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Hypothesis: Understanding the intricate molecular-level details of toxic per- and polyfluoroalkyl substances (PFAS) partitioning to the air-water interface holds paramount importance in evaluating their fate and transport, as well as for finding safer alternatives for various applications, including aqueous film forming foams. The behavior of these substances at interfaces strongly depends on molecular architecture, chemistry, and concentration, which define molecular packing, self-assembly, interfacial diffusion, and the surface tension., Simulations: Modeling of three PFAS surfactants, namely, longer-tail (perfluorooctanoate (PFOA)) and shorter-tail (perfluorobutanoate (PFBA) and 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy) propanoate (GenX)) has been conducted using atomistic molecular dynamics simulations. A systematic comparison between these representative PFAS of different sizes and structure reveals factors influencing their association behavior, mechanism of surface tension reduction, and interfacial mobility as a function of surface coverage., Findings: Shorter-chain PFAS surfactants (GenX or PFBA) require lower surface coverage compared to longer chain (PFOA) PFAS to achieve the same decrease in surface tension. However, a higher concentration of GenX and PFBA is necessary in the bulk aqueous solution to achieve the same surface coverage as PFOA, due to their higher solubility in water. The PFAS molecular orientation and mobility at the interface are found to be vastly influenced by the length and architecture of the hydrophobic fluorocarbon tail. A significant ordering of the water dipole moment near the anionic headgroup is apparent at high surface concentration. A direct correlation is established between the PFAS interfacial properties and PFAS-PFAS, PFAS-counterion, and PFAS-water interactions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

Hypothesis: Graphene oxide-based nanotechnology has aroused a great interest due to its applications in the biomedical and optoelectronic fields. The wide use of these materials makes it necessary to study its potential toxicity associated with the inhalation of Graphene Oxide (GO) nanoparticles and its interaction with the lung surfactant. Langmuir monolayers have proven to be an excellent tool for studying the properties of the lung surfactant and the effect of intercalation of nanoparticles on its structure and properties. Therefore, to know the origin of the phospholipids/GO interaction and the structure of the lipid layer with GO, in this work we study the effect of the insertion of GO sheets on a Langmuir film of 1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC)., Experiments: Surface pressure-area isotherms, Neutron (NR) and X-ray Reflectivity (XRR) and Grazing Incidence X-ray Diffraction (GIXD) measurements of hydrogenated and deuterated DPPC monolayers with and without GO have been carried out., Findings: The results outline a strong interaction between the GO and the zwitterionic form of DPPC and prove that GO is in three regions of the DPPC monolayer, the aliphatic chains of DPPC, the head groups and water in the subphase. Comparison between results obtained with hydrogenated and deuterated DPPC allows concluding that both, electrostatic attractions, and dispersion forces are responsible of the interaction GO/DPPC. Results also demonstrated that the insertion of GO into the DPPC aliphatic chains does not induce significant changes on unit cell of DPPC., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Phospholipids are the protective layer of modern cells, but it is challenging for the formation of phospholipids that require a simple abiotic synthesis before the advent of primitive cells. Here, we reported the abiotic synthesis for lysophosphatidic acids (LPAs) with prebiotically plausible reactants in aqueous microdroplets under ambient conditions. The LPAs formation is carried out by fusing two microdroplets streams: one contains glycerol and pyrophosphate in water and the other one contains fatty acids in acetonitrile. Compared with the bulk solution, LPAs were generated in microdroplets without the addition of catalyst and heating. Conditions of reactant concentrations and microdroplet size varied and suggested that LPAs formation occurred near or at the microdroplet surface. The LPAs formation also showed chemoselective toward on chain-length of fatty acids. Finally, the formation of LPAs underwent two-step reactions with glycerol phosphorylation eliminating one water molecule followed by esterification with fatty acids. These results also implicated that pyrophosphate functioned as both catalysts and precursors in prebiotic LPAs synthesis. The approach using fusion aqueous microdroplets has desirable features in studying the substance exchange and interaction in atmosphere., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Hypothesis: Although the dynamics of colloids in the vicinity of a solid interface has been widely characterized in the past, experimental studies of Brownian diffusion close to an air-water interface are rare and limited to particle-interface gap distances larger than the particle size. At the still unexplored lower distances, the dynamics is expected to be extremely sensitive to boundary conditions at the air-water interface. There, ad hoc experiments would provide a quantitative validation of predictions., Experiments: Using a specially designed dual wave interferometric setup, the 3D dynamics of 9 μm diameter particles at a few hundreds of nanometers from an air-water interface is here measured in thermal equilibrium., Findings: Intriguingly, while the measured dynamics parallel to the interface approaches expected predictions for slip boundary conditions, the Brownian motion normal to the interface is very close to the predictions for no-slip boundary conditions. These puzzling results are rationalized considering current models of incompressible interfacial flow and deepened developing an ad hoc model which considers the contribution of tiny concentrations of surface active particles at the interface. We argue that such condition governs the particle dynamics in a large spectrum of systems ranging from biofilm formation to flotation process., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Hypothesis: Analytical expressions for calculating Hamaker constant (HC) and van der Waals (VDW) energy/force for interaction of a particle with a solid water interface has been reported for over eighty years. This work further developed novel analytical expressions and numerical approaches for determining HC and VDW interaction energy/force for the particle approaching and penetrating air-water interface (AWI), respectively., Methods: The expressions of HC and VDW interaction energy/force before penetrating were developed through analysis of the variation in free energy of the interaction system with bringing the particle from infinity to the vicinity of the AWI. The surface element integration (SEI) technique was modified to calculate VDW energy/force after penetrating., Findings: We explain why repulsive VDW energy exists inhibiting the particle from approaching the AWI. We found very significant VDW repulsion for a particle at a concave AWI after penetration, which can even exceed the capillary force and cause strong retention in water films on a solid surface and at air-water-solid interface line. The methods and findings of this work are critical to quantification and understanding of a variety of engineered processes such as particle manipulation (e.g., bubble flotation, Pickering emulsion, and particle laden interfaces)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Hypothesis: The air-solution interface of supersaturated calcium hydrogen carbonate (Ca(HCO 3 ) 2 ) represents the highest saturation state due to evaporation/CO 2 -degassing, where calcite crystals are expected to nucleate and grow along the interface. Hence, it should be possible to form a free-standing mineral-only calcium carbonate (CaCO 3 ) microfilm at the air-solution interface of Ca(HCO 3 ) 2 . The air-solution interface of phosphate buffered saline (PBS) could represent a phase boundary to introduce a hybrid microstructure of CaCO 3 and carbonate-rich dicalcium hydroxide phosphate (carbonate-rich hydroxylapatite)., Experiments: Supersaturated Ca(HCO 3 ) 2 was prepared at high pressure and heated to form CaCO 3 microfilms, which were converted to bone-like microfilms at the air-solution interface of PBS by dissolution-recrystallisation. The microfilms were characterised by scanning electron microscopy, 3D confocal microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, laser Raman microspectroscopy, and X-ray photoelectron spectroscopy. An in situ X-ray diffraction (XRD) system that simulates the aforementioned interfacial techniques was developed to elucidate the microfilms formation mechanisms., Findings: The CaCO 3 and bone-like microfilms were free-standing, contiguous, and crystalline. The bone-like microfilms exhibited a hybrid structure consisting of a surface layer of remnant calcite and a carbonate-rich hydroxylapatite core of plates. The present work shows that the air-solution interface can be used to introduce hybrid microstructures to mineral microfilms., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Hypothesis: Some ions can prevent bubbles from coalescing in water. The Gibbs-Marangoni pressure has been proposed as an explanation of this phenomenon. This repulsive pressure occurs during thin film drainage whenever surface enhanced or surface depleted solutes are present. However, bubble coalescence inhibition is known to depend on which particular combination of ions are present in a peculiar and unexplained way. This dependence can be explained by the electrostatic surface potential created by the distribution of ions at the interface, which will alter the natural surface propensity of the ions and hence the Gibbs-Marangoni pressure., Calculations: A generalised form of the Gibbs-Marangoni pressure is derived for a mixture of solutes and the modified Poisson-Boltzmann equation is used to calculate this pressure for five different electrolyte solutions made up of four different ions., Findings: Combining ions with differing surface propensities, i.e., one enhanced and one depleted, creates a significant electrostatic surface potential which dampens the natural surface propensity of these ions, resulting in a reduced Gibbs-Marangoni pressure, which allows bubble coalescence. This mechanism explains why the ability of electrolytes to inhibit bubble coalescence is correlated with surface tension for pure electrolytes but not for mixed electrolytes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The formation of surface multilayer structures, induced by the addition of multivalent counterions in dilute surfactant solutions, has been widely observed in a range of anionic surfactants. The phenomenon is associated with the ability to manipulate surface properties, especially in the promotion of enhanced surface wetting, and in the presence of an extensive near surface reservoir for rapid surface delivery of surfactant and other active components., Hypothesis: In the single alkyl chain anionic surfactants, such as sodium dodecysulfate, SDS, sodium alkylethoxylsulfate, SAES, and alkylestersulfonate, AES, surface multilayer formation is promoted by trivalent counterions such as Al 3+ , and is generally not observed with divalent counterions, such as Ca 2+ or with monovalent counterions. In the di-alkyl chain anionic surfactant, dodecylbenzenesulfonate, LAS, surface multilayer formation now occurs in the presence of divalent counterions. It is attributed to the closer proximity of a bulk lamellar phase, resulting in a greater tendency for surface multilayer formation, and hence should occur in other di-alkyl chain anionic surfactants., Experiments: Aerosol-OT, AOT, is one of the most commonly used di-alkyl chain anionic surfactants, and is extensively used as an emulsifying, wetting and dispersing agent. This paper reports on predominantly neutron reflectivity, NR, measurements which explore the nature of surface multilayer formation of the sodium salt of AOT at the air-solution interface with the separate addition of Ca 2+ and Al 3+ counterions., Findings: In the AOT concentration range 0.5 to 2.0 mM surface multilayer formation occurs at the air-solution interface with the addition of Ca 2+ or Al 3+ counterions. Although the evolution in the surface structure with surfactant and counterion concentration is broadly similar to those reported for SDS, SAES and AES, some notable differences occur. In particular the surfactant and counterion concentration thresholds for surface multilayer formation are higher for Ca 2+ than for Al 3+ . The differences encountered reflect the greater affinity of the di-alkyl chain structure for lamellar formation, and how the surface packing is controlled in part by the headgroup structure and the associated counterion binding affinity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Saponins are naturally occurring biosurfactants present in a wide range of plant species. They are highly surface active glycosides, and are used to stabilise foams and emulsions in foods, beverages and cosmetics. They have great potential for an even wider range of applications, especially when mixed with different synthetic surfactants. Understanding those mixing properties are key to the exploitation of saponins in that wider range of potential applications. The surface adsorption properties of the saponin, escin, with two conventional nonionic surfactants, polyethylene glycol surfactants, have been studied at the air-water interface using neutron reflectivity, NR, and surface tension, ST. Although the saponin and polyethylene glycol, C n EO m , surfactants are both nonionic the disparity in the relative surface activities and packing constraints result in non-ideal mixing. Comparison with the predictions of the pseudo phase approximation requires the inclusion of the quadratic, cubic and quartic terms in the expansion of the excess free energy of mixing to explain the variations in the surface composition. For escin/pentaethylene glycol monododecyl ether, C 12 EO 5, the interaction is attractive and close to ideal. For escin/octaethylene glycol monododecyl ether, C 12 EO 8 , it is repulsive and close to the criteria for demixing. The differences in mixing behaviour are attributed to greater packing constraints imposed by the larger ethylene oxide headgroup of the C 12 EO 8 compared to C 12 EO 5 ., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Fabrication of a multipurpose superhydrophobic mesh via modification of a galvanized steel mess using black titanium oxide nanoparticles and perfluorodecyltriethoxysilane is reported. Modified mesh exhibits superhydrophobicity with a water static contact angle of 157° ± 2 along with a tilt angle of 5° ± 1 and suitable chemical, thermal, mechanical stability, and self-cleaning ability. The droplet dynamic behavior of superhydrophobic mesh revels the impact velocity is 1.5 ms -1 for splashing of the water droplet. The developed mesh is studied for freshwater generation from oily water and seawater via efficient oil-water separation and solar evaporation, respectively. A proficiency of 99% and 88% is achieved for oil-water separation from mixture and emulsion, respectively. Solar evaporation efficiency of 64% and 76% are recorded under low-intensity light (225 Wm -2 ) and natural sunlight (591 Wm -2 ), respectively, from distilled water. For seawater, the evaporation efficiency of 69% is achieved under natural sunlight. Present approach can be applied to any size and shape of the mesh and has great industrial applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The formation of surface multilayer structures, with the addition of multivalent electrolytes, has been observed in a range of different anionic surfactants; and notably the sodium oxyethylene glycol alkyl sulfate, SAES, and alkyl ester sulfonate, AES, surfactants. The addition of increasing amounts of AlCl 3 results in increasing surface layering, with a transition from monolayer to bilayer to ultimately more extended multilayer structures at the interface. The headgroup structures of these SAES and AES surfactants and their hydrophilic / hydrophobic balance give a degree of tolerance to the precipitation induced by multivalent counterions. This was considered to be important factor associated with the multivalent counterion induced surface layering. In this paper the impact of sodium dodecyl sulfate, SDS, an anionic surfactant more susceptible to precipitation in the presence of multivalent counterions, on the surface multilayer formation and solution self-assembly of sodium diethylene glycol monododecyl sulfate, SLES, is explored using surface tension, neutron reflectivity and small angle neutron scattering. The results show that SDS exhibits a similar progressive evolution in surface structures with increasing AlCl 3 concentrations, as observed in SLES and related SAES surfactants, and in MES, sodium methyl ester dodecyl sulfonate surfactant. However in the SLES / SDS mixtures the structural evolution is different, and more complex pattern with increasing AlCl 3 concentration is observed. The initial transition from monolayer to bilayer / trilayer structures exists, but the surface at higher AlCl 3 concentration reverts to monolayer adsorption before extended multilayer structures are formed. Complementary small angle neutron scattering measurements indicate a more complex evolution in the micelle structure which broadly correlates with the surface behaviour. The results illustrate how subtle changes in headgroup structure and packing affect relative counterion binding and hence the surface and solution structures. The results reinforce and extend the observations of related structures on different SAES and AES surfactants, and highlight the opportunity for manipulating surface adsorption behaviour with surfactant mixtures., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Understanding the structure of polymer/surfactant mixtures at the air-water interface is of fundamental importance and also of relevance to a variety of practical applications. Here, the complexation between a neutral 'tardigrade' comb co-polymer (consisting of a hydrophilic polyethylene glycol backbone with hydrophobic polyvinyl acetate grafts, PEG-g-PVAc) with an anionic surfactant (sodium dodecyl sulfate, SDS) at the air-water interface has been studied. Contrast-matched neutron reflectivity (NR) complemented by surface tension measurements allowed elucidation of the interfacial composition and structure of these mixed systems, as well as providing physical insights into the polymer/surfactant interactions at the air-water interface. For both polymer concentrations studied, below and above its critical aggregation concentration, cac, (0.2 cac and 2 cac, corresponding to 0.0002 wt% or 0.013 mM and 0.002 wt% or 0.13 mM respectively), we observed a synergistic cooperative behaviour at low surfactant concentrations with a 1-2 nm mixed interfacial layer; a competitive adsorption behaviour at higher surfactant concentrations was observed where the polymer was depleted from the air-water interface, with an overall interfacial layer thickness ~1.6 nm independent of the polymer concentration. The weakly associated polymer layer "hanging" proximally to the interface, however, played a role in enhancing foam stability, thus was relevant to the detergency efficacy in such polymer/surfactant mixtures in industrial formulations., (Copyright © 2019 Elsevier Inc. All rights reserved.)

In this study, we investigated the tannic acid (TA)-, Ca 2+ -, and mica-enabled interfacial assembly of nC 60 fullerene (FWS) and Na-saturated kaolinite (Na-Kl) with in and ex situ atomic force microscopy (AFM). The epitaxial growth of herringbone motif, two dimensional (2D) chiral clusters and 3D mounds were detected. π-π electron donor-acceptor (EDA) interactions drove the transformation of the FWS, and the symmetry of the muscovite substrate directed the epitaxial ordering of self-assembled herringbone motifs. A ternary mixture of Na-Kl/FWS/TA in the presence of Ca 2+ produced double-stranded (ds) helices and 2D platelets of chiral clusters with a nano-porous monolayer on K + -treated muscovite surfaces. The weak hydration of exchangeable K + and stronger electric fields possibly contributed to the 1D and 2D propagation of aggregates. However, the local increment in carbon content due to the nucleation of functionalized FWS on mica diminished the K + -induced electric field effect and facilitated the 3D growth of helical mounds. The diffusion limited mass-transfer of particulates across the Ehrlich-Schwoebel barrier (ESB) and screw dislocation assisted motion of particulates specifically at higher steps aided mound growth. Thus, the structural incorporation of FWS can substantially impede its interfacial transport and produce hierarchical hybrid mineral-enriched graphitic aggregates., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Hypothesis: Rotational Brownian diffusions of colloidal particles at a fluid interface play important roles in particle self-assembly and in surface microrheology. Recent experiments on translational Brownian motion of spherical particles at the air-water interface show a significant slowing down of the translational diffusion with respect to the hydrodynamic predictions (Boniello et al., 2015). For the rotational diffusions of partially wetted colloids, slowing down of the particle dynamics can be also expected., Experiments: Here, the rotational dynamics of Janus colloids at the air-water interface have been experimentally investigated using optical microscopy. Bright field and fluorescent microscopies have been used to measure the in-plane and out-of-plane particle rotational diffusions exploiting the Janus geometry of the colloids we fabricated., Findings: Our results show a severe slowing down of the rotational diffusion D r, ⊥ connected to the contact line motion and wetting-dewetting dynamics occurring on particle regions located at opposite liquid wedges. A slowing down of the particle rotational diffusion about an axis parallel to the interfacial normal D r, || was also observed. Contact line fluctuations due to partial wetting dynamics lead to a rotational line friction that we have modelled in order to describe our results., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The interface between water and a textured hydrophobic surface can exist in two regimes; either the Wenzel (surface-engulfed) or Cassie-Baxter (water-suspended) state. Better understanding of the influence of pattern geometry and spacing is crucial for the design of functional (super)hydrophobic surfaces, as inspired by numerous examples in nature. In this work, we have employed amplitude modulated - atomic force microscopy to visualize the air-water interface with an unprecedented degree of clarity on a superhydrophobic and a highly hydrophobic nanostructured surface. The images obtained provide the first real-time experimental visualization of the Cassie-Baxter wetting on the surface of biomimetic silicon nanopillars and a naturally superhydrophobic cicada wing. For both surfaces, the air-water interface was found to be remarkably well-defined, revealing a distinctly nanostructured air-water interface in the interstitial spacing. The degree of interfacial texture differed as a function of surface geometry. These results reveal that the air-water interface is heterogeneous in its structure and confirmed the presence of short-range interfacial ordering. Additionally, the overpressure values for each point on the interface were calculated, quantifying the difference in wetting behavior for the biomimetic and natural surface. Results suggest that highly-ordered, closely spaced nanofeatures facilitate robust Cassie-Baxter wetting states and therefore, can enhance the stability of (super)hydrophobic surfaces., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Gliadins are edible wheat storage proteins well known for their surface active properties. In this paper, we present experimental results on the interfacial properties of acidic solutions of gliadin studied over 5 decades of concentrations, from 0.001 to 110 g/L. Dynamic pendant drop tensiometry reveals that the surface pressure Π of gliadin solutions builds up in a multistep process. The series of curves of the time evolution of Π collected at different bulk protein concentrations C can be merged onto a single master curve when Π is plotted as a function of αt where t is the time elapsed since the formation of the air/water interface and α is a shift parameter that varies with C as a power law with an exponent 2. The existence of such time-concentration superposition, which we evidence for the first time, indicates that the same mechanisms govern the surface tension evolution at all concentrations and are accelerated by an increase of the bulk concentration. The scaling of α with C is consistent with a kinetic of adsorption controlled by the diffusion of the proteins in the bulk. Moreover, we show that the proteins adsorption at the air/water interface is kinetically irreversible. Correlated evolutions of the optical and elastic properties of the interfaces, as probed by ellipsometry and surface dilatational rheology respectively, provide a consistent physical picture of the building up of the protein interfacial layer. A progressive coverage of the interface by the proteins occurs at low Π. This stage is followed, at higher Π, by conformational rearrangements of the protein film, which are identified by a strong increase of the dissipative viscoelastic properties of the film concomitantly with a peculiar evolution of its optical profile that we have rationalized. In the last stage, at even higher surface pressure, the adsorption is arrested; the optical profile is not modified while the elasticity of the interfacial layer dramatically increases with the surface pressure, presumably due to the film ageing., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The methyl ester sulfonates represent a promising group of anionic surfactants which have the potential for improved performance and biocompatibility in a range of applications. Their solution properties, in particular their tolerance to hard water, suggests that surface ordering may occur in the presence of multi-valent counterion. Understanding their adsorption properties in a range of different circumstances is key to the exploitation of their potential. Neutron reflectivity and surface tension have been used to characterise the adsorption at the air-aqueous solution interface of the anionic surfactant sodium tetradecanoic 2-sulfo 1-methyl ester, C 14 MES, in the absence of electrolyte and in the presence of mono, di, and tri-valent counterions, Na + , Ca 2+ , and Al 3+ . In particular the emphasis has been on exploring the tendency to form layered structures at the interface. In the absence of electrolyte and in the presence of NaCl and CaCl 2 and AlCl 3 at low concentrations monolayer adsorption is observed, and the addition of electrolyte results in enhanced adsorption. In the presence of NaCl and CaCl 2 only monolayer adsorption is observed. However at higher AlCl 3 concentrations surface multilayer formation is observed, in which the number of bilayers at the surface depends upon the surfactant and AlCl 3 concentrations., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The antimicrobial property of silver nanoparticles (AgNPs) is believed to be associated to their interaction with biointerfaces such as microbial cell membranes, encouraging research on the identification of membrane sites capable of AgNPs binding. Although significant progress has been made in that regard, the exact molecular mechanism of action is yet to be fully understood. In this study, AgNPs dispersed in aqueous media and stabilized with polyvinylpyrrolidone were incorporated in Langmuir monolayers of selected lipids that served as cell membrane models. Results from pressure-area isotherms, vibrational spectroscopy and Brewster angle microscopy revealed condensation of glycoside-free lipid monolayers, evidencing that the AgNPs interact mostly with the lipid hydrophilic head groups. In contrast, the monolayers of systems containing glycoside derivatives were found to expand upon AgNPs incorporation, indicating that the glycosidic compounds might facilitate the incorporation of these nanoparticles in cellular membranes. These data can be therefore correlated with the possible toxicity and microbicide effect of AgNPs in lipidic surfaces of mammalian and microbial membranes., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The effects of carbon quantum dots (CQDs) on the dynamic properties of bovine serum albumin (BSA) were investigated using pendant drop profile analysis method. Moreover, the effects of CQDs on the competitive adsorption of BSA and dipalmitoyl phosphatidylcholine (DPPC) were examined. CQDs reduce the fluorescence intensity of BSA and cause a red shift in fluorescence emission. The quenching constant at pH 4.3 is almost twice as large as that of the value obtained at pH 6.0. A small amount of CQDs does not influence the dynamic surface adsorption properties of BSA molecules. As the CQD concentration increases, a gradual increase in adsorption rate of BSA molecules is observed. Moreover, the addition of CQDs results in a significant transition of kinetic dependencies of surface elasticity of BSA solution when the CQD concentration exceeds a critical value. The appearance of the maximum surface elasticity value is probably attributed to the formation of tails and loops. When the dynamic surface properties are dominated by BSA molecules, the effects of CQDs on the surface properties of BSA/DPPC mixture are similar to those of BSA alone. However, when the surface film mainly consists of DPPC, CQDs can obviously change the interfacial properties of DPPC monolayer., (Copyright © 2017 Elsevier Inc. All rights reserved.)

In this work, silver nanoparticles (AgNPs) dispersed in non-aqueous media and stabilized with polyether block polymers amide (PEBA) were incorporated in Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC), which served as a cell membrane model. The AgNPs presented surface activity, disturbing the viscoelastic properties of the floating film. They expanded the monolayers decreasing their surface elasticity as observed with surface pressure-area isotherms. Polarization modulation reflection-absorption spectroscopy showed that the permanence of AgNPs at the air-water interface is favored by PEBA, affecting both the hydrophilic and the hydrophobic groups of the phospholipid. Brewster angle microscopy showed that the AgNPs lead to the formation of aggregates at the air-water interface, establishing domains that shear with each other due to the low lateral viscosity of irregular and non-monomolecular domains. These data can be correlated to the possible toxicity and microbicide effect of AgNPs in lipidic surfaces such as in mammalian and microbial membranes., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Hypothesis: Owing to structural similarities between sulfobetaine lipids and phospholipids it should be possible to form stable Langmuir monolayers from long tail sulfobetaines. By modification of the density of lipid tail group (number of carbon chains) it should also be possible to modulate the two-dimensional phase behaviour of these lipids and thereby compare with that of equivalent phospholipids. Potentially this could enable the use of such lipids for the wide array of applications that currently use phospholipids. The benefit of using sulfobetaine lipids is that they can be synthesised by a one-step reaction from cheap and readily available starting materials and will degrade via different pathways than natural lipids. The molecular architecture of the lipid can be easily modified allowing the design of lipids for specific purposes. In addition the reversal of the charge within the sulfobetaine head group relative to the charge orientation in phospholipids may modify behaviour and thereby allow for novel uses of these surfactants., Experiments: Stable Langmuir monolayers were formed composed of single and double tailed sulfobetaine lipids. Surface pressure-area isotherm, Brewster Angle Microscopy and X-ray and neutron reflectometry measurements were conducted to measure the two-dimensional phase behaviour and out-of-plane structure of the monolayers as a function of molecular area., Findings: Sulfobetaine lipids are able to form stable Langmuir monolayers with two dimensional phase behaviour analogous to that seen for the well-studied phospholipids. Changing the number of carbon tail groups on the lipid from one to two promotes the existence of a liquid condensed phase due to increased Van der Waals interactions between the tail groups. Thus the structure of the monolayers appears to be defined by the relative sizes of the head and tail groups in a predictable way. However, the presence of sub-phase ions has little effect on the monolayer structure, behaviour that is surprisingly different to that seen for phospholipids., (Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.)

Oligoamines and biogenic amines (naturally occurring oligoamines) are small flexible polycations. They interact strongly with anionic surfactants such as sodium dodecyl sulfate, SDS. This results in enhanced adsorption and the formation of layered structures and the formation of layered structures at the air-water interface which depends on surfactant concentration and solution pH. The effect of changing the surfactant headgroup geometry on that interaction and subsequent adsorption is reported here. Neutron reflectivity, NR, results for the surface adsorption of the anionic surfactant sodium diethylene glycol monododecyl ether sulfate, SLES, with the biogenic amine, spermine, are presented, and contrasted with previous data for SDS/spermine mixtures. The enhancement in the adsorption of the surfactant at the air-water interface where monolayer adsorption occurs is similar for both surfactants. However the regions of surfactant concentration and solution pH where surface multilayer adsorption occurs is less extensive for the SLES/spermine mixtures, and occurs only at low pH. The results show how changing the headgroup geometry by the introduction of the ethylene oxide linker group between the alkyl chain and sulfate headgroup modifies the polyamine - surfactant interaction. The increased steric constraint from the polyethylene oxide group disrupts the conditions for surface multilayer formation at the higher pH values. This has important consequences for applications where the modification or manipulation of the surface properties are required., (Copyright © 2015 Elsevier Inc. All rights reserved.)

The oligoamines, such as ethylenediamine to pentaethylenetetramine, and the aliphatic biogenic amines, such as putrescine, spermidine and spermine, strongly interact with anionic surfactants, such as sodium dodecylsulfate, SDS. It has been shown that this results in pronounced surfactant adsorption at the air-water interface and the transition from monolayer to multilayer adsorption which depends upon solution pH and oligoamine structure. In the neutron reflectivity, NR, and surface tension, ST, results presented here the role of the oligoamine structure on the adsorption of SDS is investigated more fully using a range of different biogenic amines. The effect of the extent of the intra-molecular spacing between amine groups on the adsorption has been extended by comparing results for cadavarine with putrescine and ethylenediamine. The impact of more complex biogenic amine structures on the adsorption has been investigated with the aromatic phenethylamine, and the heterocyclic amines histamine and melamine. The results provide an important insight into how surfactant adsorption at interfaces can be manipulated by the addition of biogenic amines, and into the role of solution pH and oligoamine structure in modifying the interaction between the surfactant and oligoamine. The results impact greatly upon potential applications and in understanding some of the important biological functions of biogenic amines., (Copyright © 2015 Elsevier Inc. All rights reserved.)

We have compared the behavior of ovotransferrin at the air-solution interface in the presence of a monovalent ion (acetate), or a divalent ion (citrate), the latter being known to induce conformational changes of this protein upon interaction with its iron-binding sites. We have characterised the adsorption layer at the air-water interface in terms of homogeneity, surface concentration excess and rheological properties at pH 4.0. Besides we have investigated the bulk conformation in the presence of the two anions. In the presence of citrate only, interfacial layers display well-defined domains of higher overall surface concentration suggesting multilayers adsorption. Citrate also induces higher helical content and stabilizes the protein against thermal denaturation. Hence we propose that these changes are involved in the propensity of ovotransferrin to self-assemble at the air-water interface resulting in thick and heterogeneous interfacial layer., (Copyright © 2014 Elsevier Inc. All rights reserved.)

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as [Im-n-Im], 2Br(-) (n=2, 5, 6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units [-(CH2)n-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units [-(CH2)n-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Understanding colloid mobilization during transient flow in soil is important for addressing colloid and contaminant transport issues. While theoretical descriptions of colloid detachment exist for saturated systems, corresponding mechanisms of colloid mobilization during drainage and imbibition have not been considered in detail. In this work, theoretical force and torque analyses were performed to examine the interactive effects of adhesion, drag, friction, and surface tension forces on colloid mobilization and to outline conditions corresponding to the mobilization mechanisms such as lifting, sliding, and rolling. Colloid and substrate contact angles were used as variables to determine theoretical criteria for colloid mobilization mechanisms during drainage and imbibition. Experimental mobilization of hydrophilic and hydrophobic microspheres with drainage and imbibition fronts was investigated in hydrophilic and hydrophobic channels using a confocal microscope. Colloid mobilization differed between drainage and imbibition due to different dynamic contact angles and interfacial geometries on the contact line. Experimental results did not fully follow the theoretical criteria in all cases, which was explained with additional factors not included in the theory such as presence of aggregates and trailing films. Theoretical force and torque analyses resulted in similar mobilization predictions and suggested that all mobilization mechanisms contributed to the observed colloid mobilization., (Copyright © 2013 Elsevier Inc. All rights reserved.)