Irreversible Multilayer Adsorption

Random sequential adsorption (RSA) models have been studied due to their relevance to deposition processes on surfaces. The depositing particles are represented by hard-core extended objects; they are not allowed to overlap. Numerical Monte Carlo studies and analytical considerations are reported for 1D and 2D models of multilayer adsorption processes. Deposition without screening is investigated, in certain models the density may actually increase away from the substrate. Analytical studies of the late stage coverage behavior show the crossover from exponential time dependence for the lattice case to the power law behavior in the continuum deposition. 2D lattice and continuum simulations rule out some "exact" conjectures for the jamming coverage. For the deposition of dimers on a 1D lattice with diffusional relaxation we find that the limiting coverage (100%) is approached according to the ~1/t**0.5 power-law preceded, for fast diffusion, by the mean-field crossover regime with the intermediate ~1/t behavior. In case of k-mer deposition (k>3) with diffusion the void fraction decreases according to the power-law t**[-1/(k-1)]. In the case of RSA of lattice hard squares in 2D with diffusional relaxation the approach to the full coverage is ~t**(-0.5).Comment: 5 pages (plain LaTeX

Comparative study of osteogenic activity of multilayers made of synthetic and biogenic polyelectrolytes

Polyelectrolyte multilayer (PEM) coatings on biomaterials are applied to tailor adhesion, growth, and function of cells on biomedical implants. Here, biogenic and synthetic polyelectrolytes (PEL) are used for layer-by-layer assembly to study the osteogenic activity of PEM with human osteosarcoma MG-63 cells in a comparative manner. Formation of PEM is achieved with biogenic PEL fibrinogen (FBG) and poly-l-lysine (PLL) as well as biotinylated chondroitin sulfate (BCS) and avidin (AVI), while poly(allylamine hydrochloride) (PAH) and polystyrene sulfonate (PSS) represent a fully synthetic PEM used as a reference system here. Surface plasmon resonance measurements show highest layer mass for FBG/PLL and similar for PSS/PAH and BCS/AVI systems, while water contact angle and zeta potential measurements indicate larger differences for PSS/PAH and FBG/PLL but not for BCS/AVI multilayers. All PEM systems support cell adhesion and growth and promote osteogenic differentiation as well. However, FBG/PLL layers are superior regarding MG-63 cell adhesion during short-term culture, while the BCS/AVI system increases alkaline phosphatase activity in long-term culture. Particularly, a multilayer system based on affinity interaction like BCS/AVI may be useful for controlled presentation of biotinylated growth factors to promote growth and differentiation of cells for biomedical applications

Polyelectrolyte multilayer formation: electrostatics and short-range interactions

We investigate the phenomenon of multilayer formation via layer-by-layer deposition of alternating charge polyelectrolytes. Using mean-field theory, we find that a strong short-range attraction between the two types of polymer chains is essential for the formation of multilayers. The dependence of the required short-range attraction on the polymer charge fraction and salt concentration is calculated. For weak short-range attraction between any two adjacent layers, the adsorbed amount (per added layer) decays as the distance from the surface increases, until the chains stop adsorbing altogether. For strong short-range attraction, the adsorbed amount per layer increases after an initial decrease, and finally it stabilizes in the form of a polyelectrolyte multilayer that can be repeated many times.Comment: 8 pages, 7 figure

On the thickness of the double layer in ionic liquids

In this study, we examined the thickness of the electrical double layer (EDL) in ionic liquids using density functional theory (DFT) calculations and molecular dynamics (MD) simulations. We focused on the BF4- anion adsorption from 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) ionic liquid on the Au(111) surface. At both DFT and MD levels, we evaluated the capacitance-potential dependence for the Helmholtz model of the interface. Using MD simulations, we also explored a more realistic, multilayer EDL model accounting for the ion layering. Concurrent analysis of the DFT and MD results provides a ground for thinking whether the electrical double layer in ionic liquids is one- or multi-ionic-layer thick

Thermal desorption of ammonia from crystalline forsterite surfaces

The thermal desorption of ammonia (NH$_3$) from single crystal forsterite (010) has been investigated using temperature-programmed desorption. The effect of defects on the desorption process has been probed by the use of a rough cut forsterite surface prepared from the cleaved forsterite sample. Several approaches have been used to extract the desorption energy and pre-exponential factor describing the desorption kinetics. In the sub-monolayer coverage regime, the NH$_3$ desorption shows a broad distribution of desorption energies, indicating the presence of different adsorption sites, which results in an apparent coverage-dependent desorption energy. This distribution is sensitive to the surface roughness with the cut forsterite surface displaying a significantly broader distribution of desorption energies compared to the cleaved forsterite surface. The cut forsterite surface exhibits sites with desorption energies up to 62.5 kJ mol$^{-1}$ in comparison to a desorption energy of up to 58.0 kJ mol$^{-1}$ for the cleaved surface. Multilayer desorption is independent of the nature of the forsterite surface used, with a desorption energy of ($25.8\pm0.9$) kJ mol$^{-1}$. On astrophysically relevant heating time-scales, the presence of a coverage dependent desorption energy distribution results in a lengthening of the NH$_3$ desorption time-scale by $5.9\times 10^4$ yr compared to that expected for a single desorption energy. In addition, the presence of a larger number of high-energy adsorption sites on the rougher cut forsterite surface leads to a further lengthening of ca. 7000 yr.Comment: 12 Pages, 9 Figures. Accepted for publication in MNRA

Interactions of adsorbed CO2_2 on water ice at low temperatures

We present a computational study into the adsorption properties of CO$_2$ on amorphous and crystalline water surfaces under astrophysically relevant conditions. Water and carbon dioxide are two of the most dominant species in the icy mantles of interstellar dust grains and a thorough understanding of their solid phase interactions at low temperatures is crucial for understanding the structural evolution of the ices due to thermal segregation. In this paper, a new H$_2$O-CO$_2$ interaction potential is proposed and used to model the ballistic deposition of CO$_2$ layers on water ice surfaces, and to study the individual binding sites at low coverages. Contrary to recent experimental results, we do not observe CO$_2$ island formation on any type of water substrate. Additionally, density functional theory calculations are performed to assess the importance of induced electrostatic interactions.Comment: Accepted for publication in Physical Chemistry Chemical Physic

Reflection absorption infrared spectroscopy and temperature programmed desorption investigations of the interaction of methanol with a graphite surface

Reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to investigate the adsorption of methanol (CH3OH) on the highly oriented pyrolytic graphite (HOPG) surface. RAIRS shows that CH3OH is physisorbed at all exposures and that crystalline CH3OH can be formed, provided that the surface temperature and coverage are high enough. It is not possible to distinguish CH3OH that is closely associated with the HOPG surface from CH3OH adsorbed in multilayers using RAIRS. In contrast, TPD data show three peaks for the desorption of CH3OH. Initial adsorption leads to the observation of a peak assigned to the desorption of a monolayer. Subsequent adsorption leads to the formation of multilayers on the surface and two TPD peaks are observed which can be assigned to the desorption of multilayer CH3OH. The first of these shows a fractional order desorption, assigned to the presence of hydrogen bonding in the overlayer. The higher temperature multilayer desorption peak is only observed following very high exposures of CH3OH to the surface and can be assigned to the desorption of crystalline CH3OH. (C) 2005 American Institute of Physics