arXiv subjects

Nir Kampf

Publications and source records attributed to Nir Kampf.

6 recordsLinked to original sources

arXiv2026

Cytoskeleton-inspired, adaptive nanolipogels as superlubricating delivery vehicles

Phosphatidylcholine liposomes fill a special niche in alleviating osteoarthritis via intra-articular (IA) administration, attributed to their superlubricity at the articular cartilage surface, but their co-utilization as drug delivery vesicles in such therapy remains challenging as they may rupture under mechanical stress. Here, we describe cytoskeleton-inspired, supramolecular, self-assembled nanolipogels (NLGs), encompassing liposome-encased nanogels with a dynamic network formed by hydrogen bonding and cation-pi interactions, as a platform for simultaneous robust drug-delivery and massive reduction of interfacial frictional dissipation. We use a surface force balance to assess such dissipation at the sub-nanometer level, elucidating the mechanism involved, and atomic force microscopy to probe the NLGs structural stability. A useful proxy for the interfacial dissipation is the coefficient of friction, which remains as low as 10-4 at contact pressures at least up to 2 MPa, while under higher pressures exceeding the H-bonding energy density it increases abruptly and irreversibly to the still-low value 10-2. Under sustained sliding above this threshold, however, friction gradually decreases again, indicating recovery of the lubricating interface. Molecular dynamics simulations identify the compressive stress decrease due to hydrogen-bond rupture/rearrangement within the nanogel as a buried supramolecular transition associated with lubrication breakdown and recovery, while cargo release during sliding emphasizes the drug-delivery potential of such NLGs. These findings reveal how supramolecular core-shell reinforcement regulates load-bearing hydration lubrication, and provides a framework for designing adaptive biomimetic lubricants which are at the same time load-bearing intra-articular cargo-delivery vehicles.

physics.bio-ph↗

arXiv2023

Cell-inspired, massive electromodulation of interfacial energy dissipation

Transient electric fields across cell bilayer membranes can lead to electroporation, as well as to cell fusion, and have been extensively studied. We find that transmembrane electric fields similar to those in cells can lead to a massive, reversible modulation--by up to 200-fold--of the interfacial energy dissipation between surfaces sliding across the lipid bilayer membranes. Atomistic simulations reveal that this arises from (fully reversible) electroporation of the interfacially-confined bilayers, and formation of bilayer bridges analogous to stalks preceding intermembrane fusion. These cell-membrane-mimicking effects topologically-force the slip to partially-revert from the low-dissipation, hydrated lipid-headgroups plane to the intra-bilayer, high-dissipation acyl tail interface. Our results demonstrate that lipid bilayers under transmembrane electric fields can have striking materials-modification properties, and shed new light on membrane hemifusion.

cond-mat.mtrl-sci↗

arXiv2023

Multi-lipid synergy in synovial lubrication: natural redundancy vs. natural selection

The very low sliding friction of articular cartilage in the major synovial joints such as hips and knees is crucial for their well-being, and has been attributed to lubrication by phospholipid boundary layers. While single-component lipid layers have demonstrated efficient lubricity in model studies, in living joints there is a large number of different lipids, raising the question of whether this is natural redundancy, or whether this multiplicity confers any benefits. Here we examine lubrication by progressively more complex mixtures of lipids representative of those in joints, using a surface forces balance at physiologically-relevant salt concentrations and pressures. We find that different lipid combinations differ very significantly in their lubricating ability, as manifested by their robustness to hemifusion under physiological loads, pointing to a clear lubrication synergy arising from multiple lipid types in the lubricating layers. Insight into the origins of this synergy is provided by molecular dynamics (MD) simulations of the different lipid mixtures used in the experiments, which directly reveal how hemifusion - associated with greatly increased friction - depends on the detailed lipid composition. Our results provide insight into the role of lipid type proliferation in healthy synovial joints, and point to new treatment modalities for osteoarthritis.

cond-mat.mtrl-sci↗

arXiv2022

Neutral polyphosphocholine-modified liposomes as boundary superlubricants

Boundary lubrication is associated with two sliding molecularly thin lubricated film-coated surfaces, where the energy dissipation occurs at the slip-plane between lubricated films. The hydration lubrication paradigm, which accounts for ultralow friction in aqueous media, has been extended to various systems, with phosphatidylcholine (PC) lipids recognized as extremely efficient lubrication elements due to their high hydration level. In this work, we extend a previous study (Lin et al., Langmuir 35 (2019) 6048-6054), where a charged lipid-poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) conjugate was prepared, to the very different case of a neutral lipid-PMPC) conjugate. This neutral molecule stabilizes the liposomes by attaching highly water-soluble PMPC to the surface of liposomes with its lipid moieties incorporated in the lipid bilayers. Such neutral polyphosphocholinated liposomes provide a surface lubricity which is well within the superlubrication regime (coefficient of friction = ca. 10-3 or even lower). In contrast, negatively charged lipid/polyphosphocholine conjugates modified liposomes were unable to adsorb on negatively-charged (mica) surfaces. Our method provides stable liposomes that can adsorb on negatively charged surfaces and provide superlubricity.

cond-mat.soft↗

arXiv2022

Interactions Between Bilayers of Phospholipids Mixture Extracted from Human Osteoarthritic Synovial Fluid

Duncan Dowson, whom this issue commemorates, was a world leader in the field of biotribology, with prolific contributions both in fluid-based and boundary lubrication of biological tissues, in particular articular cartilage, a central issue in biotribology due to its importance for joint homeostasis. Here we explore further the issue of cartilage boundary lubrication, which has been attributed to phospholipid (PL)-exposing layers at the cartilage surface in part. A surface force balance (SFB) with unique sensitivity is used to investigate the normal and frictional interactions of the boundary layers formed by PLs extracted from osteoarthritic (OA) human synovial fluid (hSF). Our results reveal that vesicles of the OA-hSF lipids rupture spontaneously to form bilayers on the mica substrate (which, like the in-vivo articular cartilage surface in synovial joints, is negatively-charged) which then undergo hemifusion at quite low pressures in the SFB, attributed to the large heterogeneity of the hSF lipids. Nanometric friction measurements reveal friction coefficients mu = ca. 0.03 across the hemi-fused bilayer of these lipids, indicating residual hydration lubrication at the lipid-headgroup vs. substrate interface. Addition of calcium ions causes an increase in friction to mu = ca. 0.2, attributed either to calcium-bridging attraction of lipid headgroups to the negatively-charged substrate, or a shift of the slip plane to the more dissipative hydrophobic-tail vs. hydrophobic-tail interface. Our results suggest that the heterogeneity and composition of the OA-hSF lipids may be associated with higher friction at the cartilage boundary layers, and thus a connection with greater wear and degradation, due to hemifusion of the exposed lipid bilayers.

cond-mat.soft↗

arXiv2011

Long-ranged attraction between disordered heterogeneous surfaces

Long-ranged attractions across water between two surfaces that are randomly covered with (mobile) positive and negative charge domains have been attributed to induced correlation of the charges (positive lining up with negative) as the surfaces approach. Here we show, by directly measuring normal forces under a rapid shear field, that these attractions may not in fact be due to such correlations. It is rather the inherent interaction-asymmetry between equally- and between oppositely-charged domains that results in the long-ranged attraction even in the complete absence of any charge correlation.

cond-mat.soft↗