Maja S. Hellsing

Adsorption of a water treatment protein from Moringa oleifera seeds to a silicon oxide surface studied by neutron reflection.

An extract from the seeds of the Moringa oleifera tree that is principally a low molecular mass protein is known to be efficient as a coagulating agent for water treatment. The present paper investigates the adsorption of the purified protein to silica interfaces in order to elucidate the mechanism of its function as a flocculent. Neutron reflection permits the determination of the structure and composition of interfacial layers at the solid/solution interface. Dense layers of protein with about 5.5 mg m(-2) were found at concentrations above 0.025% wt. The overall thickness with a dense layer in excess of 60 A at 0.05 wt % suggests strong co-operative binding rather than single isolated molecules. An ionic surfactant, sodium dodecyl sulfate, was also seen to coadsorb. This strong adsorption of protein in combination with the tendency for the protein to associate suggests a mechanism for destabilizing particulate dispersions to provide filterable water. This can occur even for the protein that has previously been identified as being of low mass (about 7 kDaltons) and thus is unlikely to be efficient in bridging or depletion flocculation.

Adsorption of aerosol-OT to sapphire: lamellar structures studied with neutrons.

The adsorption of sodium bis 2-ethylhexyl sulfosuccinate, NaAOT, to a sapphire surface from aqueous solution has been studied by neutron reflection at concentrations above the critical micelle concentration (cmc). Complementary measurements of the bulk structure were made with small-angle neutron scattering and grazing incidence small-angle neutron scattering. At a concentration of about 1% wt (10 × cmc), lamellar phase NaAOT was observed both at the surface and in the bulk. The structure seen at the interface for a solution of 2% wt NaAOT is a 35 ± 2 Å thick bilayer adsorbed to the sapphire surface at maximum packing density, followed by an aligned stack of fluctuating bilayers of thickness 51 ± 2 Å and with an area per molecule of 40 ± 2 Å(2). Each bilayer is separated by a water: at 25 °C, this layer is 148 ± 2 Å. A simple model for the reflectivity from fluctuating layers is presented, and for 2.0% wt NaAOT the fluctuations were found to have an amplitude of 25 ± 5 Å. The temperature sensitivity of the structure at the surface was investigated in the range 15-30 °C. The effect of temperature was pronounced, with the solvent layer becoming thinner and the volume occupied by the NaAOT molecules in a bilayer increasing with temperature. The amplitude of the fluctuations, however, is approximately temperature independent in this range. The adsorption of NaAOT at the sapphire surface resembles that previously found at hydrophilic and hydrophobic silica surfaces. The coexisting bulk lamellar phase has a spacing of layers similar to that observed at the surface. These observations are an indication that the major driving force for adsorption is self-assembly, independent of the chemical nature of the interface.

Effect of Concentration and Addition of Ions on the Adsorption of Aerosol-OT to Sapphire

Aerosol-OT (sodium bis 2-ethylhexyl sulfosuccinate or NaAOT) adsorbs to hydrophilic sapphire solid surfaces. The structure of the formed bilayer has been determined over the concentration range 0.2-7.4 mM NaAOT. It was found that the hydrocarbon tails pack at maximum packing limit at very low concentrations, and that the thickness of the bilayer was concentration-independent. The adsorption was found to increase with concentration, with the surfactant molecules packing closer laterally. The area per molecule was found to change from 138 ± 25 to 51 ± 4 A(2) over the concentration range studied, with the thickness of the layer being constant at 33 ± 2 A. Addition of small amounts of salt was found to increase the surface excess, with the bilayer being thinner with a slightly larger area per molecule. Addition of different salts of the same valency was found to have a very similar effect, as had the addition of NaOH and HCl. Hence, the effects of adding acid or base should be considered an effect of ionic strength rather than an effect of pH. Adsorption of NaAOT to the sapphire surface that carries an opposite charge to the anionic surfactant is similar in many respects to the adsorption reported previously for hydrophilic and hydrophobic silica surfaces. This suggests that the adsorption of NaAOT to a surface is driven primarily by NaAOT self-assembly rather than effects of electrostatic attraction to the interface.

A holder to rotate sample cells to avoid sedimentation in small-angle neutron scattering and ultra small-angle neutron scattering experiments

Sedimentation, or creaming, of samples can significantly alter the amount of material in the beam during small-angle scattering experiments. Simple rotating mounts that ameliorate this effect are described and the design criteria are carefully discussed. A modular design permits simple adaptation to various instruments and different sample cells. Temperature control in the range 10 degrees C below ambient to about +40 degrees C has been implemented using air flow and a Peltier device. Example ultra small-angle neutron scattering data are shown that exploit the simplicity of the mounts and the capability to position several samples close together on a translation stage.

Sorption of perfluoroalkyl substances to two types of minerals.

The sorption of perfluoroalkyl substances (PFASs) was investigated for two model soil mineral surfaces, alumina (Al2O3) and silica (SiO2), on molecular level using neutron scattering. The PFASs were selected (i.e. perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonic acid (PFOS)) to examine the role of hydrophobic chain length and hydrophilic functional group on their sorption behaviour. All four PFASs were found to sorb to alumina surface (positively charged) forming a hydrated layer consisting of 50% PFASs. The PFAS solubility limit, which decrease with chain length, was found to strongly influence the sorption behaviour. The sorbed PFAS layer could easily be removed by gentle rinsing with water, indicating release upon rainfall in the environment. No sorption was observed for PFOA and PFOS at silica surface (negatively charged), showing electrostatic interaction being the driving force in the sorption process.

Note: Sample cells to investigate solid/liquid interfaces with neutrons

The design of sample cells to study solid/liquid interfaces by neutron reflection is presented. Use of standardized components and a modular design has allowed a wide range of experiments that include grazing incidence scattering and conventional small-angle scattering. Features that reduce background scattering are emphasized. Various flow arrangements to fill and replenish the liquid in the cell as well as continuous stirring are described.

Interaction of Moringa oleifera seed protein with a mineral surface and the influence of surfactants

The paper describes the adsorption of purified protein from seeds of Moringa oleifera to a sapphire interface and the effects of addition of the anionic surfactant sodium dodecylsulfate (SDS) and the cationic surfactant hexadecyltrimethylammonium bromide (CTAB). Neutron reflection was used to determine the structure and composition of interfacial layers adsorbed at the solid/solution interface. The maximum surface excess of protein was found to be about 5.3 mg m(-2). The protein does not desorb from the solid/liquid interface when rinsed with water. Addition of SDS increases the reflectivity indicating co-adsorption. It was observed that CTAB is able to remove the protein from the interface. The distinct differences to the behavior observed previously for the protein at the silica/water interface are identified. The adsorption of the protein to alumina in addition to other surfaces has shown why it is an effective flocculating agent for the range of impurities found in water supplies. The ability to tailor different surface layers in combination with various surfactants also offers the potential for adsorbed protein to be used in separation technologies.

Crystalline order of polymer nanoparticles over large areas at solid/liquid interfaces

We report on the formation of large two-dimensional domains (about 20 cm2) of oriented and ordered structures of polystyrene particles dispersed in water at a solid/liquid interface. Gentle flow of the dispersed sample into the holder at a shear strain rate of about 0.1 s−1 caused particles at the air/latex meniscus to self-assemble in a regular structure on both solid silica or alumina surfaces. Scattering experiments show that the particle separation at the surface was the same as in the bulk and determined by repulsion arising from the charges on the particles. Close-packed planes formed parallel to the interface.

Scattering from Dilute and Lamellar Phase Solutions of Aerosol-OT Simultaneous Probe of Surface Structures and Bulk

The benefits of simultaneous studies of adsorbed layers and bulk structures are shown for solutions of the surfactant Aerosol-OT. Above the critical micelle concentration, Aerosol-OT forms an aligned lamellar phase at the sapphire/solution interface which is in equilibrium with a bulk phase that consists of coexisting micellar solution and dispersed lamellar phase. Measurements of the aligned surface layers and the bulk scattering from a 2 % wt solution by grazing incidence and small-angle neutron scattering show that the bulk consist of lamellar structures with the same d-spacing as seen at the surface but without the surface induced alignment. The surface lamellar structure corresponds to a 10 % volume fraction for a 2 % wt bulk which implies that there must be coexistence of regions of different concentration. Scattering patterns measured in grazing incidence geometry clearly show the relative contributions from small-angle scattering and specular reflectivity.

Salt induced polystyrene latex flocs investigated by neutron scattering

Studies with a model system consisting of polystyrene latex particles showed that the protein from seeds of Moringa trees adsorbs to the surface and causes flocculation as unusually dense aggregates. In this study, electrolytes sodium chloride (NaCl), ferric chloride (FeCl3) and aluminium sulfate (Al2(SO4)3) have been used to aggregate model polystyrene particles. The study augments previous work using neutron scattering on the flocculation of polystyrene latex with protein from seeds of Moringa trees that had indicated higher floc dimension, df, values as the concentration of particles increased. The measurements were made using ultra small-angle neutron scattering. Generally the fractal dimension, and thus the floc density, increased with particle concentration and salt concentration. Flocculation was apparent at much lower concentrations of FeCl3 and Al2(SO4)3 than of NaCl. The values of df were found not to simply scale with ionic strength for the three electrolytes studied with FeCl3 being the most effective flocculating agent.