Counterion Distribution Surrounding Spherical Nucleic Acid-Au Nanoparticle Conjugates Probed by Small-Angle X-ray Scattering

TitleCounterion Distribution Surrounding Spherical Nucleic Acid-Au Nanoparticle Conjugates Probed by Small-Angle X-ray Scattering
Publication TypeJournal Article
Year of Publication2013
AuthorsKewalramani, S, Zwanikken, JW, Macfarlane, RJ, Leung, C-Y, de la Cruz, MOlvera, Mirkin, CA, Bedzyk, MJ
JournalAcs Nano
Volume7
Issue12
Pagination11301 - 11309
Date Published2013/12//
ISBN Number1936-0851
Abstract

The radial distribution of monovalent cations surrounding spherical nucleic acid-Au nanoparticle conjugates (SNA-AuNPs) is determined by in situ small-angle x-ray scattering (SAXS) and classical density functional theory (DFT) calculations. Small differences in SAXS intensity profiles from SNA-AuNPs dispersed in a series of solutions containing different monovalent ions (Na+, K+, Rb+, or Cs+) are measured. Using the "heavy ion replacement" SAXS (HIRSAXS) approach, we extract the cation-distribution-dependent contribution to the SAXS intensity and show that it agrees with DFT predictions. The experiment-theory comparisons reveal the radial distribution of cations as well as the conformation of the DNA in the SNA shell. The analysis shows an enhancement to the average cation concentration in the SNA shell that can be up to 15-fold, depending on the bulk solution ionic concentration. The study demonstrates the feasibility of HIRSAXS in probing the distribution of monovalent cations surrounding nanoparticles with an electron dense core (e.g., metals).