Cyto-mechanoresponsive polyelectrolyte multilayer films

Cell adhesion processes take place through mechanotransduction mechanisms where stretching of proteins results in biological responses. In this work, we present the first cyto-mechanoresponsive surface that mimics such behavior by becoming cell-adhesive through exhibition of arginine-glycine-aspartic acid (RGD) adhesion peptides under stretching. This mechanoresponsive surface is based on polyelectrolyte multilayer films built on a silicone sheet and where RGD-grafted polyelectrolytes are embedded under antifouling phosphorylcholine-grafted polyelectrolytes. The stretching of this film induces an increase in fibroblast cell viability and adhesion.     

Polysaccharide films built by simultaneous or alternate spray: a rapid way to engineer biomaterial surfaces

We investigated polysaccharide films obtained by simultaneous and alternate spraying of a chitosan (CHI) solution as polycation and hyaluronic acid (HA), alginate (ALG), and chondroitin sulfate (CS) solutions as polyanions. For simultaneous spraying, the film thickness increases linearly with the cumulative spraying time and passes through a maximum for polyanion/CHI molar charge ratios lying between 0.6 and 1.2. The size of polyanion/CHI complexes formed in solution was compared with the simultaneously sprayed film growth rate as a function of the polyanion/CHI molar charge ratio. A good correlation was found. This suggests the importance of polyanion/polycation complexation in the simultaneous spraying process. Depending on the system, the film topography is either liquid-like or granular. Film biocompatibility was evaluated using human gingival fibroblasts. A small or no difference is observed in cell viability and adhesion between the two deposition processes. The CHI/HA system appears to be the best for cell adhesion inducing the clustering of CD44, a cell surface HA receptor, at the membrane of cells. Simultaneous or alternate spraying of CHI/HA appears thus to be a convenient and fast procedure for biomaterial surface modifications.     

An alternating direction scheme on a nonuniform mesh for reaction-diffusion parabolic problems

In this paper we develop a numerical method for two-dimensionaltime-dependent reaction-diffusion problems. This method, whichcan immediately be generalized to higher dimensions, is shownto be uniformly convergent with respect to the diffusion problems.This method, which can immediately be generalized to higherdimensions, is shown to be uniformly convergent with respectto the diffusion parameter.     

Partial poly(glutamic acid) <--> poly(aspartic acid) exchange in layer-by-layer polyelectrolyte films. Structural alterations in the three-component architectures

Layer-by-layer (LBL) polyelectrolyte films were constructed from poly(L-glutamic acid) (PGA) and poly(L-aspartic acid) (PAA) as polyanions, and from poly(L-lysine) (PLL) as the polycation. The terminating layer of the films was always PLL. According to attenuated total reflection Fourier transform infrared measurements, the PGA/PLL and PAA/PLL films, despite their chemical similarity, had largely different secondary structures. Extended beta-sheets dominated the PGA/PLL films, while alpha-helices and intramolecular beta-sheets dominated the PAA/PLL films. The secondary structure of the polyelectrolyte film affected the adsorption of human serum albumin (HSA) as well. HSA preserved its native secondary structure on the PGA/PLL film, but it became largely deformed on PAA/PLL films. Both PGA and PAA were able to extrude to a certain extent the other polyanion from the films, but the structural consequences were different. Adding PAA to a (PGA/PLL)5-PGA film resulted in a simple exchange and incorporation: PGA/PLL and PAA/PLL complexes coexisted with their unaltered secondary structures in the mixed film. The incorporation of PGA into a (PAA/PLL)5-PAA film was up to 50% and caused additional beta-structure increase in the secondary structure of the film. The proportions of the two polyanions were roughly the same on the surfaces and in the interiors of the films, indicating practically free diffusion for both polyanions. The abundance of PAA/PLL and PGA/PLL domains on the film surfaces was monitored by the analysis of the amide I region of the infrared spectrum of a reporter molecule, HSA, adsorbed onto the three-component polyelectrolyte films.     

Relationship between the growth regime of polyelectrolyte multilayers and the polyanion/polycation complexation enthalpy

The alternate deposition of polyanions and polycations leads to the formation of films called polyelectrolyte multilayer films (PEMs). Two types of growth processes are reported in the literature, leading to films that grow either linearly or exponentially with the number of deposition steps. In this article we try to establish a correlation between the nature of the growth process and the heat of complexation between the polyanions and the polycations constituting the PEM film. Isothermal titration microcalorimetry experiments performed on several polyanion/polycation systems seem to indicate that an endothermic complexation process is characteristic of an exponential film growth, whereas a strongly exothermic process corresponds to a linear growth regime. Finally, weakly exothermic processes seem to be associated with weakly exponentially growing films. These results thus show that exponentially growing processes are mainly driven by entropy. This explains why the exponential growth processes are more sensitive to temperature than the linear growing processes. This temperature sensitivity is shown on the poly-L-glutamic acid/poly(allylamine) system which grows either linearly or exponentially depending on the ionic strength of the polyelectrolyte solutions.     

Extended (n/v)-Stillinger cluster for use in the theory of homogeneous nucleation

In this paper we develop a theory for an extended version of the (n/v)-Stillinger cluster that has been used in nucleation theory, where n means the number of particles constituting the cluster characterized by the volume v. The "extended cluster" incorporates some of the surrounding supersaturated vapor. This cluster, although requiring more extensive simulation than the original (n/v)-Stillinger cluster, is almost devoid of approximation. It maintains the non-ad-hoc nature of the original (n/v)-Stillinger cluster implicitly. The theory of the cluster is also applicable to clusters which avoid redundancy by some other means than the so-called "connectivity requirement." Simulation of the extended cluster is now being implemented and will be used in the theory of the homogeneous nucleation rate.