Journal of Physical Chemistry B, Vol.107, No.32, 8172-8180, 2003
Analysis of compacted semiflexible polyanions visualized by atomic force microscopy: Influence of chain stiffness on the morphologies of polyelectrolyte complexes
The morphologies of the compacted semiflexible biological polyanions alginate, acetan, circular plasmid DNA, and xanthan were investigated using tapping mode atomic force microscopy followed by quantitative image analysis. A shape factor was calculated for each of the observed polyelectrolyte complexes and used as a basis for dividing the structures into ensembles of morphologically linear, toroidal, and globular structures for subsequent quantitative analysis. Compaction of polyanions with chitosan yielded a small fraction of the torus morphology when the persistence length, L-p, of 25 nm (acetan) was reached. For both DNA, L-p = 50 nm, and xanthan, L-p, = 120 nm, it was found that the toroids make up a substantial fraction of the complexed structures formed by the given chitosan and at room temperature. Rodlike complexes were additionally observed within DNA-chitosan complexes, whereas they do not appear as a significant fraction of chitosan-complexed high-molecular-weight xanthan. The average height of the condensates was observed to be similar to2 nm for the compacted xanthan toroids, while it was determined to be similar to5 nm for compacted DNA toroids. Reducing the degree of polymerization of xanthan yielded a decrease in the fraction of toroids. Compacted xanthan at room temperature displays a number of racquets and other morphologies similar to the reported intermediate, metastable states by simulations. The reduced abundance of such structures following annealing supports the interpretation of their metastable nature.