Understanding protein adsorption behavior on rough and wrinkled surfaces is vital to applications including biosensors and flexible biomedical devices. Despite this, there is a dearth of study on protein interaction with regularly undulating surface topographies, particularly in regions of negative curvature. Here we report nanoscale adsorption behavior of immunoglobulin M (IgM) and immunoglobulin G (IgG) on wrinkled and crumpled surfaces via atomic force microscopy (AFM). Hydrophilic plasma treated poly(dimethylsiloxane) (PDMS) wrinkles with varying dimensions exhibit higher surface coverage of IgM on wrinkle peaks over valleys. Negative curvature in the valleys is determined to reduce protein surface coverage based both on an increase in geometric hindrance on concave surfaces, and reduced binding energy as calculated in coarse-grained molecular dynamics simulations. The smaller IgG molecule in contrast shows no observable effects on coverage from this degree of curvature. The same wrinkles with an overlayer of monolayer graphene show hydrophobic spreading and network formation, and inhomogeneous coverage across wrinkle peaks and valleys attributed to filament wetting and drying effects in the valleys. Additionally, adsorption onto uniaxial buckle delaminated graphene shows that when wrinkle features are on the length scale of the protein diameter, hydrophobic deformation and spreading do not occur and both IgM and IgG molecules retain their dimensions. These results demonstrate that undulating wrinkled surfaces characteristic of flexible substrates can have significant effects on protein surface distribution with potential implications for design of materials for biological applications.
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The competing influence of surface roughness, hydrophobicity, and electrostatics on protein dynamics on a self-assembled monolayer
Surface morphology, in addition to hydrophobic and electrostatic effects, can alter how proteins interact with solid surfaces. Understanding the heterogeneous dynamics of protein adsorption on surfaces with varying roughness is experimentally challenging. In this work, we use single-molecule fluorescence microscopy to study the adsorption of α-lactalbumin protein on the glass substrate covered with a self-assembled monolayer (SAM) with varying surface concentrations. Two distinct interaction mechanisms are observed: localized adsorption/desorption and continuous-time random walk (CTRW). We investigate the origin of these two populations by simultaneous single-molecule imaging of substrates with both bare glass and SAM-covered regions. SAM-covered areas of substrates are found to promote CTRW, whereas glass surfaces promote localized motion. Contact angle measurements and atomic force microscopy imaging show that increasing SAM concentration results in both increasing hydrophobicity and surface roughness. These properties lead to two opposing effects: increasing hydrophobicity promotes longer protein flights, but increasing surface roughness suppresses protein dynamics resulting in shorter residence times. Our studies suggest that controlling hydrophobicity and roughness, in addition to electrostatics, as independent parameters could provide a means to tune desirable or undesirable protein interactions with surfaces.
more » « less- NSF-PAR ID:
- 10363532
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 156
- Issue:
- 9
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- Article No. 094707
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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