•Several natural nanostructured surfaces can kill bacteria in contact with them.•Bactericidal efficacy of bio-inspired nanostructured surfaces has been demonstrated.•Contact killing mechanism of bacteria on nanostructured surfaces not understood•Optimal geometry and density of nanostructures for killing bacteria unknown•Cost effective fabrication for large area bactericidal surfaces is important.Bacterial antibiotic resistance is becoming more widespread due to excessive use of antibiotics in healthcare and agriculture. At the same time the development of new antibiotics has effectively ground to a hold. Chemical modifications of material surfaces have poor long-term performance in preventing bacterial build-up and hence approaches for realising bactericidal action through physical surface topography have become increasingly important in recent years. The complex nature of the bacteria cell wall interactions with nanostructured surfaces represents many challenges while the design of nanostructured bactericidal surfaces is considered. Here we present a brief overview of the bactericidal behaviour of naturally occurring and bio-inspired nanostructured surfaces against different bacteria through the physico-mechanical rupture of the cell wall. Many parameters affect this process including the size, shape, density, rigidity/flexibility and surface chemistry of the surface nanotextures as well as factors such as bacteria specificity (e.g. gram positive and gram negative) and motility. Different fabrication methods for such bactericidal nanostructured surfaces are summarised.Download high-res image (173KB)Download full-size image

Understanding the structure of solid supported lipid multilayers is crucial to their application as a platform for novel materials. Conventionally, they are prepared from drop casting or spin coating of lipids dissolved in organic solvents, and lipid multilayers prepared from aqueous media and their structural characterisation have not been reported previously, due to their extremely low lipid solubility (i.e. ∼10−9 M) in water. Herein, using X-ray reflectivity (XRR) facilitated by a “bending mica” method, we have studied the structural characteristics of dioleoylphosphatidylcholine (DOPC) multilayers prepared via drop casting aqueous small unilamellar and multilamellar vesicle or liposome (i.e. SUV and MLV) dispersions on different surfaces, including mica, positively charged polyethylenimine (PEI) coated mica, and stearic trimethylammonium iodide (STAI) coated mica which exposes a monolayer of hydrocarbon tails. We suggest that DOPC liposomes served both as a delivery matrix where an appreciable lipid concentration in water (∼25 mg mL−1 or 14 mM) was feasible, and as a structural precursor where the lamellar structure was readily retained on the rupture of the vesicles at the solid surface upon solvent evaporation to facilitate rapid multilayer formation. We find that multilayers on mica from MLVs exhibited polymorphism, whereas the SUV multilayers were well ordered and showed stronger stability against water. The influence of substrate chemistry (i.e. polymer coating, charge and hydrophobicity) on the multilayer structure is discussed in terms of lipid–substrate molecular interactions determining the bilayer packing proximal to the solid–liquid interface, which then had a templating effect on the structure of the bilayers distal from the interface, resulting in the overall different multilayer structural characteristics on different substrates. Such a fundamental understanding of the correlation between the physical parameters that characterise liposomes and substrate chemistry, and the structure of lipid multilayers underpins the potential development of a simple method via an aqueous liposome dispersion route for the inclusion of hydrophilic functional additives (e.g. drugs or nanoparticles) into lipid multilayer based hybrid materials, where tailored structural characteristics are an important consideration.

Using high pressure small angle X-ray scattering (HP-SAXS), we have studied monoolein (MO) mesophases at 18 wt% hydration in the presence of 10 nm silica nanoparticles (NPs) at NP–lipid number ratios (ν) of 1 × 10−6, 1 × 10−5 and 1 × 10−4 over the pressure range 1–2700 bar and temperature range 20–60 °C. In the absence of the silica NPs, the pressure–temperature (p–T) phase diagram of monoolein exhibited inverse bicontinuous cubic gyroid (QGII), lamellar alpha (Lα), and lamellar crystalline (Lc) phases. The addition of the NPs significantly altered the p–T phase diagram, changing the pressure (p) and the temperature (T) at which the transitions between these mesophases occurred. In particular, a strong NP concentration effect on the mesophase behaviour was observed. At low NP concentration, the p–T region pervaded by the QGII phase and the Lα–QGII mixture increased, and we attribute this behaviour to the NPs forming clusters at the mesophase domain boundaries, encouraging transition to the mesophase with a higher curvature. At high NP concentrations, the QGII phase was no longer observed in the p–T phase diagram. Instead, it was dominated by the lamellar (L) phases until the transition to a fluid isotropic (FI) phase at 60 °C at low pressure. We speculate that NPs formed aggregates with a “chain of pearls” structure at the mesophase domain boundaries, hindering transitions to the mesophases with higher curvatures. These observations were supported by small angle neutron scattering (SANS) and scanning electron microscopy (SEM). Our results have implications to nanocomposite materials and nanoparticle cellular entry where the interactions between NPs and organised lipid structures are an important consideration.

⿢Polymersomes from film rehydration are polydisperse.⿢A narrow size distribution is obtained from extrusion and size exclusion chromatography.⿢Polymersome size from SEC increases over time due to elusion dilution.⿢Extruded polymersomes are more stable.⿢Storage temperature, buffer, and dilution all affect polymersome stability.In this work, stability of poly(butadiene)-poly(ethylene oxide) (PBD-PEO) polymersomes, self-assembled from two polymers with different molecular weights (PBD32-PEO21 and PBD125-PEO80) in either pure H2O or phosphate buffered saline (PBS), is studied. Polymersome dispersions usually show large polydispersity, and it is thus desirable to separate different-sized vesicles if a narrow size distribution is required, e.g. for model systems in certain applications. This is typically achieved by extrusion through a membrane with a designated pore size or, less commonly, by size exclusion chromatography (SEC). Here, we find that both extrusion and SEC of polymersome dispersions with vesicle sizes ranging from 100 to 5000 nm and polydispersity index (PDI) = 1, can yield smaller vesicles with PDIs < 0.35. With SEC, it is possible to separate fractions of polymersomes with different sizes. However, the SEC polymersome size and particularly the spread in the size increase significantly over time, whereas the extruded polymersomes are shown to be more stable. We attribute this to possible dilution of the polymersome dispersion during the SEC elusion process. The effects of temperature and the PBD-PEO molecular weight on the stability of the extruded polymersomes against dilution in pure water and phosphate buffer are further studied. It is found that the polymersomes show higher stability when stored at lower temperature, undiluted, and prepared in phosphate buffer, whereas the polymer molecular weight does not have a large influence on the stability.Figure optionsDownload full-size imageDownload high-quality image (300 K)Download as PowerPoint slide

•Nanofluids may contain soft, self-assembled nanostructures of different size, shape and surface chemistry.•Phase transitions in binary colloidal mixtures with large size and geometry asymmetry can offer relevant insights.•Direct measurement of depletion and structural forces in nanofluids is limited.•The role of proteo-nanofluids mediated depletion in cellular organisation and biological processes is under-appreciated.•Many theoretical and experimental challenges and opportunities remain.Understanding depletion forces between colloidal particles mediated by nanofluids, i.e. liquids containing hard or soft nanostructures, is immensely important in a number of industrial processes. We anticipate added complexities due to enhanced and multifactorial inter-depletant interactions associated with their size, shape, surface chemistry, and concentration. Here we briefly review recent efforts in direct measurement of depletion forces mediated by nanofluids, as well as a number of related studies on the phase transition in binary colloid mixtures with large size and shape asymmetry, a process in which depletion forces play an important role. We will also discuss the often under-appreciated importance of depletion forces mediated by proteo-nanofluids (liquids containing proteins) in facilitating cellular organisation. Some challenges and outstanding questions will emerge from the above discussions, as briefly summarised.

Understanding dendrimer structures and their interactions in concentrated solutions is important to a wide range of applications, such as drug delivery and lubrication. However, controversy has persisted concerning whether, when confined to proximity, dendrimers would entangle as observed for polymer systems, or act as deformable spheres. Furthermore, how such behavior may be related to their size-dependent molecular architecture remains unclear. Using small-angle X-ray scattering (SAXS), the intermolecular interactions and structures in aqueous nanofluids containing three generations of carboxyl-terminated poly(amidoamine) (PAMAM) dendrimers (G0.5, Rg = 9.3 Å; G3.5, Rg = 22.6 Å; G5.5, Rg = 39.9 Å, where Rg is the radius of gyration) over a mass fraction range 0.005 ≤ x ≤ 0.316 have been studied. In the highly concentrated regime (x ≥ 0.157), we observe that the solution properties depend on the dendrimer generation. Our results suggest that the smaller G0.5 dendrimers form a highly entangled polymer melt, while the larger dendrimers, G3.5 and G5.5, form densely packed and ordered structures, in which the individual dendrimers exhibit some degree of mutual overlap or deformation. Our results demonstrate the tunability of interdendrimer interactions via their molecular architecture, which in turn may be harnessed to control and tailor the physical properties of dendrimer nanofluids.

It has been recently demonstrated that molecular and molecular cluster guest species can intercalate within lamellar stacks of purple membrane (PM), and be subsequently dried to produce functional bioinorganic nanocomposite films. However, the mechanism for the intercalation process remains to be fully understood. Here we employ surface X-ray scattering to study the intercalation of aminopropyl silicic acid (APS) or aminopropyl-functionalised magnesium phyllosilicate (AMP) molecular clusters into PM films. The composite films are prepared under aqueous conditions by guest infiltration into preformed PM films, or by co-assembly from an aqueous dispersion of PM sheets and guest molecules/clusters. Our results show that addition of an aqueous solution of guest molecules to a dried preformed PM film results in loss of the lamellar phase, and that subsequent air-drying induces re-stacking of the lipid/protein membrane sheets along with retention of a 2–3 nm hydration layer within the inter-lamellar spaces. We propose that this hydration layer is necessary for the intercalation of APS molecules or AMP oligomers into the PM film, and their subsequent condensation and retention as nano-thin inorganic lamellae within the composite mesostructure after drying. Our results indicate that the intercalated nanocomposites prepared from preformed PM films have a higher degree of ordering than those produced by co-assembly.

Upon evaporation, ZnO nanorods in a nanofluid droplet undergo rapid and spontaneous chemical and morphological transformation into centimetre-long Zn(OH)2 fibres, via a mechanism very different from that for coffee rings. We show that the detailed nanostructure and micromorphology in the residual thin film depend intricately on the ambient moisture, nanofluid solvent composition and substrate surface chemistry. Upon thermal annealing, these Zn(OH)2 fibres readily undergo further chemical and morphological transformation, forming nanoporous fibres with the pore size tuneable by temperature. Our results point to a simple route for generating a self-assembled 3D structure with ultralong and nanoporous ZnO/Zn(OH)2 fibres/belts, and may also be of interest to the fields of evaporation controlled dynamic self-assembly, non-equilibrium crystallisation, and flow and fingering instabilities in nanofluids.

The self-assembly behaviour, structure, and consequently the electronic properties of electroactive organic molecules can differ significantly from those of the bulk material when confined to thin films. Here we have examined the self-organised in-plane and out-of-plane structures of aniline oligomers in thin films using surface-sensitive grazing-incidence X-ray scattering (GIXS). Thin films of the aniline tetramer (TANI) and octamer (OANI) were prepared both in their native emeraldine base (EB) oxidation state and in the doped emeraldine salt (ES) state (combined with the acid surfactant bis(ethyl hexyl)phosphate (BEHP)), using a simple drop-casting and solvent annealing process. It was found that the presence of the acid surfactant induced self-organisation into highly ordered structures. The details of these structures, such as the morphology, orientation relative to the underlying substrate and the degree of orientation were found to depend on the molecular architecture of the oligomer. The BEHP-doped TANI system formed a highly oriented hexagonal unit cell (lattice parameters: a = b = 2.53 nm, c = 2.91 nm, γ = 120°), whereas the BEHP-doped OANI complex adopted a randomly oriented lamellar structure (d-spacing = 2.25 nm). Such detailed structural information reveals that the self-assembly behaviour and the packing of oligomer–BEHP complexes, when confined to thin films, are indeed different to that of the bulk phase materials. Furthermore, the molecular architecture of the oligomers directly influenced the structural changes of the doped films in response to in situ thermal treatment. These results demonstrate that through a simple processing route the morphology of electroactive oligomer films can be tailored by molecular design. These findings are important to future applications where thin film structure is a crucial consideration for device function and performance.

Understanding the frictional properties of nanostructured surfaces is important because of their increasing application in modern miniaturized devices. In this work, lateral force microscopy was used to study the frictional properties between an AFM nanotip and surfaces bearing well-defined nanodomes comprising densely packed prolate spheroids, of diameters ranging from tens to hundreds of nanometers. Our results show that the average lateral force varied linearly with applied load, as described by Amontons’ first law of friction, although no direct correlation between the sample topographic properties and their measured friction coefficients was identified. Furthermore, all the nanodomed textures exhibited pronounced oscillations in the shear traces, similar to the classic stick–slip behavior, under all the shear velocities and load regimes studied. That is, the nanotextured topography led to sustained frictional instabilities, effectively with no contact frictional sliding. The amplitude of the stick–slip oscillations, σf, was found to correlate with the topographic properties of the surfaces and scale linearly with the applied load. In line with the friction coefficient, we define the slope of this linear plot as the stick–slip amplitude coefficient (SSAC). We suggest that such stick–slip behaviors are characteristics of surfaces with nanotextures and that such local frictional instabilities have important implications to surface damage and wear. We thus propose that the shear characteristics of the nanodomed surfaces cannot be fully described by the framework of Amontons’ laws of friction and that additional parameters (e.g., σf and SSAC) are required, when their friction, lubrication, and wear properties are important considerations in related nanodevices.Keywords: Amontons’ laws; friction; nanodomes; nanostructured surfaces; nanotextured surfaces; nanotribology; stick−slip

Lamellar structures self-assembled from purple membranes (PM) of Halobacterium salinarum are promising building units for bio-electronic devices, due to proton pumping ability of the PM. The functionality and durability of such devices are hinged on the structural integrity of PM lamellae. Using X-ray diffraction, we examined the structure of PM multilayers on silicon when challenged with two types of nanoparticles (NPs): carboxymethyl-dextran coated magnetite (2.4 nm core size) and citrate-stabilised gold (5 nm core size). We tried to infiltrate the PM multilayers with the NPs using two alternative routes: facile penetration (FP) and co-assembly (CS) by solution mixing. We found that under all conditions the NPs did not disrupt the overall lamellar structure of the PM films or enter the inter-lamellar space, although the presence of NPs affected the self-assembly process of the PM films. This caused an increase in the disorder in the film structure, as assessed by the decreasing number of layers in the multilayer stack as the NP concentration increased. Despite this, UV-Vis spectroscopic measurements showed that the conformation of the retinal residue within the protein was intact so the proton pumping functionality of PM multilayers would be retained in all samples with added NPs. Our results show that the effects of NPs on the PM structure and functionality are subtle and complex, and we will discuss the structural integrity of lipid-protein composite PM films against NP infiltration in terms of their high bending modulus as compared with that of fluid lipid bilayers.

Fluids containing nanostructures, known as nanofluids, are increasingly found in a wide array of applications due to their unique physical properties as compared with their base fluids and larger colloidal suspensions. With several tuneable parameters such as the size, shape and surface chemistry of nanostructures, as well as numerous base fluids available, nanofluids also offer a new paradigm for mediating surface forces. Other properties such as local surface plasmon resonance and size dependent magnetism of nanostructures also present novel mechanisms for imparting tuneable surface interactions. However, our fundamental understanding, experimentally and theoretically, of how these parameters might affect surface forces remains incomplete. Here we review recent results on equilibrium and dynamic surface forces between macroscopic surfaces in nanofluids, highlighting the overriding trends in the correlation between the physical parameters that characterise nanofluids and the surface forces they mediate. We also discuss the challenges that confront existing surface force knowledge as a result of this new paradigm.Highlights► Nanofluids as a new paradigm for mediating surface forces. ► Forces tuneable via nanostructure size, shape, surface chemistry and concentration. ► Many outstanding questions, challenges and opportunities.

With nanotextured surfaces and interfaces increasingly being encountered in technological and biomedical applications, there is a need for a better understanding of frictional properties involving such surfaces. Here we report friction measurements of several nanostructured surfaces using an Atomic Force Microscope (AFM). These nanostructured surfaces provide well defined model systems on which we have tested the applicability of Amontons' laws of friction. Our results show that Amontonian behaviour is observed with each of the surfaces studied. However, no correlation has been found between measured friction and various surface roughness parameters such as average surface roughness (Ra) and root mean squared (rms) roughness. Instead, we propose that the friction coefficient may be decomposed into two contributions, i.e., μ = μ0 + μg, with the intrinsic friction coefficient μ0 accounting for the chemical nature of the surfaces and the geometric friction coefficient μg for the presence of nanotextures. We have found a possible correlation between μg and the average local slope of the surface nanotextures.

•Molecular mechanisms of aqueous boundary lubrication lie in hydration lubrication.•Supramolecular synergy is an area for further investigations.•The stalk model of membrane fusion may guide molecular designs for boundary layers.•Structure and morphology of self-assembled surfactant layers remains controversial.•A new aqueous boundary lubrication regime is proposed for the Stribeck curve.The molecular mechanisms for aqueous boundary lubrication are very different from those in the classic boundary lubrication, originating from the fluidity of the hydration shells surrounding the surfactant and lipid headgroups. We discuss the important molecular and structural criteria for effective aqueous boundary lubricants, and highlight the strategy for reinforcing the interfacial structure for aqueous boundary lubrication via synergistic interactions between amphiphilic polymers and lipids/surfactants. It is proposed that the energetic considerations of different molecular elastic deformations in the stalk model of cell membrane fusion can be applied to guide our design of molecular architectures for surfactants and lipids to implement structural integrity in aqueous boundary lubrication. We discuss a controversy associated with the quiescent bilayer structure in the context of boundary lubricant interfacial structures. We also highlight other effective aqueous boundary lubrication systems, including hydrated ions and biomimetic hierarchical constructs inspired by the enigmatic and extremely efficient biological lubrication. Finally, we suggest that the Stribeck curve might be re-considered in light of recent advances in aqueous boundary lubrication, although the exact scope of this new aqueous boundary lubrication regime remains terra incognita.Figure optionsDownload full-size imageDownload high-quality image (314 K)Download as PowerPoint slide

With nanotextured surfaces and interfaces increasingly being encountered in technological and biomedical applications, there is a need for a better understanding of frictional properties involving such surfaces. Here we report friction measurements of several nanostructured surfaces using an Atomic Force Microscope (AFM). These nanostructured surfaces provide well defined model systems on which we have tested the applicability of Amontons' laws of friction. Our results show that Amontonian behaviour is observed with each of the surfaces studied. However, no correlation has been found between measured friction and various surface roughness parameters such as average surface roughness (Ra) and root mean squared (rms) roughness. Instead, we propose that the friction coefficient may be decomposed into two contributions, i.e., μ = μ0 + μg, with the intrinsic friction coefficient μ0 accounting for the chemical nature of the surfaces and the geometric friction coefficient μg for the presence of nanotextures. We have found a possible correlation between μg and the average local slope of the surface nanotextures.

Lamellar structures self-assembled from purple membranes (PM) of Halobacterium salinarum are promising building units for bio-electronic devices, due to proton pumping ability of the PM. The functionality and durability of such devices are hinged on the structural integrity of PM lamellae. Using X-ray diffraction, we examined the structure of PM multilayers on silicon when challenged with two types of nanoparticles (NPs): carboxymethyl-dextran coated magnetite (2.4 nm core size) and citrate-stabilised gold (5 nm core size). We tried to infiltrate the PM multilayers with the NPs using two alternative routes: facile penetration (FP) and co-assembly (CS) by solution mixing. We found that under all conditions the NPs did not disrupt the overall lamellar structure of the PM films or enter the inter-lamellar space, although the presence of NPs affected the self-assembly process of the PM films. This caused an increase in the disorder in the film structure, as assessed by the decreasing number of layers in the multilayer stack as the NP concentration increased. Despite this, UV-Vis spectroscopic measurements showed that the conformation of the retinal residue within the protein was intact so the proton pumping functionality of PM multilayers would be retained in all samples with added NPs. Our results show that the effects of NPs on the PM structure and functionality are subtle and complex, and we will discuss the structural integrity of lipid-protein composite PM films against NP infiltration in terms of their high bending modulus as compared with that of fluid lipid bilayers.

It has been recently demonstrated that molecular and molecular cluster guest species can intercalate within lamellar stacks of purple membrane (PM), and be subsequently dried to produce functional bioinorganic nanocomposite films. However, the mechanism for the intercalation process remains to be fully understood. Here we employ surface X-ray scattering to study the intercalation of aminopropyl silicic acid (APS) or aminopropyl-functionalised magnesium phyllosilicate (AMP) molecular clusters into PM films. The composite films are prepared under aqueous conditions by guest infiltration into preformed PM films, or by co-assembly from an aqueous dispersion of PM sheets and guest molecules/clusters. Our results show that addition of an aqueous solution of guest molecules to a dried preformed PM film results in loss of the lamellar phase, and that subsequent air-drying induces re-stacking of the lipid/protein membrane sheets along with retention of a 2–3 nm hydration layer within the inter-lamellar spaces. We propose that this hydration layer is necessary for the intercalation of APS molecules or AMP oligomers into the PM film, and their subsequent condensation and retention as nano-thin inorganic lamellae within the composite mesostructure after drying. Our results indicate that the intercalated nanocomposites prepared from preformed PM films have a higher degree of ordering than those produced by co-assembly.