DNA bending by hexamethylene-tethered ammonium ions

DNA is bent when complexed with certain proteins. We are exploring the hypothesis that asymmetric neutralization of phosphate charges will cause the DNA double helix to collapse toward the neutralized face. We have previously shown that DNA spontaneously bends toward one face of the double helix when it is partially substituted with neutral methylphosphonate linkages. We have now synthesized DNA duplexes in which cations are tethered by hexamethylene chains near specific phosphates. Electrophoretic phasing experiments demonstrate that tethering six ammonium ions on one helical face causes DNA to bend by ≃5° toward that face, in qualitative agreement with predictions. Ion pairing between tethered cottons and DNA phosphates provides a new model for simulating the electrostatic consequences of phosphate neutralization by proteins.