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Structural and functional effects of Cu metalloprotein-driven silver nanoparticle dissolution.

Andrew J Martinolich1, Grace Park, Meagan Y Nakamoto

  • 1Department of Chemistry & Biochemistry, Santa Clara University, Santa Clara, California 95053 United States.

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Copper(II) azurin catalyzes silver nanoparticle dissolution, forming silver(I) azurin species. This interaction at the nanoparticle surface influences both protein and nanoparticle reactivity, impacting biological outcomes.

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Area of Science:

  • Biochemistry
  • Nanotechnology
  • Materials Science

Background:

  • Silver nanoparticles (NPs) exhibit unique properties but their biological interactions are complex.
  • Metalloproteins, like azurin, play crucial roles in biological systems and can interact with nanomaterials.

Purpose of the Study:

  • To investigate the interaction between azurin and silver nanoparticles (NPs).
  • To elucidate the role of oxidative dissolution and protein interaction in NP biological reactivity.

Main Methods:

  • Studied interactions between a model Cu-metalloprotein, azurin, and 10-100 nm silver NPs under aerobic and anaerobic conditions.
  • Analyzed protein structural changes, Cu(II) displacement, and formation of Ag(I) azurin species.
  • Utilized dialysis experiments to assess reactivity between azurin and dissolved Ag(I) species.

Main Results:

  • Cu(II) azurin acts as a catalyst for NP oxidative dissolution, forming Ag(I) azurin species, particularly with smaller NPs (10 nm).
  • Apo-protein formation observed under anaerobic conditions and with larger NPs (>20 nm) where oxidation is slower.
  • Cu displacement from azurin occurs at the NP surface, not with dissolved Ag(I) species.

Conclusions:

  • Silver NP interactions significantly alter protein structure and function.
  • Protein interactions modulate NP reactivity, influencing targeting, uptake, and cytotoxicity.
  • Proposed mechanisms for azurin-silver NP interactions provide insights into nanomaterial-biomolecule behavior.