Percus-Yevick theory of adsorption

We study adsorption of hard sphere particles on to a plane surface with a delta function adsorption potential. The calculation takes account of exclusion via the Percus-Yevick approximation. At low and intermediate bulk adsorbate densities, both type II and type III BET adsorption isotherms can be found for the surface excess density and for the monolayer surface density. The surface excess isotherm agrees with an expansion of the exact surface excess isotherm to second order in the density. We mention some biochemical ramifications of the results.     

A density-functional theory of hydrogen adsorption on indium nitride nanotubes

First-principles calculations based on density functional theory (DFT) are used to study the chemisorption properties of one, two, and four hydrogen atoms on the zigzag and armchair single-walled InN nanotubes (InNNTs).The results indicate that the H atom is strongly bounded to the exterior wall of (4, 4) InNNTs compared with the (7, 0) InNNTs, while the chemisorption energies corresponding to the most stable configuration of H₂ dissociation and a single H atom are found to be–3.85 and–3.26 eV, respectively. Furthermore, the effect of the hydrogen storage on the geometries and electronic properties of related InN nanotubes were also discussed. The computed density of states (DOS) indicates that the energy gap of the zigzag and armchair InN nanotubes on hydrogen adsorptions are significantly decreased which can increase the electrical conductance of the tubes. Therefore, InN nanotubes due to the high binding energy can be used for hydrogen storage.     

A density functional theory study of hydrogen adsorption in MOF-5

Ab initio molecular dynamics in the generalized gradient approximation to density functional theory and ground-state relaxations are used to study the interaction between molecular hydrogen and the metal-organic framework with formula unit Zn4O(O2C-C6H4-CO2)3. Five symmetrically unique adsorption sites are identified, and calculations indicate that the sites with the strongest interaction with hydrogen are located near the Zn4O clusters. Twenty total adsorption sites are found around each Zn4O cluster, but after 16 of these are populated, the interaction energy at the remaining four sites falls off significantly. The adsorption of hydrogen on the pore walls creates an attractive potential well for hydrogen in the center of the pore. The effect of the framework on the physical structure and electronic structure of the organic linker is calculated, suggesting ways by which the interaction between the framework and hydrogen could be modified.     

Quantum theory of adsorption of isolated adatoms

Various trends in the development of modern quantum-mechanical theory of absorption of isolated adatoms on the surface of crystals are considered. Particular attention is given to the generalization of Anderson's adsorption model and to the studies concerned with its substantiation with the use of the equations of the Lippman-Schwinger type.It is shown that different equilibrium and nonequilibrium processes arising due to adsorption can be described by means of a finite number of microscopic parameters.The applications of the theory to the thermodynamics of adsorption and its dynamic manifestations in field-emission, modulation spectroscopy and some other processes are discussed.     

General aspects of protein adsorption

The study of protein adsorption on a mechanistic and quantitative basis is still a relatively young science and a general theory encompassing all aspects cannot be given. Till now the possibility of synthesizing surfaces in a controlled way, to elucidate the mechanism of protein adsorption - a possibility existing since the advent of affinity chromatography nearly two decades ago - has only been utilized to a small extent. Since this technique, however, has allowed the derivation of some general principles of protein adsorption and protein adsorption kinetics, which would otherwise not have been amenable for study, these results will be mainly referred to here.     

Ge adsorption on Ag(111): A density-functional theory investigation

First-principles density-functional theory has been used to investigate the adsorptions of Ge on Ag(111) surfaces for a wide range of coverage. Preferred adsorption sites, adsorption energies, surface structures, and the electronic properties are studied. Our results show that adsorption on the surface in fcc- sites is energetically favorable. The adsorption energies decrease as increasing Ge atoms, while the work functions of Ag surface decrease. The contour maps of the difference charge show that there exists covalent bonding in lower coverage systems to some extent for Ge on Ag(111) surface, and the interaction of Ge and Ag atoms becomes weaker with the increase of adsorption degree. The calculated density of states indicates that the adsorption structures have metallic character, while the number of electron transition is small and the interaction is not strong between Ge and Ag atoms.     

The theory of polymer adsorption during polymerization reactions

Exact values are obtained for the grand canonical partition function of model chains absorbed at a surface. On a six-choice simple cubic lattice, chains are generated as function of the activity of chain bonds. The molecular weight distribution of adsorbed chains and of solution chains in equilibrium with them is obtained. It is shown that the average molecular weight of adsorbed chains is higher than that of solution chains. The difference is the more pronounced the flatter the chain is when adsorbed at the surface. When the activity of chain bond; increases the surface coverage increases, more segments occur in loops extending into the solution, and the average molecular weight of solution chains approaches that of adsorbed chains. The segment density in loops as function of distance from the surface is shown to be exponential, in agreement with previous results. If polymer adsorption is high and the concentration in solution is small, the number of segments in tails is amall. The dimensions of the adsorbed polymer chain are smaller than those in solution of the same molecular weight. It is suggested that if polymer adsorption during polycondensation reactions with bond interchanges is measured, the bothersome tirne effects, invariably observed, might be eliminated. In this manner a valid comparison between theoretical and experimental results might become feasible.     

Reduced protein adsorption by osmolytes

Osmolytes are substances that affect osmosis and are used by cells to adapt to environmental stress. Here, we report a neutron reflectivity study on the influence of some osmolytes on protein adsorption at solid-liquid interfaces. Bovine ribonuclease A (RNase) and bovine insulin were used as model proteins adsorbing at a hydrophilic silica and at a hydrophobic polystyrene surface. From the neutron reflectivity data, the adsorbed protein layers were characterized in terms of layer thickness, protein packing density, and adsorbed protein mass in the absence and presence of urea, trehalose, sucrose, and glycerol. All data point to the clear effect of these nonionic cosolvents on the degree of protein adsorption. For example, 1 M sucrose leads to a reduction of the adsorbed amount of RNase by 39% on a silica surface and by 71% on a polystyrene surface. Trehalose was found to exhibit activity similar to that of sucrose. The changes in adsorbed protein mass can be attributed to a decreased packing density of the proteins in the adsorbed layers. Moreover, we investigated insulin adsorption at a hydrophobic surface in the absence and presence of glycerol. The degree of insulin adsorption is decreased by even 80% in the presence of 4 M of glycerol. The results of this study demonstrate that nonionic cosolvents can be used to tune and control nonspecific protein adsorption at aqueous-solid interfaces, which might be relevant for biomedical applications.     

Poisson-Boltzmann theory of the charge-induced adsorption of semi-flexible polyelectrolytes

A model is suggested for the structure of an adsorbed layer of a highly charged semi-flexible polyelectrolyte on a weakly charged surface of opposite charge sign. The adsorbed phase is thin, owing to the effective reversal of the charge sign of the surface upon adsorption, and ordered, owing to the high surface density of polyelectrolyte strands caused by the generally strong binding between polyelectrolyte and surface. The Poisson-Boltzmann equation for the electrostatic interaction between the array of adsorbed polyelectrolytes and the charged surface is solved for a cylindrical geometry, both numerically, using a finite element method, and analytically within the weak curvature limit under the assumption of excess monovalent salt. For small separations, repulsive surface polarization and counterion osmotic pressure effects dominate over the electrostatic attraction and the resulting electrostatic interaction curve shows a minimum at nonzero separations on the Angstrom scale. The equilibrium density of the adsorbed phase is obtained by minimizing the total free energy under the condition of equality of chemical potential and osmotic pressure of the polyelectrolyte in solution and in the adsorbed phase. For a wide range of ionic conditions and charge densities of the charged surface, the interstrand separation as predicted by the Poisson-Boltzmann model and the analytical theory closely agree. For low to moderate charge densities of the adsorbing surface, the interstrand spacing decreases as a function of the charge density of the charged surface. Above about 0.1 M excess monovalent salt, it is only weakly dependent on the ionic strength. At high charge densities of the adsorbing surface, the interstrand spacing increases with increasing ionic strength, in line with the experiments by Fang and Yang [J. Phys. Chem. B 101, 441 (1997)].     

Density functional theory of adsorption in pillared slit-like pores

We propose a density functional theory to describe adsorption of Lennard-Jones fluid in pillared slit like pores. Specifically, the pillars are built of chains that are bonded by their ends to the opposite pore walls. The approach we propose combines theory of quenched-annealed systems and theory of nonuniform fluids involving chain molecules. We compare the results of theoretical predictions with grand canonical ensemble Monte Carlo simulations and compute theoretical capillary condensation phase diagrams for several model systems.     

A predictive approach to correlating protein adsorption isotherms on ion-exchange media

The equilibrium adsorption of three small basic proteins was measured on cation exchangers under various solution conditions and was used as the basis for developing a predictive approach for correlating adsorption behavior. A mechanistically based isotherm model is used to model the equilibrium adsorption so as to facilitate isotherm prediction using minimal experimental data. The model explicitly considers the contributions of protein-surface and protein-protein interactions, and decoupling them allows each to be correlated with different experimental measurements. Specifically, protein-surface interactions are related to chromatographic data in the form of the isocratic retention factor (k'), while protein-protein interactions are analyzed on the basis of high-coverage isotherm data on an arbitrary stationary phase. Analysis of experimental data within this framework reveals a high level of consistency. The model is also used to facilitate prediction of adsorption isotherms on other ion-exchange media using isotherms on one adsorbent.     

On the theory of polyelectrolyte adsorption : The effect on adsorption behavior of the electrostatic contribution to the adsorption free energy

A theory has been developed for the adsorption of polyelectrolytes on charged interfaces from an aqueous salt solution. This adsorption is determined by the electrical charge density of the polyelectrolyte, the adsorption energy, the salt concentration, the molecular weight, solubility, flexibility, and concentration of polymer. The theory relates these parameters to the properties of the adsorbed polymer layer, i.e., the amount of polymer adsorbed, the fraction of the adsorbent interface covered, the fraction of the segments actually adsorbed on the interface versus the fraction of the segments in the dangling loops, the final surface charge density, and the thickness of the adsorbed layer. As polyelectrolyte adsorption should resemble nonionic polymer adsorption at high ionic strength of the solution or low charge density on the polymer, this work is an extension of the nonionic polymer adsorption theory to polyelectrolyte adsorption. The following effects are taken into account: (a) the conformational change upon adsorption of a coil in solution into a sequence of adsorbed trains interconnected by loops dangling in solution; (b) the interactions of the adsorbed trains with the interface and with each other; (c) the interaction of the dangling loops with the solvent; (d) the change in surface charge density of the adsorbent due to adsorption of charged trains and the accompanying changes in the electrical double layer which contains “small” ions as well as charged loops; (e) the (induced) dipole interaction of the adsorbed trains with the charged adsorbent interface. The theory is worked out for low potentials (Debye—Hückel approximation); in Appendix B an outline of a more complete treatment is given. The predicted adsorption isotherms have the experimentally observed high-affinity character. A relation between the adsorption energy, the surface charge density on the adsorbent, the degree of dissociation of the polymer, and the salt concentration predicts the conditions under which no adsorption will occur. For adsorbent and polymer carrying the same type of charge (both positive or both negative) the adsorption is predicted to decrease with increased charge density on polymer or adsorbent and to increase with salt concentration. If adsorbent and polymer carry different type charges, the adsorption as a function of the degree of dissociation, α, goes through a maximum at a relatively low value of α and, depending on the adsorption energy, an increase in the salt concentration can then increase or decrease the adsorption. At finite polymer concentration in solution the number of adsorbed segments and the fraction of the interface covered practically do not change with an increase in polymer concentration, whereas the total number of polymer molecules adsorbed increases slightly, as does the average fraction of segments in loops. The experimental results for polyelectrolyte adsorption have been reviewed in general and, as far as data are available, the predictions of the theory seem to follow the experimentally observed trends quite closely, except for the thickness of the adsorbed layer. This thickness is systematically overestimated by the theory and two reasons for this are given. The theoretical model implies a not too low ionic strength of the solution. Extrapolation of results to solutions of very low ionic strength is not warranted.     

Electrofusion of protoplasts modified by protein adsorption

The synergistic influence of proteins at lowest concentrations (below mg ml⁻¹) on barley protoplast electrofusion together with dielectrophoresis for adhesion of protoplast membranes has been studied by determination of the relative electrofusion yield F_r, which allows further insight into `protein modified electroporation and electrofusion'. As a general rule all proteins with isoelectric points pI>8 stimulate fusion: F_r>1 in buffer free mannitol solution (pH 6.5) reaching levels at F_r=2∼3. Proteins with pI<8 show at lowest concentrations (<1 mg ml⁻¹) also a stimulating effect: F_r>1 followed by the inhibition of F_r—sometimes reaching zero—accompanied by rising conductivity with increasing concentrations. These results are important for resealing, insertion, transfection and the role of integral membrane proteins for the mechanism of fusion.