3 research outputs found
Hydrogen Bond Networks Near Supported Lipid Bilayers from Vibrational Sum Frequency Generation Experiments and Atomistic Simulations
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<p>We report vibrational sum frequency generation (SFG) spectra in which the CāH
stretches of lipid alkyl tails in fully hydrogenated single- and dual-component supported lipid
bilayers are detected along with the OāH stretching continuum above the bilayer. As the salt
concentration is increased from ~10 Ī¼M to 0.1 M, the SFG intensities in the OāH stretching
region decrease by a factor of 2, consistent with significant absorptive-dispersive mixing
between Ļ(2) and Ļ(3) contributions to the SFG signal generation process from charged interfaces.
A method for estimating the surface potential from the second-order spectral lineshapes (in the
OH stretching region) is presented and discussed in the context of choosing truly zero-potential
reference states. Aided by atomistic simulations, we find that the strength and orientation
distribution of the hydrogen bonds over the purely zwitterionic bilayers are largely invariant
between sub-micromolar and hundreds of millimolar concentrations. However, specific interactions between water molecules and lipid headgroups are observed upon replacing phosphocholine (PC) lipids with negatively charged phosphoglycerol (PG) lipids, which
coincides with SFG signal intensity reductions in the 3100 cm-1 to 3200 cm-1 frequency region.
The atomistic simulations show that this outcome is consistent with a small, albeit statistically
significant, decrease in the number of water molecules adjacent to both the lipid phosphate and
choline moieties per unit area, supporting the SFG observations. Ultimately, the ability to probe
hydrogen-bond networks over lipid bilayers holds the promise of opening paths for
understanding, controlling, and predicting specific and non-specific interactions between
membranes and ions, small molecules, peptides, polycations, proteins, and coated and uncoated
nanomaterials.<br></p></div></div
Hydrogen-Bond Networks near Supported Lipid Bilayers from Vibrational Sum Frequency Generation Experiments and Atomistic Simulations
We
report vibrational sum frequency generation (SFG) spectra in
which the CāH stretches of lipid alkyl tails in fully hydrogenated
single- and dual-component supported lipid bilayers are detected along
with the OāH stretching continuum above the bilayer. As the
salt concentration is increased from ā¼10 Ī¼M to 0.1 M,
the SFG intensities in the OāH stretching region decrease by
a factor of 2, consistent with significant absorptiveādispersive
mixing between Ļ<sup>(2)</sup> and Ļ<sup>(3)</sup> contributions
to the SFG signal generation process from charged interfaces. A method
for estimating the surface potential from the second-order spectral
lineshapes (in the OH stretching region) is presented and discussed
in the context of choosing truly zero-potential reference states.
Aided by atomistic simulations, we find that the strength and orientation
distribution of the hydrogen bonds over the purely zwitterionic bilayers
are largely invariant between submicromolar and hundreds of millimolar
concentrations. However, specific interactions between water molecules
and lipid headgroups are observed upon replacing phosphocholine (PC)
lipids with negatively charged phosphoglycerol (PG) lipids, which
coincides with SFG signal intensity reductions in the 3100ā3200
cm<sup>ā1</sup> frequency region. The atomistic simulations
show that this outcome is consistent with a small, albeit statistically
significant, decrease in the number of water molecules adjacent to
both the lipid phosphate and choline moieties per unit area, supporting
the SFG observations. Ultimately, the ability to probe hydrogen-bond
networks over lipid bilayers holds the promise of opening paths for
understanding, controlling, and predicting specific and nonspecific
interactions between membranes and ions, small molecules, peptides,
polycations, proteins, and coated and uncoated nanomaterials
Lipid Corona Formation from Nanoparticle Interactions with Bilayers and Membrane-Specific Biological Outcomes
<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 Ī¶-potentials. Computer simulations show contact
ion pairing between the lipid headgroups and the polycationsā 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