skip to main content


Title: Binding, unbinding and aggregation of crescent-shaped nanoparticles on nanoscale tubular membranes
Using molecular dynamics simulations of a coarse-grained implicit solvent model, we investigate the binding of crescent-shaped nanoparticles (NPs) on tubular lipid membranes. The NPs adhere to the membrane through their concave side. We found that the binding/unbinding transition is first-order, with the threshold binding energy being higher than the unbinding threshold, and the energy barrier between the bound and unbound states at the transition that increases with increasing the NP's arclength L np or curvature mismatch μ = R c / R np , where R c and R np are the radii of curvature of the tubular membrane and the NP, respectively. Furthermore, we found that the threshold binding energy increases with increasing either L np or μ . NPs with curvature larger than that of the tubule ( μ > 1) lie perpendicularly to the tubule's axis. However, for μ smaller than a specific arclength-dependent mismatch μ *, the NPs are tilted with respect to the tubule's axis, with the tilt angle that increases with decreasing μ . We also investigated the self-assembly of the NPs on the tubule at relatively weak adhesion strength and found that for μ > 1 and high values of L np , the NPs self-assemble into linear chains, and lie side-by-side. For μ < μ * and high L np , the NPs also self-assemble into chains, while being tilted with respect to the tubule's axis.  more » « less
Award ID(s):
1931837
NSF-PAR ID:
10211697
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Soft Matter
ISSN:
1744-683X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Lipid-coated noble metal nanoparticles (L-NPs) combine the biomimetic surface properties of a self-assembled lipid membrane with the plasmonic properties of a nanoparticle (NP) core. In this work, we investigate derivatives of cholesterol, which can be found in high concentrations in biological membranes, and other terpenoids, as tunable, synthetic platforms to functionalize L-NPs. Side chains of different length and polarity, with a terminal alkyne group as Raman label, are introduced into cholesterol and betulin frameworks. The synthesized tags are shown to coexist in two conformations in the lipid layer of the L-NPs, identified as “head-out” and “head-in” orientations, whose relative ratio is determined by their interactions with the lipid–water hydrogen-bonding network. The orientational dimorphism of the tags introduces orthogonal functionalities into the NP surface for selective targeting and plasmon-enhanced Raman sensing, which is utilized for the identification and Raman imaging of epidermal growth factor receptor–overexpressing cancer cells.

     
    more » « less
  2. The adhesion modes and endocytosis pathway of spherocylindrical nanoparticles (NPs) are investigated numerically using molecular dynamics simulations of a coarse-grained implicit-solvent model. The investigation is performed systematically with respect to the adhesion energy density ξ, NP’s diameter D, and NP’s aspect ratio α. At weak ξ, the NP adheres to the membrane through a parallel mode, i.e., its principal axis is parallel to the membrane. However, for relatively large ξ, the NP adheres through a perpendicular mode, i.e., the NP is invaginated, such as its principal axis is nearly perpendicular to the membrane. The value of ξ at the transition from the parallel to the perpendicular mode decreases with increasing the D or α, in agreement with theoretical arguments based on the Helfrich Hamiltonian. As ξ is further increased, the NP undergoes endocytosis, with the value of ξ at the endocytosis threshold that is independent of the aspect ratio but decreases with increasing D. The kinetics of endocytosis depends strongly on ξ and D. While for low values of D, the NP first rotates to a parallel orientation then to a perpendicular orientation. At high values of ξ or D, the NP is endocytosed while in the parallel orientation. 
    more » « less
  3. Abstract

    How nanoparticle (NP) mechanical properties impact multivalent ligand–receptor‐mediated binding to cell surfaces, the avidity, propensity for internalization, and effects due to crowding remains unknown or unquantified. Through computational analyses, the effects of NP composition from soft, deformable NPs to rigid spheres, effect of tethers, the crowding of NPs at the membrane surface, and the cell membrane properties such as cytoskeletal interactions are addressed. Analyses of binding mechanisms of three distinct NPs that differ in type and rigidity (core‐corona flexible NP, rigid NP, and rigid‐tethered NP) but are otherwise similar in size and ligand surface density are reported; moreover, for the case of flexible NP, NP stiffness is tuned by varying the internal crosslinking density. Biophysical modeling of NP binding to membranes together with thermodynamic analysis powered by free energy calculations is employed, and it is shown that efficient cellular targeting and uptake of NP functionalized with targeting ligand molecules can be shaped by factors including NP flexibility and crowding, receptor–ligand binding avidity, state of the membrane cytoskeleton, and curvature inducing proteins. Rational design principles that confer tension, membrane excess area, and cytoskeletal sensing properties to the NP which can be exploited for cell‐specific targeting of NP are uncovered.

     
    more » « less
  4. In this study, hydrophilic silica nanoparticles (Si NPs) were used to modify α-alumina tubular membranes to improve their performance in terms of flux, oil rejection, and anti-fouling properties. Our work focuses on enhancing membrane performance, particularly for difficult applications such as produced water treatment. The prepared membranes were applied for oil-in-water emulsion treatment. After coating hydrophilic Si NPs, the oil contact angle improved from 133.8° to 171.4°. To prevent Si NPs from leaching off the surface of α-alumina tubular membranes, polyvinyl alcohol was used to coat the membranes as a pre-treatment step before Si NP modification. After coating the membrane with Si NPs, the roughness of the membrane surface decreased, likely leading to less fouling. After coating Si NPs, Total Organic Carbon rejection increased from 93.1% for pristine α-alumina tubular membranes to 97.7% for silica-modified membranes because of hydrophilic improvements of the modified membranes. The Si NP coating improved the anti-fouling property of membranes with the flux recovery ratio increasing from 71.3% for pristine α-alumina tubular membranes to 85.9% for silica-modified membranes. Scanning Electron Microscopy, Energy- dispersive X-ray spectroscopy, oil contact angle, and Atomic Force Microscopy characterization tests were done. The tests showed successful Si NPs impregnation and altered wettability. 
    more » « less
  5. Abstract

    Gels self‐assembled from colloidal nanoparticles (NPs) translate the size‐dependent properties of nanostructures to materials with macroscale volumes. Large spanning networks of NP chains provide high interconnectivity within the material necessary for a wide range of properties from conductivity to viscoelasticity. However, a great challenge for nanoscale engineering of such gels lies in being able to accurately and quantitatively describe their complex non‐crystalline structure that combines order and disorder. The quantitative relationships between the mesoscale structural and material properties of nanostructured gels are currently unknown. Here, it is shown that lead telluride NPs spontaneously self‐assemble into a spanning network hydrogel. By applying graph theory (GT), a method for quantifying the complex structure of the NP gels is established using a topological descriptor of average nodal connectivity that is found to correlate with the gel's mechanical and charge transport properties. GT descriptions make possible the design of non‐crystalline porous materials from a variety of nanoscale components for photonics, catalysis, adsorption, and thermoelectrics.

     
    more » « less