Search

Osteoarthritis is the most common arthropathy in western civilization. It is primarily caused by the degeneration of lipid-coated cartilage, leading to increased friction in joints. Hyaluronic acid (HA), a negatively charged polysaccharide and the main component of the synovial fluid, is held responsible for joint lubrication. It is believed that HA, adsorbed to the lipid-coated cartilage, forms a protective layer against wear. Studies have shown that the concentration and molecular weight (MW) of HA are reduced in joints suffering from osteoarthritis. On the basis of these observations, local joint injections of HA or mixtures of HA and surface-active phospholipids (SAPLs) have been applied as medical cures to restore the functionality of the joints in a procedure called viscosupplementation. However, this cure is still disputed, and no consensus has been reached with respect to optimum HA concentration and MW. To provide detailed insight in the structural rearrangement of lipid films upon contact with HA or polymeric analogues, we studied the interaction of the polyelectrolyte poly(allylamine hydrochloride) (PAH) with surface-bound oligobilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) by neutron reflectivity (NR) and ellipsometry. Using this model system, we found a drastic swelling of the lipid films as a function of PAH concentration, whose strength compares to that in previous studies on HA incubation. In contrast, no significant dependence of film thickness on PAH MW was observed. A detailed picture of the film architecture was developed which inter alia shows that charged PAH is adsorbed to the lipid headgroups, leading to electrostatic repulsion. The swelling behavior is well explained by the equilibrium of Coulomb and van der Waals interactions in a DLVO-based model. Our detailed structural analysis of the PAH/lipid interfacial layer may help to elucidate the mechanisms of viscosupplementation and derive a structure-function relationship for the lubricating interface in mammalian joints.

Combination of neutron and X-ray reflectometry was used to study the depth profile of 100 nm thin copper films with implanted oxygen ions with energy E = 10–30 keV and fluencies D = (0.2–5.4) ×1016 cm–2. The oxygen ion implantation at 30 keV was shown to lead to formation of 3 nm thick layer on the surface. Density and copper–oxygen stoichiometry of the observed surface layer was close to Cu2O oxide. We attribute the Cu2O oxide formation to highly mobilized copper atoms generated by stimulated ion implantation.

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich., This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively., The complex interaction of polyelectrolyte multilayers (PEMs) physisorbed onto end-grafted polymer brushes with focus on the temperature-responsive behavior of the system is addressed in this work. The investigated brush/multilayer composite consists of a poly(styrene sulfonate)/poly(diallyldimethylammonium chloride) (PSS/PDADMAC) multilayer deposited onto the poly(N-isopropylacrylamide-b-dimethylaminoethyl methacrylate) P(NIPAM-b-DMAEMA) brush. Ellipsometry and neutron reflectometry were used to monitor the brush collapse with the thickness decrease as a function of temperature and the change in the monomer distribution perpendicular to the substrate at temperatures below, across and above the phase transition, respectively. It was found that the adsorption of PEMs onto polymer brushes had a hydrophobization effect on PDMAEMA, inducing the shift of its phase transition to lower temperatures, but without suppressing its temperature-responsiveness. Moreover, the diffusion of the free polyelectrolyte chains inside the charged brush was proved by comparing the neutron scattering length density profile of pure and the corresponding PEM-capped brushes, eased by the enhanced contrast between hydrogenated brushes and deuterated PSS chains. The results presented herein demonstrate the possibility of combining a temperature-responsive brush with polyelectrolyte multilayers without quenching the responsive behavior, even though significant interpolyelectrolyte interactions are present. This is of importance for the design of multicompartment coatings, where the brush can be used as a reservoir for the controlled release of substances and the multilayer on the top as a membrane to control the diffusion in/out by applying different stimuli.

We have investigated the interactions between cationic poly(amidoamine) (PAMAM) dendrimers of generation 4 (G4), a potential gene transfection vector, with net-anionic model biomembranes composed of different ratios of zwitterionic phosphocholine (PC) and anionic phospho-L-serine (PS) phospholipids. Two types of model membranes were used: solid-supported bilayers, prepared with lipids carrying palmitoyl-oleoyl (PO) and diphytanoyl (DPh) acyl chains, and free-standing bilayers, formed at the interface between two aqueous droplets in oil (droplet interface bilayers, DIBs) using the DPh-based lipids. G4 dendrimers were found to translocate through POPC:POPS bilayers deposited on silica surfaces. The charge density of the bilayer affects translocation, which is reduced when the ionic strength increases. This shows that the dendrimer-bilayer interactions are largely controlled by their electrostatic attraction. The structure of the solid-supported bilayers remains intact upon translocation of the dendrimer. However, the amount of lipids in the bilayer decreases and dendrimer/lipid aggregates are formed in bulk solution, which can be deposited on the interfacial layers upon dilution of the system with dendrimer-free solvent. Electrophysiology measurements on DIBs confirm that G4 dendrimers cross the lipid membranes containing PS, which then become more permeable to ions. The obtained results have implications for PAMAM dendrimers as delivery vehicles to cells.

A common feature of ionic liquids composed of cations with long aliphatic side chains is structural heterogeneities on the nanometer length scale. This so-called microphase separation arises from the clustering of aliphatic moieties. The temperature dependence of the liquid bulk structure was studied by small-angle X-ray and neutron scattering for a set of methylimidazolium ([C18C1im]+, [C22C1im]+) based ionic liquids with tris(pentafluoroethyl)trifluorophosphate ([FAP]−), bis(trifluoromethylsulfonyl)imide ([NTf2]−), and bis(nonafluorobutylsulfonyl)imide ([NNf2]−) anions. The experimental data is quantitatively analyzed using a generalized Teubner–Strey model. Discussion of the resulting periodicity d and correlation length ξ shows that the structural heterogeneities are governed by the interplay between the alkyl chain length, the geometry of the anion, and entropic effects. Connections between the mesoscopic correlation functions, density, and entropy of fusion are discussed in comparison to alcohols. T...

Using neutron reflectivity, the internal structure of polyelectrolyte multilayers is described on the nanoscale. Each film consists of a protonated and a deuterated block, built from x protonated and y deuterated polycation/polyanion bilayers, respectively. The number of bilayers N = x + y is kept constant; the position of the interface between the blocks is varied systematically. The polyanion is poly(styrenesulfonate) (PSS), and the polycation is poly(allylamine hydrochloride) (PAH) or poly(diallyldimethylammonium chloride) (PDADMAC). Always, the first four to five bilayers are thinner than the average bilayer thickness, but the three terminating bilayers are sometimes thicker. In the core zone, the bilayer thickness is constant. The internal roughness is smallest next to the film/air interface and increases with the number of bilayers away from the film/air interface. This suggests that each deposition step promotes the interdiffusion of the supporting layers. At the selected preparation conditions, th...

To describe the swelling of polyelectrolyte multilayers (PEMs) on a molecular scale, the PEM architecture is varied. The polyanion is poly(styrenesulfonate) (PSS) and the polycation poly(allylamine...

We show for the first time that 1,2-dilauroyl-sn-glycero-3-phosphatidyladenosine nucleolipid surface complexes with cationic poly(amidoamine) dendrimers can be used to selectively bind DNA including oligonucleotides. This molecular recognition has high potential for applications involving biomedical and bioanalytic devices as well as drug delivery systems based on nucleic acids.