Graphene-Based Nanomaterials and Their Interactions with Lipid Membranes.

Graphene-based nanomaterials (GNMs) have captured increasing attention in the recent advancement of materials science and nanotechnology owing to their excellent physicochemical properties. Despite having unquestionable advances, the application of GNMs in biological and medical sciences is still limited due to the lack of knowledge and precise control over their interaction with the biological milieu. The cellular membrane is the first barrier with which GNMs interact before entering a cell. Therefore, understanding how they interact with cell membranes is important from the perspective of safe use in biological and biomedical fields. In this review, we systematically summarize the recent efforts in predicting the interactions between GNMs and model cellular membranes. This review provides insights into how GNMs interact with lipid membranes and self-assemble in and around them. Both the computational simulations and experimental observations are summarized. The interactions are classified depending on the physicochemical properties (structure, chemistry, and orientation) of GNMs and various model membranes. The thermodynamic parameters, structural details, and supramolecular forces are listed to understand the interactions which would help circumvent potential risks and provide guidance for safe use in the future. At the end of this review, future prospective and emerging challenges in this research field are discussed.

Self-Healing, Robust, Liquid-Repellent Coatings Exploiting the Donor-Acceptor Self-Assembly.

Liquid-repellent coatings with rapid self-healing and strong substrate adhesion have tremendous potential for industrial applications, but their formulation is challenging. We exploit synergistic chemistry between donor-acceptor self-assembly units of polyurethane and hydrophobic metal-organic framework (MOF) nanoparticles to overcome this challenge. The nanocomposite features a nanohierarchical morphology with excellent liquid repellence. Using polyurethane as a base polymer, the incorporated donor-acceptor self-assembly enables high strength, excellent self-healing property, and strong adhesion strength on multiple substrates. The interaction mechanism of donor-acceptor self-assembly was revealed via density functional theory and infrared spectroscopy. The superhydrophobicity of polyurethane was achieved by introducing alkyl-functionalized MOF nanoparticles and post-application silanization. The combination of the self-healing polymer and nanohierarchical MOF nanoparticles results in self-cleaning capability, resistance to tape peel and high-speed liquid jet impacts, recoverable liquid repellence over a self-healed notch, and low ice adhesion up to 50 icing/deicing cycles. By exploiting the porosity of MOF nanoparticles in our nanocomposites, fluorine-free, slippery liquid-infused porous surfaces with stable, low ice adhesion strengths were also achieved by infusing silicone oil into the coatings.

Bioinspired micro/nano structured aluminum with multifaceted applications.

Inspired by many biological systems such as lotus leaves, insect wings and rose petals, great attention has been devoted to the study and fabrication of artificial superhydrophobic surfaces with multiple functionalities. In the present study, a simple and ecological synthesis route has been employed for large scale fabrication of self-assembled, sustainable nanostructures on unprocessed and micro imprinted aluminum surfaces named 'Nano' and 'Hierarchy'. The processed samples show extreme wettability ranging from superhydrophilicity to superhydrophobicity depending on post-processing conditions. The densely packed ellipsoidal nanostructures exhibited superhydrophobicity with excellent water, bacterial and dust repellency when modified by low surface energy material 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FOTES), characterized by a static contact angle of 163 ± 1° and contact angle hysteresis (CAH) ~3°. These coated surfaces show significant corrosion resistance with current density of 6 nA/cm2 which is 40 times lower than unprocessed counterpart and retain chemical stability after prolonged immersion in corrosive media. These surfaces show excellent self-cleaning ability with significantly low water consumption (< 0.1 µl/mm2-mg) and prevent biofouling which ensures its applicability in biological environment and marine components. The nanostructured superhydrophilic aluminum shows maximum antibacterial activity due to disruption of cell membrane. This work can offer a simple strategy to large scale fabrication of multifunctional biomimetic metallic surfaces.

Partitioning of a Hybrid Lipid in Domains of Saturated and Unsaturated Lipids in a Model Cellular Membrane.

The cellular membranes are composed of hundreds of components such as lipids, proteins, and sterols that are chemically and physically distinct from each other. The lipid-lipid and lipid-protein interactions form domains in this membrane, which play vital roles in membrane physiology. The hybrid lipids (HLs) with one saturated and one unsaturated chain can control the shape and size of these domains, ensuring the thermodynamic stability of a membrane. In this study, the thermodynamics of mixing of a HL and its structural effects on the phase separated domains in a model membrane composed of a saturated and an unsaturated lipid have been investigated. The HL is observed to mix into an unsaturated lipid reducing the Gibbs free energy, whereas the mixing is unfavorable in a saturated lipid. The presence of an HL in an unsaturated lipid tends to increase its area fraction, which is reflected in the enhanced correlation length across the bilayers in a multilayered sample. There is a feeble effect on the domain structure of the saturated lipid due to the presence of the HLs at the phase boundary. This study concludes that the HLs preferentially participate in the unsaturated lipid regions compared to that of a saturated lipid.

Self-Assembly of Graphene Oxide Nanoflakes in a Lipid Monolayer at the Air-Water Interface.

The graphene family, especially graphene oxide (GO), has captured increasing prospects in the biomedical field due to its excellent physicochemical properties. Understanding the health and environmental impact of GO is of great importance for guiding future applications. Although their interactions with living organisms are omnipresent, the exact molecular mechanism is yet to be established. The cellular membrane is the first barrier for a foreign molecule to interact before entering into the cell. In the present study, a model system consisting of a lipid monolayer at the air-water interface represents one of the leaflets of this membrane. Surface pressure-area isotherms and advanced synchrotron X-ray scattering techniques have been employed to comprehend the interaction by varying the electrostatics of the membrane. The results depict a strong GO interaction with positively charged phospholipids, weak interaction with zwitterionic lipids, and interestingly negligible interaction with negatively charged lipids. GO flakes induce significant changes in the out-of-plane organization of a positively charged lipid monolayer with a minor influence on in-plane assembly of lipid chains. This interaction is packing-specific, and the influence of GO is much stronger at lower surface pressure. Even though for zwitterionic phospholipids, the GO flakes may partly insert into the lipid chains, the X-ray scattering results indicate that the flakes preferentially lie horizontally underneath the positively charged lipid monolayer. This in-depth structural description may pave new perspectives for the scientific community for the development of GO-based biosensors and biomedical materials.

Ultrasonic cavitation erosion-corrosion behavior of friction stir processed stainless steel.

Cavitation erosion remains the primary cause of material degradation in fluid machinery components operating at high speed. Micro-jets/shock waves caused by implosion of bubbles on material surface results in significant material loss and premature failure of the components. The presence of corrosive medium further exuberates this effect, causing rapid degradation. Here, we demonstrate a novel pathway to control cavitation erosion-corrosion by tailoring the surface properties using submerged friction stir processing (FSP), a severe plastic deformation process. FSP parameters were varied over wide range of strain-rates to generate tailored microstructures. High strain-rate processing resulted in nearly single phase fine grained structure while low strain-rate processing resulted in phase transformation in addition to grain refinement. As-received and processed samples were subjected to ultrasonic cavitation in distilled water as well as in corrosive environment of 3.5% NaCl solution. Individual roles of cavitation erosion, corrosion and their synergistic effects were analyzed. Depending on the microstructure, processed samples showed nearly 4-6 times higher cavitation erosion resistance compared to as-received alloy. Superior cavitation erosion-corrosion resistance of processed samples was attributed to surface strengthening, higher strain-hardening ability and quick passivation kinetics. The results of current study could be potentially transformative in designing robust materials for hydro-dynamic applications.