J. Mieke Kleijn

Adsorption of the protein bovine serum albumin in a planar poly(acrylic acid) brush layer as measured by optical reflectometry.

The adsorption of bovine serum albumin (BSA) in a planar poly(acrylic acid) (PAA) brush layer has been studied by fixed-angle optical reflectometry. The influence of polymer length, grafting density, and salt concentration is studied as a function of pH. The results are compared with predictions of an analytical polyelectrolyte brush model, which incorporates charge regulation and excluded volume interactions. A maximum in adsorption is found near the point of zero charge (pzc) of the protein. At the maximum, BSA accumulates in a PAA brush to at least 30 vol %. Substantial adsorption continues above the pzc, that is, in the pH range where a net negatively charged protein adsorbs into a negatively charged brush layer, up to a critical pH value. This critical pH value decreases with increasing ionic strength. The adsorbed amount increases strongly with both increasing PAA chain length and increasing grafting density. Experimental data compare well with the analytical model without having to include a nonhomogeneous charge distribution on the protein surface. Instead, charge regulation, which implies that the protein adjusts its charge due to the negative electrostatic potential in the brush, plays an important role in the interpretation of the adsorbed amounts. Together with nonelectrostatic interactions, it explains the significant protein adsorption above the pzc.

Bipolar electrode behaviour of the aluminium surface in a lateral electric field

Abstract This paper reports on the electrochemical processes at the surface of conducting materials such as aluminium in a thin-layer cell usually employed for electrokinetic measurements. The cell contains one or more planar Al wafers in contact with an electrolyte solution, which is subjected to an external electric field parallel to the surfaces of the wafers. Beyond a certain threshold value of the magnitude of the field, the current through the cell increases more than proportionally with the field strength. This is due to faradaic processes occurring at the two ends of the conducting substrates, i.e. reduction at the positive side of the electric field in the solution and oxidation at the negative side. In the case of Al wafers, anodic dissolution of the metal takes place and the progression of the ‘corroding’ edge can be followed visually. The overall electrolytic process, corresponding with the distributed current along the surface of the wafer, could be explained and modeled on the basis of the conventionally measured Butler–Volmer characteristics of the monopolar Al electrode.

Adsorption of Anionic Surfactants in a Nonionic Polymer Brush: Experiments, Comparison with Mean-Field Theory, and Implications for Brush−Particle Interaction

The adsorption of the anionic surfactants sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS) in poly(ethylene oxide) (PEO) brushes was studied using a fixed-angle optical flow-cell reflectometer. We show that, just as in solution, there is a critical association concentration (CAC) for the surfactants at which adsorption in the PEO brush starts. Above the critical micelle concentration (CMC) the adsorption is found to be completely reversible. At low brush density the adsorption per PEO monomer is equal to the adsorption of these surfactants in bulk solution. However, with increasing brush density, the number of adsorbed surfactant molecules per PEO monomer decreases rapidly. This decrease is explained in terms of excluded volume interactions plus electrostatic repulsion between the negatively charged surfactant micelles. Experimentally, a plateau value in the total adsorption is observed as a function of grafting density. The experimental results were compared to the results of an analytical self-consistent field (aSCF) model, and we found quantitative agreement. Additionally, the model predicts that the plateau value found is in fact a maximum. Both experiments and model calculations show that the adsorption scales directly with the polymerization degree of the polymers in the brush. They also show that an increase in the ionic strength leads to an increase in the adsorbed amount, which is explained as being due to a decrease in the electrostatic penalty for the adsorption of the SDS micelles. The adsorption of SDS micelles changes the interactions of the PEO brush with a silica particle. This is illustrated by atomic force microscopy (AFM) measurements of the pull-off force of a silica particle from a PEO brush: at high enough PEO densities, the addition of SDS leads to a very strong reduction in the force necessary to detach the colloidal silica particle from the PEO brush. We attribute this effect to the large amount of negative charge incorporated in the PEO brush due to SDS adsorption.

Ultradense Polymer Brushes by Adsorption

Standing room only: Dense polymer brushes can be prepared by adsorbing a diblock copolymer comprising a neutral block and a polyelectrolyte block to an oppositely charged polyelectrolyte brush (see picture). The density of the resulting neutral brush is determined by charge compensation, leading to brush densities well over 1 nm(-2). The diblock copolymer can be desorbed by changing the solution conditions.

The toxicity of plastic nanoparticles to green algae as influenced by surface modification, medium hardness and cellular adsorption

To investigate processes possibly underlying accumulation and ecological effects of plastic nano-particles we have characterized their interaction with the cell wall of green algae. More specifically, we have investigated the influence of particle surface functionality and water hardness (Ca2+ concentration) on particle adsorption to algae cell walls. Polystyrene nanoparticles with different functional groups (non-functionalized, -COOH and -NH2) as well as coated (starch and PEG) gold nanoparticles were applied in these studies. Depletion measurements and atomic force microscopy (AFM) showed that adsorption of neutral and positively charged plastic nanoparticles onto the cell wall of P. subcapitata was stronger than that of negatively charged plastic particles. Results indicated that binding affinity is a function of both inter-particle and particle-cell wall interactions which are in turn influenced by the medium hardness and particle concentration. Physicochemical modelling using DLVO theory was used to interpret the experimental data, using also values for interfacial surface free energies. Our study shows that material properties and medium conditions play a crucial role in the rate and state of nanoparticle bio-adsorption for green algae. The results show that the toxicity of nanoparticles can be better described and assessed by using appropriate dose metrics including material properties, complexation/agglomeration behavior and cellular attachment and adsorption. The applied methodology provides an efficient and feasible approach for evaluating potential accumulation and hazardous effects of nanoparticles to algae caused by particle interactions with the algae cell walls.

Charge-driven and reversible assembly of ultra-dense polymer brushes: formation and antifouling properties of a zipper brush

We investigated a new type of polymer brushes: the zipper brush. By adsorbing a diblock-copolymer with one charged block and one neutral block to an oppositely charged polyelectrolyte brush, a neutral polymer brush is formed on top of an almost neutral complex layer of polyelectrolytes. This neutral brush can be adsorbed in minutes and desorbed in seconds to restore the original polyelectrolyte brush. The zipper brush can be used, for example, as an antifouling layer to prevent protein adsorption. These characteristics are shown by fixed-angle optical reflectometry for the system of poly(N-methyl-2-vinyl pyridinium)-block-poly(ethylene oxide) (P2MVP-PEO) adsorbed to a poly(acrylic acid) (PAA) brush. After the diblock-copolymer has adsorbed (at pH 6), the charges of the PAA brush are almost completely compensated by the charges of the P2MVP block. The grafting density of the formed neutral brush can be controlled by the chain length and grafting density of the PAA brush, and by the chain length of P2MVP block. As the P2MVP blocks used in this study are much smaller than the PAA chains in the brush, the grafting density of the PEO brushes are found to be a multiplication of that of the PAA brush, and much higher grafting densities (up to 1.59 chains per nm2) can be obtained than previously reported for polymer brushes prepared by adsorption. At low pH, when the PAA is uncharged, only a few mg m−2 adsorb probably because of hydrogen bonding between uncharged PAA and PEO. As the pH increases the PAA becomes more charged and the adsorbed amount of diblock-copolymer increases strongly until pH 6 and then levels off between pH 6 and pH 10. At pH 6 and 10 high salt concentrations (above 250 mM) are needed to significantly reduce the adsorbed amount. The antifouling properties of the zipper brush were tested by exposing the brush to a number of different protein solutions. For the proteins lysozyme, fibrinogen, bovine serum albumin, and b-lactoglobuline the zipper brush completely prevented any adsorption, for cytochrome C a small amount of adsorption was observed.

Colloidal interactions in liquid CO2 — A dry-cleaning perspective

Liquid CO(2) is a viable alternative for the toxic and environmentally harmful solvents traditionally used in dry-cleaning industry. Although liquid CO(2) dry-cleaning is being applied already at a commercial scale, it is still a relatively young technique which poses many challenges. The focus of this review is on the causes of the existing problems and directions to solve them. After presenting an overview of the state-of-the-art, we analyze the detergency challenges from the fundamentals of colloid and interface science. The properties of liquid CO(2) such as dielectric constant, density, Hamaker constant, refractive index, viscosity and surface tension are presented and in the subsequent chapters their effects on CO(2) dry-cleaning operation are delineated. We show, based on theory, that the van der Waals forces between a model soil (silica) and model fabric (cellulose) through liquid CO(2) are much stronger compared to those across water or the traditional dry-cleaning solvent PERC (perchloroethylene). Prevention of soil particle redeposition in liquid CO(2) by electrostatic stabilization is challenging and the possibility of using electrolytes having large anionic parts is discussed. Furthermore, the role of different additives used in dry-cleaning, such as water, alcohol and surfactants, is reviewed. Water is not only used as an aid to remove polar soils, but also enhances adhesion between fabric and soil by forming capillary bridges. Its role as a minor component in liquid CO(2) is complex as it depends on many factors, such as the chemical nature of fabrics and soil, and also on the state of water itself, whether present as molecular solution in liquid CO(2) or phase separated droplets. The phenomena of wicking and wetting in liquid CO(2) systems are predicted from the Washburn-Lucas equation for fabrics of various surface energies and pore sizes. It is shown that nearly complete wetting is desirable for good detergency. The effect of mechanical action and fluid dynamic conditions on dry-cleaning is analyzed theoretically. From this it follows that in liquid CO(2) an order of magnitude higher Reynolds number is required to exceed the binding forces between fabric and soil as opposed to PERC or water, mainly due to the strong van der Waals forces and the low viscosity of CO(2) at dry-cleaning operational conditions.

The production of PEO polymer brushes via Langmuir-Blodgett and Langmuir-Schaeffer methods: incomplete transfer and its consequences.

Using fixed-angle ellipsometry, we investigate the degree of mass transfer upon vertically dipping a polystyrene surface through a layer of a polystyrene-poly(ethylene oxide) (PS-PEO) block copolymer at the air water interface (Langmuir-Blodgett or LB transfer). The transferred mass is proportional to the PS-PEO grafting density at the air-water interface, but the transferred mass is not equal to the mass at the air-water interface. We find that depending on the chain length of the PEO block only a certain fraction of the polymers at the air-water interface is transferred to the solid surface. For the shortest PEO chain length (PS36-PEO148), the mass transfer amounts to 94%, while for longer chain lengths (PS36-PEO370 and PS38-PEO770), a transfer of, respectively 57% and 19%, is obtained. We attribute this reduced mass transfer to a competition for the PS surface between the PEO block and the PS block. Atomic force microscopy shows that after transfer the material is evenly spread over the surface. However, upon a short heating of these transferred layers (95 degrees C, 5 min) a dewetting of the PS-PEO layer takes place. These results have a significant impact on the interpretation of the results in a number of papers in which the above-described transfer method was used to produce PEO polymer brushes, in a few cases in combination with heating. We briefly review these papers and discuss their main results in light of this new information. Furthermore, we show that, by using Langmuir-Schaeffer (LS, horizontal) dipping, much higher mass transfers can be reached than with the LB method. When the LB or LS methods are carefully applied, it is a very powerful technique to produce PEO brushes, as it gives full control over both the grafting density and the chain length.

Adsorption of a linear polyelectrolyte on a gold electrode

The adsorption of quaternized poly-2-vinyl pyridine (PVP+), which has a fixed charge per monomer, onto a gold electrode was investigated using reflectometry. The double layer charge and potential of the gold substrate were controlled by means of either the solution pH or by applying an external potential. The adsorption process was monitored for various molecular masses and concentrations of PVP+, and as a function of the electrolyte concentration, the pH of the solution, and the externally applied potential on the gold electrode. The adsorption isotherms and the dependence on the background electrolyte concentration point to a high non-electrostatic affinity of PVP+ for the gold surface. The results for the two charging mechanisms (pH or applied potential) are very similar when compared by plotting the adsorbed amounts as a function of the double layer potential of the gold. The total adsorbed amount decreases linearly with the double layer potential of the gold. Adsorption takes place up to a relatively high double layer potential, in line with a relatively high contribution of non-electrostatic interactions. The electrostatic barrier for adsorption is always low, since in practically all measurements the initial adsorption rate is completely determined by the transport of molecules towards the gold surface, even near the threshold potential for adsorption.

Subtle Charge Balance Controls Surface-Nucleated Self-Assembly of Designed Biopolymers

We report the surface-nucleated self-assembly into fibrils of a biosynthetic amino acid polymer synthesized by the yeast Pichia pastoris. This polymer has a block-like architecture, with a central silk-like block labeled SH, responsible for the self-assembly into fibrils, and two collagen-like random coil end blocks (C) that colloidally stabilize the fibers in aqueous solution. The silk-like block contains histidine residues (pKa≈6) that are positively charged in the low pH region, which hinders self-assembly. In aqueous solution, CSHC self-assembles into fibers above a pH-dependent critical nucleation concentration Ccb. Below Ccb, where no self-assembly occurs in solution, fibril formation can be induced by a negatively charged surface (silica) in the pH range of 3.5-7. The density of the fibers at the surface and their length are controlled by a subtle balance in charge between the protein polymer and the silica surface, which is evidenced from the dependence on pH. With increasing number density of the fibers at the surface, their average length decreases. The results can be explained on the basis of a nucleation-and-growth mechanism: the surface density of fibers depends on the rate of nucleation, while their growth rate is limited by transport of proteins from solution. Screening of the charges on the surface and histidine units by adding NaCl influences the nucleation-and-growth process in a complicated fashion: at low pH, the growth is improved, while at high pH, the nucleation is limited. Under conditions where nucleation in the bulk solution is not possible, growth of the surface-nucleated fibers into the solution--away from the surface--can still occur.