Assembly of oppositely charged macromolecules (proteins, DNA, polyelectrolytes) is often used for surface modification and functionalization. Yet, it remains a challenge to control the position and mobility of the molecules within the assembly. Using polyelectrolyte multilayers as model systems, we study the diffusion constant of the polyanion PSS. D PSS could be varied by 5 orders of magnitude. Two parameters were found to be important: (i) the conformation of the polyelectrolytes and (ii) the molecular weight of the polycation (M w(PDADMA)); the latter was the dominant parameter. Independent of conformation, by increasing M w(PDADMA), D PSS decreased by at least 3 orders of magnitude when M w(PDADMA) increased by a factor of seven. The decrease was stronger than predicted by any scaling law; it was either exponential or abrupt after D PSS was almost constant for low M w(PDADMA). The polymer conformation was adjusted with the salt concentration in the preparation solution. Flatter and less entangled chains led to an increase in D PSS. These findings on the time dependence of the internal structure of assemblies are discussed in the context of network theory.

Typically, laterally patterned films are fabricated by lithographic techniques, external fields, or di-block copolymer self-assembly. We investigate the self-patterning of polyelectrolyte multilayers, poly(diallyldimethylammonium) (PDADMA)/poly(styrenesulfonate) (PSS) short . The low PSS molecular weight (M w (PSS short ) = 10.7 kDa) is necessary because PSS short is somewhat mobile within a PDADMA/PSS short film, as demonstrated by the exponential growth regime at the beginning of the PDADMA/PSS short multilayer build-up. No self-patterning was observed when the PDADMA/PSS film consisted of only immobile polyelectrolytes. Atomic force microscopy images show that self-patterning begins when the film consists of seven deposited PDADMA/PSS short bilayers. When more bilayers are added, the surface ribbing evolved into bands, and circular domains were finally observed. The mean distance between the surface structures increased monotonously with the film thickness, from 70 to 250 nm. Scanning electron microscopy images showed that exposure to vacuum resulted in thinning of the film and an increase in the mean distance between domains. The effect is weaker for PSS short -terminated films than for PDADMA-terminated films. The mechanism leading to domain formation during film build-up and the effect of post-preparation treatment are discussed.

In the eye lens cell membrane, the lipid composition changes during the aging process: the proportion of sphingomyelins (SM) increases, that of phosphatidylcholines decreases. To investigate the protective role of the SMs in the lens cell membrane against oxidative damage, analytical techniques such as electrochemistry, high-resolution mass spectrometry (HR-MS), and atomic force microscopy (AFM) were applied. Supported lipid bilayers (SLB) were prepared to mimic the lens cell membrane with different fractions of PLPC/SM (PLPC: 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine). The SLBs were treated with cold physical plasma. A protective effect of 30% and 44% in the presence of 25%, and 75% SM in the bilayer was observed, respectively. PLPC and SM oxidation products were determined via HR-MS for SLBs after plasma treatment. The yield of fragments gradually decreased as the SM ratio increased. Topographic images obtained by AFM of PLPC-bilayers showed SLB degradation and pore formation after plasma treatment, no degradation was observed in PLPC/SM bilayers. The results of all techniques confirm the protective role of SM in the membrane against oxidative damage and support the idea that the SM content in lens cell membrane is increased during aging in the absence of effective antioxidant systems to protect the eye from oxidative damage and to prolong lens transparency.

Lipid rafts are discrete, heterogeneous domains of phospholipids, sphingolipids, and sterols that are present in the cell membrane. They are responsible for conducting cell signaling and maintaining lipid-protein functionality. Redoxstress-induced modifications to any of their components can severely alter the mechanics and dynamics of the membrane causing impairment to the lipid-protein functionality. Here, we report on the effect of sphingomyelin (SM) in controlling membrane permeability and its role as a regulatory lipid in the presence of nitric oxide (NO). Force spectroscopy and atomic force microscopy imaging of raft-like phases (referring here to the coexistence of ''liquid-ordered'' and ''liquid-disordered'' phases in model bilayer membranes) prepared from lipids: 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC):SM:cholesterol (CH) (at three ratios) showed that the adhesion forces to pull the tip out of the membrane increased with increasing SM concentration, indicating decreased membrane permeability. However, in the presence of NO radical (1 and 5 mM), the adhesion forces decreased depending on SM concentration. The membrane was found to be stable at the ratio POPC:SM:CH (2:1:1) even when exposed to 1 mM NO. We believe that this is a critical ratio needed by the raft-like phases to maintain homeostasis under stress conditions. The stability could be due to an interplay existing between SM and CH. However, at 5 mM NO, membrane deteriorations were detected. For POPC:SM:CH (2:2:1) ratio, NO displayed a pro-oxidant behavior and damaged the membrane at both radical concentrations. These changes were reflected by the differences in the height profiles of the raft-like phases observed by atomic force microscopy imaging. Malondialdehyde (a peroxidation product) detection suggests that lipids may have undergone lipid nitroxidation. The changes were instantaneous and independent of radical concentration and incubation time. Our study underlines the need for identifying appropriate ratios in the lipid rafts of the cell membranes to withstand redox imbalances caused by radicals such as NO.

The self-patterning of thin films is relevant for both fundamental research and applications. We investigate polyelect r o l y t e m u l t i l a y e r fi l m s m a d e f r o m p o l y -(diallyldimethylammonium) chloride and poly(styrene sulfonate) sodium salt (PDADMA/PSS). Various PSS with low molecular weight were used. First, the film thickness increases exponentially with the number of deposited PDADMA/PSS bilayers. The separation and height of the pillar-like domains increase significantly with each deposited PDADMA/PSS bilayer, as AFM images show. After the exponential growth regime, either a parabolic (and then a linear) or a linear growth regime follows, depending on the PSS molecular weight. The domain separation changes less and correlates with the vertical growth regimes. The domain separation varies between 70 and 750 nm and always exceeds the domain height. PSS-terminated films show the same domain distance in water and air. However, when PDADMA-terminated films are dried, the domain distance in air increases while the domain height decreases, causing a reduction in total area. In the air, the surface energy is greater than in water and a highly textured surface costs a lot of energy. We propose that the changed surface pattern is attributable to energy minimization. Furthermore, the domains are stable when exposed to 1 M NaCl solution but shrink enormously in 2 M NaCl, while their separation increases slightly. Under certain conditions, 50 nm broad filaments consisting of PDADMA/PSS complexes are observed. We suggest that these complexes diffuse between the domains and adjust their separation.