The odd-even effect, i.e., the influence of the outermost layer of polyelectrolyte multilayers (PEMs) on their swelling behavior, is investigated. For that purpose poly(styrene sodium sulfonate) (PSS)/poly(diallyl-dimethylammonium chloride) (PDADMAC) polyelectrolyte multilayers are studied in air with 1% relative humidity (RH), 30% RH, 95% RH, and in liquid water by ellipsometry, atomic force microscopy (AFM), and X-ray reflectometry (XRR). Since the total amount of water uptake in swollen PEMs is divided into two fractions, the void water and the swelling water, a correct evaluation of the odd-even effect is only possible if both fractions are examined separately. In order to allow measuring samples over a larger thickness regime the investigation of a larger amount of samples is required. Therefore, the concept of separating void water from swelling water using neutron reflectometry is for the first time transferred to ellipsometry. The subsequent analysis of swelling water, void water, and roughness revealed the existence of two types of odd-even effects: an odd-even effect which addresses only the surface of the PEM (surface-odd-even effect) and an odd-even effect which addresses also the bulk of the PEM (bulk-odd-even effect). The appearance of both effects is dependent on the environment; the surface-odd-even effect is only detectable in humid air while the bulk-odd-even effect is only detectable in liquid water. The bulk-odd-even effect is related to the osmotic pressure between the PEM and the surrounding water. A correlation between the amount of void water and both odd-even effects is not found. The amount of void water is independent of the terminated layer and the thickness of PEMs.

Protein immobilization on electrodes is a key concept in exploiting enzymatic processes for bioelectronic devices. For optimum performance, an in-depth understanding of the enzyme-surface interactions is required. Here, we introduce an integral approach of experimental and theoretical methods that provides detailed insights into the adsorption of an oxygen-tolerant [NiFe] hydrogenase on a biocompatible gold electrode. Using atomic force microscopy, ellipsometry, surface-enhanced IR spectroscopy, and protein film voltammetry, we explore enzyme coverage, integrity, and activity, thereby probing both structure and catalytic H2 conversion of the enzyme. Electrocatalytic efficiencies can be correlated with the mode of protein adsorption on the electrode as estimated theoretically by molecular dynamics simulations. Our results reveal that pre-activation at low potentials results in increased current densities, which can be rationalized in terms of a potential-induced re-orientation of the immobilized enzyme.

Polymer coatings are frequently utilized to control and modify substrate properties. The performance of the coatings is often determined by the first polymer layers between the substrate and the bulk polymer material, which are termed interphase. Standard methods have failed to completely characterize this interphase, because its properties change significantly over a few nanometers. Here we determine the spatially resolved adhesion properties of the interphase in polyelectrolyte multilayers (PEMs) by desorbing a single polymer covalently bound to an atomic force microscope cantilever tip from PEMs with varying thickness. We show that the adhesion properties of the first few layers (up to three double layers) is dominated by the surface potential of the substrate, while thicker PEMs are controlled by cohesion in between the PEM polymers. For cohesion, the local film conformation is the crucial parameter. This finding is generalized by utilizing oligoelectrolyte multilayer (OEM) as coatings and both hydrophilic and hydrophobic polymers as polymeric force sensors.

Ultrathin films of complexed polycation poly(diallyldimethylammonium), PDADMA, and polyanion poly(styrenesulfonate), PSS, were prepared on silicon wafers using the layer-by-layer adsorption technique. When terminated with PDADMA, all films had excess PDADMA, which was balanced by counterions. Neutron reflectivity of these as-made multilayers was compared with measurements on multilayers which had been further processed to ensure 1 : 1 stoichiometry of PDADMA and PSS. The compositions of all films, including polymers and counterions, were determined experimentally rather than by fitting, reducing the number of fit parameters required to model the reflectivity. For each sample, acetate, either protiated, CHCOO, or deuterated, CDCOO, served as the counterion. All films were maintained dry under vacuum. Scattering length density profiles were constrained to fit reflectivity data from samples having either counterion. The best fits were obtained with uniform counterion concentrations, even for stoichiometric samples that had been exposed to PDADMA for ca. 5 minutes, showing that surprisingly fast and complete transport of excess cationic charge occurs throughout the multilayer during its construction.

The paper addresses the swelling of polyelectrolyte multilayers (PEMs) at varying humidity. In particular, a new model will be presented, which takes the gradual filling of voids into account. Absorption of water results in PEM swelling. This absorbed water can be distinguished into swelling and void water. Swelling water leads to an increase in thickness and a change of the optical properties of PEMs, while the void water results only in a change of the optical properties. In former studies, neutron reflectometry was used to distinguish between swelling and void water. However, as we show in this study, it is possible to resolve the two different kinds of water in PEMs by ellipsometry, a much simpler tool. The present study evaluates and interprets the refractive index of polystyrenesulfonate/polydiallyldimethylammonium chloride (PSS/PDADMAC) PEMs. Both the swelling behavior and the refractive index change as a function of relative humidity and were found to be independent of the layer number. The void model and the extended void model were used to describe the data. The void model allows fitting the experimentally determined refractive index at humidity beyond 20% RH but fails for humidity lower than 20% RH. Therefore, we modified the existing model in order to account for air-water exchange. The extended void model assumes a gradual air-water exchange at low h and describes the refractive index over the entire humidity range in a precise way. Up to 30% RH, air and water coexist. Above this threshold, the voids are completely filled with water and this threshold does not change either with layer number or with the outermost layer. Furthermore, this model allows the determination of the volume fraction of the voids (0.05 ± 0.01) and the refractive index of the pure polymer matter (1.592 ± 0.002).