Adsorption hierarchy of surfactants and polymers to a damaged hair model: effect of composition, order and polymer size.

A comprehensive understanding of chemical interactions at the surface of hair represents an important area of research within the cosmetic industry and is essential to obtain new products that exhibit both performance and sustainability. This paper aims at contributing to this research by applying a combination of surface techniques (neutron reflectometry, quartz-crystal microbalance and atomic force microscopy) to study adsorption of surface active ingredients onto hair-mimetic surfaces. The surface of hair is not homogeneous due to chemical and physical damage, and this work focuses on partly damaged hair models, in which both hydrophobic and charged moieties are present.

Understanding interactions of plasticisers with a phospholipid monolayer.

The use of DEHP (diethylhexyl phthalate) is now banned for most applications in Europe; the exception is for blood bags, where its toxicity is overshadowed by its ability to extend the storage life of red blood cells. Another plasticiser, BTHC (butanoyl trihexyl citrate), is used in paediatric blood bags but does not stabilise blood cells as effectively. Interactions between plasticisers and lipids are investigated with a phospholipid, DMPC, to understand the increased stability of blood cells in the presence of DEHP as well as bioaccumulation and identify differences with BTHC.

Experimental and simulation study of self-assembly and adsorption of glycerol monooleate in -dodecane with varying water content onto iron oxide.

The self-assembly and surface adsorption of glycerol monooleate (GMO) in -dodecane are studied using a combination of experimental and molecular dynamics simulation techniques. The self-assembly of GMO to form reverse micelles, with and without added water, is studied using small-angle neutron scattering and simulations. A large-scale simulation is also used to investigate the self-assembly kinetics.

Fully Aqueous Self-Assembly of a Gold-Nanoparticle-Based Pathogen Sensor.

Surface plasmon resonance (SPR) is a very sensitive measure of biomolecular interactions but is generally too expensive for routine analysis of clinical samples. Here we demonstrate the simplified formation of virus-detecting gold nanoparticle (AuNP) assemblies on glass using only aqueous buffers at room temperature. The AuNP assembled on silanized glass and displayed a distinctive absorbance peak due to the localized SPR (LSPR) response of the AuNPs.

Effect of Anionic Lipids on Mammalian Plasma Cell Membrane Properties.

The effect of lipid composition on models of the inner leaflet of mammalian cell membranes has been investigated. Grazing incidence X-ray diffraction and X-ray and neutron reflectivity have been used to characterize lipid packing and solvation, while electrochemical and infrared spectroscopic methods have been employed to probe phase behavior in an applied electric field. Introducing a small quantity of the anionic lipid dimyristoylphosphatidylserine (DMPS) into bilayers of zwitterionic dimyristoylphosphatidylethanolamine (DMPE) results in a significant change in the bilayer response to an applied field: the tilt of the hydrocarbon chains increases before returning to the original tilt angle on detachment of the bilayer.

Structural Characterization of Nanoparticle-Supported Lipid Bilayer Arrays by Grazing Incidence X-ray and Neutron Scattering.

Arrays of nanoparticle-supported lipid bilayers (nanoSLB) are lipid-coated nanopatterned interfaces that provide a platform to study curved model biological membranes using surface-sensitive techniques. We combined scattering techniques with direct imaging, to gain access to sub-nanometer scale structural information on stable nanoparticle monolayers assembled on silicon crystals in a noncovalent manner using a Langmuir-Schaefer deposition. The structure of supported lipid bilayers formed on the nanoparticle arrays via vesicle fusion was investigated using a combination of grazing incidence X-ray and neutron scattering techniques complemented by fluorescence microscopy imaging.

Adsorption Behavior of the Coenzyme NADH at the Carbon/Electrolyte Interface Determined by Neutron Reflectometry.

The adsorption behavior of β-nicotinamide adenine dinucleotide (NADH) at the carbon/electrolyte interface has been studied using a combination of neutron reflectometry (NR) and solution depletion isotherms. Coupling the NR technique with an electrochemical cell allowed observation of the reversible adsorption and desorption of the molecule at the electrode surface over a range of applied potentials. The overall surface coverage was low (30-50%), suggesting adsorption only at specific defect sites on the surface.

Systematic hydration neutron reflectometry study on Nafion thin films.

Reported herein is a neutron reflectometry (NR) study on hydrated Nafion thin films (∼30 nm) on a silicon substrate with native oxide. The Nafion morphology is investigated systematically across the whole relative humidity range using both HO and DO vapours to enable a comparative study. By utilising this systematic approach two key results have been obtained.

Probing the Separation Distance between Biological Nanoparticles and Cell Membrane Mimics Using Neutron Reflectometry with Sub-Nanometer Accuracy.

Nanoparticle interactions with cellular membranes are controlled by molecular recognition reactions and regulate a multitude of biological processes, including virus infections, biological nanoparticle-mediated cellular communication, and drug delivery applications. Aided by the design of various supported cell membrane mimics, multiple methods have been employed to investigate these types of interactions, revealing information on nanoparticle coverage, interaction kinetics, as well as binding strength; however, precise quantification of the separation distance across which these delicate interactions occur remains elusive. Here, we demonstrate that carefully designed neutron reflectometry (NR) experiments followed by an attentive selection and application of suitable theoretical models offer a means to quantify the distance separating biological nanoparticles from a supported lipid bilayer (SLB) with sub-nanometer precision.

MUC5B mucin films under mechanical confinement: A combined neutron reflectometry and atomic force microscopy study.

Hypothesis: Among other functions, mucins hydrate and protect biological interfaces from mechanical challenges. Mucins also attract interest as biocompatible coatings with excellent lubrication performance. Therefore, it is of high interest to understand the structural response of mucin films to mechanical challenges.

Water-Resistant Surface Modification of Hydrophobic Polymers with Water-Soluble Surfactant Additives.

Water-soluble nonionic surfactant, pentaethylene glycol monododecyl ether, CE, spontaneously blooms to the surface of spin-cast hydrophobic polyisoprenes, generating hydrophilic surfaces. This system provides a simple model for hydrophilic chemical modification of rubbery polymers that demonstrates surprisingly rich, complex, and unexpected behaviour. The vertical depth profiles were quantified using neutron reflectometry (NR) using a novel procedure to account for undulations in the film thickness.

Interfacial complexation of a neutral amphiphilic 'tardigrade' co-polymer with a cationic surfactant: Transition from synergy to competition.

Hypothesis: Neutral amphiphilic PEG-g-PVAc co-polymer (a "tardigrade" polymer consisting of a hydrophilic polyethylene glycol, PEG, backbone with hydrophobic polyvinyl acetate, PVAc, grafts) can form complexes at the air-water interface with cationic dodecyltrimethylammonium bromide (DTAB) via self-assembly. Compared to anionic SDS, cationic DTAB headgroups are expected to interact strongly with the negatively charged OH groups from the partial dissociation of the PVAc grafts. We anticipate a transition from synergistic to competitive behaviour, which is expected to be dependent on the surfactant structural characteristics and concentration.

Effect of nonionic and amphoteric surfactants on salivary pellicles reconstituted in vitro.

Surfactants are important components of oral care products. Sodium dodecyl sulfate (SDS) is the most common because of its foaming properties, taste and low cost. However, the use of ionic surfactants, especially SDS, is related to several oral mucosa conditions.

Towards a neutron and X-ray reflectometry environment for the study of solid-liquid interfaces under shear.

A novel neutron and X-ray reflectometry sample environment is presented for the study of surface-active molecules at solid-liquid interfaces under shear. Neutron reflectometry was successfully used to characterise the iron oxide-dodecane interface at a shear rate of [Formula: see text] [Formula: see text] using a combination of conventional reflectometry theory coupled with the summation of reflected intensities to describe reflectivity from thicker films. Additionally, the structure adopted by glycerol monooleate (GMO), an Organic Friction Modifier, when adsorbed at the iron oxide-dodecane interface at a shear rate of [Formula: see text] [Formula: see text] was studied.

Influence of surfactants on a pre-adsorbed cationic layer: Removal and modification.

Removal of organic species from solid surfaces is a crucial process. The use of oppositely charged surfactants provides a potential method for enhanced removal. Neutron reflectometry has been used to investigate the complex behaviour of a pre-adsorbed and tenacious layer of the cationic surfactant didodecyldimethylammonium bromide (DDAB) on a mica surface, during exposure to different organic species in solution.

Effect of water on the electroresponsive structuring and friction in dilute and concentrated ionic liquid lubricant mixtures.

The effect of water on the electroactive structuring of a tribologically relevant ionic liquid (IL) when dispersed in a polar solvent has been investigated at a gold electrode interface using neutron reflectivity (NR). For all solutions studied, the addition of small amounts of water led to clear changes in electroactive structuring of the IL at the electrode interface, which was largely determined by the bulk IL concentration. At a dilute IL concentration, the presence of water gave rise to a swollen interfacial structuring, which exhibited a greater degree of electroresponsivity with applied potential compared to an equivalent dry solution.

A comparison between the structures of reconstituted salivary pellicles and oral mucin (MUC5B) films.

Hypothesis: Salivary pellicles i.e., thin films formed upon selective adsorption of saliva, protect oral surfaces against chemical and mechanical insults.

Morphology of bile salts micelles and mixed micelles with lipolysis products, from scattering techniques and atomistic simulations.

Hypotheses: Bile salts (BS) are biosurfactants released into the small intestine, which play key and contrasting roles in lipid digestion: they adsorb at interfaces and promote the adsorption of digestive enzymes onto fat droplets, while they also remove lipolysis products from that interface, solubilising them into mixed micelles. Small architectural variations on their chemical structure, specifically their bile acid moiety, are hypothesised to underlie these conflicting functionalities, which should be reflected in different aggregation and solubilisation behaviour.

Experiments: The micellisation of two BS, sodium taurocholate (NaTC) and sodium taurodeoxycholate (NaTDC), which differ by one hydroxyl group on the bile acid moiety, was assessed by pyrene fluorescence spectroscopy, and the morphology of aggregates formed in the absence and presence of fatty acids (FA) and monoacylglycerols (MAG) - typical lipolysis products - was resolved by small-angle X-ray/neutron scattering (SAXS, SANS) and molecular dynamics simulations.

Interfacial structuring of non-halogenated imidazolium ionic liquids at charged surfaces: effect of alkyl chain length.

Control of the interfacial structures of ionic liquids (ILs) at charged interfaces is important to many of their applications, including in energy storage solutions, sensors and advanced lubrication technologies utilising electric fields. In the case of the latter, there is an increasing demand for the study of non-halogenated ILs, as many fluorinated anions have been found to produce corrosive and toxic halides under tribological conditions. Here, the interfacial structuring of a series of four imidazolium ILs ([CnC1Im]) of varying alkyl chain lengths (n = 5, 6, 7, 10), with a non-halogenated borate-based anion ([BOB]), have been studied at charged interfaces using sum frequency generation (SFG) spectroscopy and neutron reflectivity (NR).

Spontaneous Formation of Cushioned Model Membranes Promoted by an Intrinsically Disordered Protein.

In this article, it is shown that by exposing commonly used lipids for biomembrane mimicking studies, to a solution containing the histidine-rich intrinsically disordered protein histatin 5, a protein cushion spontaneously forms underneath the bilayer. The underlying mechanism is attributed to have an electrostatic origin, and it is hypothesized that the observed behavior is due to proton charge fluctuations promoting attractive electrostatic interactions between the positively charged proteins and the anionic surfaces, with concomitant counterion release. Hence, we anticipate that this novel "green" approach of forming cushioned bilayers can be an important tool to mimic the cell membrane without the disturbance of the solid substrate, thereby achieving a further understanding of protein-cell interactions.

Structural Changes in Adsorbed Cytochrome c upon Applied Potential Characterized by Neutron Reflectometry.

The structural behavior of an electron-transfer protein, cytochrome c, at the 316L stainless steel electrode/aqueous interface was investigated over a range of applied potentials using neutron reflectometry supported by solution depletion isotherms, X-ray reflectometry, and quartz crystal microbalance measurements. A custom-made electrochemical cell allowed in situ observation of the adsorbed protein across a range of applied potentials; models fitted to the NR data showed a compact inner protein layer at the metal/electrolyte interface and a further thicker but highly diffuse layer that could be removed by rinsing. The overall amount adsorbed was found to be strongly dependent on the applied potential and buffer pH.

Potassium, Calcium, and Magnesium Bridging of AOT to Mica at Constant Ionic Strength.

The bridging effect of a series of common cations between the anionic mica surface and the AOT anion has been studied in a condition of constant ionic strength and surfactant concentration. It was found that sodium ions did not show any bridging effect in this system; however, calcium, magnesium, and potassium all caused adsorption of the organic to the mica surface. The concentrations at which bridging occurred was probed, revealing that only a very low bridging cation concentration was required for binding.

Coadsorption of a Monoclonal Antibody and Nonionic Surfactant at the SiO/Water Interface.

During the formulation of therapeutic monoclonal antibodies (mAbs), nonionic surfactants are commonly added to attenuate structural rearrangement caused by adsorption/desorption at interfaces during processing, shipping, and storage. We examined the adsorption of a mAb (COE-3) at the SiO/water interface in the presence of pentaethylene glycol monododecyl ether (CE), polysorbate 80 (PS80-20EO), and a polysorbate 80 analogue with seven ethoxylates (PS80-7EO). Spectroscopic ellipsometry was used to follow COE-3 dynamic adsorption, and neutron reflection was used to determine interfacial structure and composition.