Carbon nanoparticles (CNP) have significant impact on the Pulmonary Surfactant (PS), the first biological barrier in the respiratory system. CNPs – abundant in the environment due to combustion – can translocate into our bodies by crossing the alveolar epithelium barrier, and they can be retained in the lungs due to slow clearance. The physical mechanisms of how CNPs perturb PS remain unclear yet such knowledge is crucial for developing effective strategies against the adverse effects of CNPs. Molecular dynamics (MD) simulations of model PS monolayers in the presence of C₆₀ fullerenes were performed at time scales of tens of microseconds and varying C₆₀ content. In contrast to bilayers, fullerenes affected both structural and dynamic properties of the PS monolayer. Surface tension/area isotherms of the monolayer were changed by fullerenes and perturbations of the physical structure of the PS monolayer became major at high fullerene concentrations due to fullerene aggregation. At high compression (area per molecule of 0.48 nm²), the monolayer became unstable and collapsed forming a bilayer in the water phase. At low compression, pore formation occurred. Free energy calculations suggest that increasing fullerene concentration leads to decreased preference for the fullerenes to reside inside the monolayer. However, the free energy barrier for transferring fullerene out of the monolayer is rather large at all fullerene concentrations; spontaneous translocation of fullerene out of the monolayer is thermodynamically unfavorable. The results illustrate some of the potentially harmful effects of CNPs on the respiratory system and also the physical mechanism of how CNPs disturb pulmonary surfactant. This may be related to the difficulty of CNP clearance from lung surfactant. The total simulation time was 370 microseconds.

It is well-known that fullerenes aggregate inside lipid membranes and that increasing the concentration may lead to (lethal) membrane rupture. It is not known, however, how aggregation and rupture depend on the lipid type, what physical mechanisms control this behavior and what experimental signatures detect such changes in membranes. In this paper, we attempt to answer these questions with molecular simulations, and we show that aggregation and membrane damage depend critically on the degree of saturation of the lipid acyl chains: unsaturated bonds, or “kinks”, impose a subtle but crucial compartmentalization of the bilayer into core and surface regions leading to three distinct fullerene density maxima. In contrast, when the membrane has only fully saturated lipids, fullerenes prefer to be located close to the surface under the head groups until the concentration becomes too large and the fullerenes begin clustering. No clustering is observed in membranes with unsaturated lipids. The presence of “kinks” reverses the free energy balance; although the overall free energy profiles are similar, entropy is the dominant component in unsaturated bilayers whereas enthalpy controls the fully saturated ones. Fully saturated systems show two unique signatures: 1) membrane thickness behaves non-monotonously while the area per lipid increases monotonously. We propose this as a potential reason for the observations of low fullerene concentrations being effective against bacteria. 2) The fullerene-fullerene radial distribution function (RDF) shows splitting of the second peak indicating the emergence short-range order and the importance of the second-nearest neighbor interactions. Similar second peak splitting has been reported in metal glasses.

Understanding the interactions between carbon nanoparticles (CNPs) and biological membranes is critically important for applications of CNPs in biomedicine and toxicology. Due to the complexity and diversity of the systems, most molecular simulation studies have focused on the interactions of CNPs and single component bilayers. In this work, we performed coarse-grained molecular dynamic (CGMD) simulations to investigate the behaviors of fullerenes in the presence of multiple lipid components in the plasma membranes with varying fullerene concentrations. Our results reveal that fullerenes can spontaneously penetrate the plasma membrane. Interestingly, fullerenes prefer to locate themselves in the region of the highly unsaturated lipids that are enriched in the inner leaflet of the plasma membrane. This causes fullerene aggregation even at low concentrations. When increasing fullerene concentrations, the fullerene clusters grow, and budding may emerge at the inner leaflet of the plasma membrane. Our findings suggest by tuning the lipid composition, fullerenes can be loaded deeply inside the plasma membrane, which can be useful for designing drug carrier liposomes. Moreover, the mechanisms of how fullerenes perturb multicomponent cell membranes and how they directly enter the cell are proposed. These insights can help to determine fullerene toxicity in living cells.

Coarse-grained molecular dynamics (CGMD) simulations were employed to investigate the effects of phospholipids on the aggregation of hydrophilic, modified carbon-nanoparticle fillers in cis-polyisoprene (cis-PI) composites. The MARTINI force field was applied to model dipalmitoylphosphatidylcholine (DPPC) lipids and hydrophilic modified fullerenes (HMFs). The simulations of DPPC in cis-PI composites show that the DPPC lipids self-assemble to form a reverse micelle in a rubber matrix. Moreover, HMF molecules readily aggregate into a cluster, in agreement with the previous studies. Interestingly, the mixture of the DPPC and HMF in the rubber matrix shows a cluster of HMF is encapsulated inside the DPPC reverse micelle. The HMF encapsulated micelles disperse well in the rubber matrix, and their sizes are dependent on the lipid concentration. Mechanical and thermal properties of the composites were analyzed by calculating the diffusion coefficients (D), bulk modulus (κ), and glass transition temperatures (T_g). The results suggest that DPPC acts as a plasticizer and enhances the flexibility of the HMF-DPPC rubber composites. These findings provide valuable insights into the design and process of high-performance rubber composites, offering improved mechanical and thermal properties for various applications.