A comprehensive study is reported on the effect of salt concentration, polyelectrolyte block length, and polymer concentration on the morphology and structural properties of nanoaggregates self-assembled from BAB single-strand DNA (ssDNA) triblock polynucleotides in which A represents polyelectrolyte blocks and B represents hydrophobic neutral blocks. A morphological phase diagram above the gelation point is developed as a function of solvent ionic strength and polyelectrolyte block length utilizing an implicit solvent ionic strength method for dissipative particle dynamics simulations. As the solvent ionic strength increases, the self-assembled DNA network structures shrinks considerably, leading to a morphological transition from a micellar network to worm-like or hamburger-shape aggregates. This study provides insight into the network morphology and its changes by calculating the aggregation number, number of hydrophobic cores, and percentage of bridge chains in the network. The simulation results are corroborated through cryogenic transmission electron microscopy on the example of the self-assembly of ssDNA triblocks.
Bibliographical noteFunding Information:
This work was supported by the National Science Foundation (NSF) DMR-1410462, NSF’s Research Triangle Materials Research Science and Engineering Center (MRSEC) (DMR-1121107), and NSF.CMMI-1150682. The computer support was provided by the High Performance Computing Center at North Carolina State University.
- block copolymers
- dissipative particle dynamics simulations
- responsive morphology