The electronic structure of plasmid DNA both prior to and after its conjugation with Hg nanoparticles (NP) has been investigated here. The DNA molecules undergo severe perturbation on their interaction with Hg-NP. The circular plasmid DNA becomes predominantly linearised on interaction with 10 mM Hg salt solution. These perturbations are also reflected in the electronic structure of C1s and O1s suggesting severe modi. cations in the exocyclic groups, of the nucleic acid bases, participating in the hydrogen bondings. The results reflect the rupturing of the purine-pyrimidine bonds after interaction with the NP. The study also suggests selective and specific interactions of DNA bases with the Hg nanoparticles leading to the formation of metal-purine-pyrimidine complexes through rupturing of G-C base pairs. Hg-NP exclusively interact with the nitrogen bases of the DNA molecule and do not cause any significant modi. cation to the phosphate backbone of DNA. (C) 2009 Elsevier B.V. All rights reserved.