title: Counterion distribution surrounding spherical nucleic acid-Au nanoparticle conjugates probed by small-angle x-ray scattering.
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).
authors.affiliation: Department of Materials Science and Engineering, ‡Department of Chemistry, and §Department of Physics and Astronomy, Northwestern University , Evanston, Illinois 60208, United States.
authors.forename: Sumit
authors.initials: S
authors.lastname: Kewalramani
authors.forename: Jos W
authors.initials: JW
authors.lastname: Zwanikken
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Macfarlane
authors.forename: Cheuk-Yui
authors.initials: CY
authors.lastname: Leung
authors.forename: Monica
authors.initials: M
authors.lastname: Olvera de la Cruz
authors.forename: Chad A
authors.initials: CA
authors.lastname: Mirkin
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bedzyk
mesh_terms: D002412:Cations; D004247:DNA / Q000737:chemistry; D004583:Electrons; D006046:Gold / Q000737:chemistry*; D007477:Ions; D053758:Nanoparticles / Q000737:chemistry*; D036103:Nanotechnology; D009690:Nucleic Acid Conformation; D009696:Nucleic Acids / Q000737:chemistry*; D009841:Oligonucleotides / Q000737:chemistry; D016012:Poisson Distribution; D012542:Scattering, Radiation; D053838:Scattering, Small Angle; D013438:Sulfhydryl Compounds; D014961:X-Ray Diffraction; D014965:X-Rays
chemical_list: D002412:Cations; D007477:Ions; D009696:Nucleic Acids; D009841:Oligonucleotides; D013438:Sulfhydryl Compounds; D006046:Gold; D004247:DNA