Lipid Corona Formation from Nanoparticle Interactions with Bilayers and Membrane-Specific Biological Outcomes

Abstract

<a></a><a>While mixing nanoparticles with certain biological molecules can result in coronas that afford some control over how engineered nanomaterials interact with living systems, corona formation mechanisms remain enigmatic. Here, we report spontaneous lipid corona formation, i.e. without active mixing, upon attachment to stationary lipid bilayer model membranes and bacterial cell envelopes, and present ribosome-specific outcomes for multi-cellular organisms. Experiments show that polycation-wrapped particles disrupt the tails of zwitterionic lipids, increase bilayer fluidity, and leave the membrane with reduced ζ-potentials. Computer simulations show contact ion pairing between the lipid headgroups and the polycations’ ammonium groups leads to the formation of stable, albeit fragmented, lipid bilayer coronas, while microscopy shows fragmented bilayers around nanoparticles after interacting with <i>Shewanella oneidensis</i>. Our mechanistic insight can be used to improve control over nano-bio interactions and to help understand why some nanomaterial/ligand combinations are detrimental to organisms, like <i>Daphnia magna</i>, while others are not. </a>

Hydrogen-Bond Networks near Supported Lipid Bilayers from Vibrational Sum Frequency Generation Experiments and Atomistic Simulations

“…This result further supports recent molecular dynamics simulations indicating that the major contribution in the 3000–3200 cm –1 frequency region originates from polarized water molecules that bridge phosphate and choline in the zwitterionic lipid headgroup . Ultimately, the ability to probe H-bond networks over lipid bilayers holds the promise of opening paths for understanding, controlling, and predicting specific and nonspecific interactions of membranes with solutes such as ions and small molecules such as peptides, or larger species such as polycations, , and coated and uncoated nanomaterials. ,,− …”

Polycation Interactions with Zwitterionic Phospholipid Monolayers on Oil Nanodroplet Suspensions in Water (D2O) Probed by Sum Frequency Scattering

“…Polycations are an important component of many chemical applications, where they are used, for instance, as ligands for engineered nanomaterials, in drug delivery systems, as antimicrobials, and as additives in polymer resins used in consumer products . While the benefits of polycations are numerous, these compounds also have the potential to be harmful once they enter the environment, as they may interact strongly with bacterial membranes even at relatively modest concentrations, as reported recently for the common polycation poly­(allylamine hydrochloride) (PAH). − The interaction between another cationic polymer, poly­(ethlenimine), and mouse fibroblast cells has been shown to induce necrotic cell death . Similarly, polycation–DNA polyplexes have been reported to adhere to cells by interacting with negatively charged phospholipids in cell membranes, while the polycationic bioadhesive chitosan has been reported to disturb the protective boundary of the outer membrane of Gram-negative bacteria .…”

Hydrogen Bond Networks Near Supported Lipid Bilayers from Vibrational Sum Frequency Generation Experiments and Atomistic Simulations

“…2 Ultimately, the ability to probe H-bond networks over lipid bilayers holds the promise of opening paths for understanding, controlling, and predicting specific and non-specific interactions membranes with solutes such as ions 34 and small molecules such as peptides, 70 or larger species such as polycations, 30,38 and coated and uncoated nanomaterials. 31,33,[78][79][80][81][82][83][84] The lines represent the data that have been binned by over nine points in x and y between 3000 cm -1 and 3600 cm -1 .…”