopy, Electron, Transmission; D009391:Nephelometry and Turbidimetry; D009502:Neutrons; D011095:Polyethylenes / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012212:Rheology; D012710:Serum Albumin, Bovine / Q000737:chemistry*; D013057:Spectrum Analysis; D017186:Titrimetry; D014783:Viscosity
D004573:Electrolytes; D011095:Polyethylenes; D000644:Quaternary Ammonium Compounds; C041004:poly-N,N-dimethyl-N,N-diallylammonium chloride; D012710:Serum Albumin, Bovine; D048271:Chitosan