Nanoparticle charge-transfer interactions induce surface dependent   conformational changes in apolipoprotein biocorona
  Upon introduction into a biological system, engineered nanomaterials (ENMs) rapidly associate with a variety of biomolecules such as proteins and lipids to form a biocorona. The presence of biocorona influences nano-bio interactions considerably, and could ultimately result in altered biological responses. Apolipoprotein A-I (ApoA-I), the major constituent of high-density lipoprotein (HDL), is one of the most prevalent proteins found in ENM-biocorona irrespective of ENM nature, size, and shape. Given the importance of ApoA-I in HDL and cholesterol transport, it is necessary to understand the mechanisms of ApoA-I adsorption and the associated structural changes for assessing consequences of ENM exposure. Here, we used a comprehensive array of microscopic and spectroscopic tools to elucidate the interactions between ApoA-I and 100 nm Ag nanoparticles (AgNPs) with four different surface functional groups. We found that the protein adsorption and secondary structural changes are highly dependent on the surface functionality. Our electrochemical studies provided new evidence for charge transfer interactions that influence ApoA-I unfolding. While the unfolding of ApoA-I on AgNPs did not significantly modify their cellular uptake and short-term cytotoxicity, we observed that it strongly altered the ability of only some AgNPs to generate reactive oxygen species in macrophages. Our results shed new light on the importance of surface functionality and charge transfer interactions in biocorona formation. 
Achyut J Raghavendra, Nasser Alsaleh, Jared M. Brown, and Ramakrishna   Podilaa
physics.bio-ph cond-mat.mes-hall cond-mat.mtrl-sci cond-mat.soft