Calcium mediated polyelectrolyte adsorption on like-charged surfaces

Monte Carlo simulations within the primitive model of calcium-mediated adsorption of linear and comb polyelectrolytes onto like-charged surfaces are described, focusing on the effect of calcium and polyion concentrations as well as on the ion pairing between polymers and calcium ions. We use a combination of Monte Carlo simulations and experimental data from titration and calcium binding to quantify the ion pairing. The polymer adsorption is shown to occur as a result of surface overcharging by Ca(2+) and ion pairing between charged monomers and Ca(2+). In agreement with experimental observations, the simulations predict that the polymer adsorption isotherm goes through a maximum as the calcium or the polymer concentration is increased. The non-Langmuir isotherms are rationalized in terms of charge-charge correlations.     

Structuring of macroions confined between like-charged surfaces

We investigate the structuring of charged spherical nanoparticles and micelles (i.e., "macroions") between two surfaces as a function of bulk macroion concentration. Structuring is deduced from measured force profiles between a silica particle and a silica plate in the presence of an aqueous macroion (Ludox silica nanoparticle or sodium dodecyl sulfate micelle) solution, obtained with an atomic force microscope. We observe oscillatory force profiles that decay with separation. We find that the wavelength of the force profiles scales with the bulk number density as rho(-)(1/3), rather than with the effective macroion size. Only at very high silica nanoparticle concentration (above 10 vol %) in a low ionic strength solution does the wavelength become smaller than that predicted by the simple rho(-)(1/3) scaling; however, the original scaling is recovered upon the addition of a small amount of electrolyte. A comparison between the measured wavelength and the predicted spacing between the macroions in the bulk shows that the two variables differ in both magnitude and bulk density scaling. This finding suggests that confined macroions are more ordered than those in the bulk and the nature of this ordering is maintained over a relatively wide range of bulk concentration.     

Silica surfaces lubrication by hydrated cations adsorption from electrolyte solutions

Adsorption of hydrated cations on hydrophilic surfaces has been related to a variety of phenomena associated with the short-range interaction forces and mechanisms of the adhesive contact between the surfaces. Here we have investigated the effect of the adsorption of cations on the lateral interaction. Using lateral force microscopy (LFM), we have measured the friction force between a silica particle and silica wafer in pure water and in electrolyte solutions of LiCl, NaCl, and CsCl salts. A significant lubrication effect was demonstrated for solutions of high electrolyte concentrations. It was found that the adsorbed layers of smaller and more hydrated cations have a higher lubrication capacity than the layers of larger and less hydrated cations. Additionally, we have demonstrated a characteristic dependence of the friction force on the sliding velocity of surfaces. A mechanism for the observed phenomena based on the microstructures of the adsorbed layers is proposed.     

Direct observation of phenylalanine orientations in statherin bound to hydroxyapatite surfaces

Extracellular biomineralization proteins such as salivary statherin control the growth of hydroxyapatite (HAP), the principal component of teeth and bones. Despite the important role that statherin plays in the regulation of hard tissue formation in humans, the surface recognition mechanisms involved are poorly understood. The protein-surface interaction likely involves very specific contacts between the surface atoms and the key protein side chains. This study demonstrates for the first time the power of combining near-edge X-ray absorption fine structure (NEXAFS) spectroscopy with element labeling to quantify the orientation of individual side chains. In this work, the 15 amino acid N-terminal binding domain of statherin has been adsorbed onto HAP surfaces, and the orientations of phenylalanine rings F7 and F14 have been determined using NEXAFS analysis and fluorine labels at individual phenylalanine sites. The NEXAFS-derived phenylalanine tilt angles have been verified with sum frequency generation spectroscopy.     

Direct 23Na NMR observation of mixed cations residing inside a G-quadruplex channel

We report direct (23)Na NMR observation for the presence of mixed cations (Na(+)/K(+), Na(+)/Rb(+), Na(+)/Sr(2+)) inside the G-quadruplex channel formed by the self-association of guanosine 5'-monophosphate at pH 8.     

Restructuring of hydrophobic surfaces created by surfactant adsorption to mica surfaces

Hydrophobic surfaces created by the adsorption of a monolayer of surfactants, such as CTAB or DODAB, to mica display long-range mutual attraction when placed in water. Initially, this attraction was considered to be due to hydrophobic interaction, but more careful measurements using AFM showed that the surfactant monolayer undergoes rearrangements to produce charged patches on the surface; therefore, the nature of the long-range interaction is due to the electrostatic interaction between patches. The monolayer rearrangement depends on the nature of the surfactant and its counterion. To study possible monolayer rearrangements in molecular detail, we performed detailed molecular dynamics computer simulations on systems containing a monolayer of surfactants RN(CH(3))(3)(+)Cl(-) (R indicates a saturated hydrocarbon chain) adsorbed on a mica surface and immersed in water. We observe that when chain R is 18 carbons long the monolayer rearranges into a micelle but it remains a monolayer when the chain contains 24 carbons.     

A revisit to the Gibbs dividing surfaces and helium adsorption

This paper addresses the long-standing problem of the so-called Gibbs dividing surface and the use of helium as a “non-adsorbing” gas for the determination of the “helium”-void volume and thence the Gibbs excess. Using helium is subject to some uncertainty because helium does adsorb (to call it a non-adsorbing gas is misleading) and it is able to access pore spaces that other larger adsorbates cannot. On the other hand, even helium atoms can not physically probe all the space described by the helium-void volume. To avoid these difficulties, we suggest an alternative to the formulation of the Gibbs dividing surface and the definition of the excess amount. We illustrate this with the two common tools to study adsorption—the volumetric and gravimetric techniques, and justify our new analysis with a computer simulation of a number of model adsorption systems. Furthermore, we also show that by using the correct accessible volume and inaccessible volume the excess amount obtained from a volumetric experiment is exactly the same as that obtained from a gravimetric experiment.     

Direct observation of internal fluidity in a water droplet during sliding on hydrophobic surfaces

In the current study, we used a high-speed camera system with particle image velocimetry to observe the internal fluidity of water droplets during sliding. The droplets' velocity during sliding was controlled by slipping and rolling motions. On the superhydrophobic surface, with a contact angle of 150 degrees, the droplet fell at high velocity by slipping. However, on a normal hydrophobic surface whose water contact angle was around 100 degrees, both slipping and rolling controlled the droplet's velocity during sliding. In addition, the advancing velocity might be large when the slip velocity is large and the contact area is small.     

Using ferroelectric poling to change adsorption on oxide surfaces

Adsorption has been invoked to explain many phenomena in ferroelectric materials including the unanticipated stability of ultrathin ferroelectric films; however, the intrinsic surface properties of ferroelectric oxides have been largely unexplored. Therefore, the effect of ferroelectric poling on the adsorption/desorption of two polar molecules, acetic acid and 2-propanol, and one nonpolar molecule, dodecane, on LiNbO3(0001) was compared. The two polar molecules were found to adsorb significantly more strongly on the positive surface. Temperature-programmed desorption (TPD) data yielded desorption pre-exponentials of the two polar molecules more than 11 orders of magnitude lower than expected. Ferroelectric materials are also intrinsically pyroelectric, and it is shown that the unusually low desorption pre-exponentials can be explained by temperature dependent heats of adsorption that result from changes in the surface dipole as the samples are heated. This conclusion was supported by dodecane adsorption/desorption, which was independent of polarity with normal desorption pre-exponentials. The differences between the polar and nonpolar molecules indicate that interactions between polar molecules and ferroelectric surfaces are dominated by electrostatics. It is shown that adsorption energy differences between positive and negative surfaces are large enough to switch the polarity of ferroelectric thin films.     

Direct determination of adsorption heats

Energy changes occurring during adsorption in gas-solid and solution-solid systems are considered in connection with measurement of the adsorption enthalpies. Some experimental apparatuses allowing determination both of heat evolved and adsorbed amounts are described, with special regard to those using heat-flow microcalorimeters. Calibration techniques and experimental data reliability are also discussed.     

Antibody adsorption and orientation on hydrophobic surfaces

The orientation of a monoclonal, anti-streptavidin human IgG1 antibody on a model hydrophobic, CH(3)-terminated surface (1-dodecanethiol self-assembled monolayer on gold) was studied by monitoring the mechanical coupling between the adsorbed layer and the surface as well as the binding of molecular probes to the antibodies. In this study, the streptavidin antigen was used as a probe for the Fab portions of the antibody, while bacteria-derived Protein G' was used as a probe for the Fc region. Bovine serum albumin (BSA) acted as a blocking protein. Monolayer coverage occurred around 468 ng/cm(2). Below 100 ng/cm(2), antibodies were found to adsorb flat-on, tightly coupled to the surface and unable to capture their antigen, whereas the Fc region was able to bind Protein G'. At half-monolayer coverage, there was a transition in the mechanism of adsorption to allow for vertically oriented antibodies, as evidenced by the binding of both Protein G' and streptavidin as well as looser mechanical coupling with the surface. Monolayer coverage was characterized by a reduced level in probe binding per antibody and an even less rigid coupling to the surface.     

Voltammetric study of the ion-exchange binding of non-electroactive metal cations to DNA-modified surfaces

We describe a simple electrochemical protocol for studying the ion-exchange binding of non-electroactive ions, specifically mono- and divalent metal cations of biological relevance (Mg(2+), Ca(2+), and K(+)), to DNA-modified surfaces. After incubation in a dilute solution of multiply charged transition metal complex (5.0 microM [Ru(NH(3))(6)]Cl(3)), gold electrodes modified with thiolate-DNA monolayers respond to the presence of these non-electroactive metal cations by producing significant changes in the cyclic voltammograms (i.e., decrease of the integrated charge and shift of formal potential) of the surface-bound redox complex ([Ru(NH(3))(6)](3+)). The divalent cations (particularly Mg(2+)) can be detected at very low concentrations (<10 microM), while the on-set value for K(+) is substantially higher (50 mM). The equilibrium binding constants for Mg(2+) and Ca(2+) to DNA-modified surfaces were calculated.     

Direct detection of radical cations of NADH analogues

The radical cation of an NADH analogue (BNAH: 1-benzyl-1,4-dihydronicotinamide) has been successfully detected as the transient absorption and ESR spectra in the thermal electron transfer from BNAH to Fe(bpy)33+ (bpy = 2,2'-bipyridine). The ESR spectra of the radical cations of BNAH and the dideuterated compound (BNAH-4,4'-d2) indicate that the observed radical cation is the keto form rather than the enol form in the tautomerization. The deprotonation rate and the kinetic isotope effects of the keto form of BNAH*+ were determined from the kinetic analysis of the electron-transfer reactions.     

Adsorption of cations onto the surfaces of silver nanoparticles

The effects of cations on the absorption spectra of silver sols have been investigated by the UV-vis spectrometry and TEM. Experiments showed that injection of certain amounts of transition metal cations into silver sols resulted not only in the aggregation of silver nanoparticles but also in the appearance of a new band centered near 510 nm in the absorption spectra of silver sols. However, the new band was not observed in the presence of alkaline earth metal cations or the Mv2+ cations. The peak position of the new band depends on the nature as well as the concentration of metal cations used. Comparing the peak positions of the new bands, it was found that the new band induced by the injection of Cr3+ was red-shifted with respect to those induced by Cu2+, Zn2+, or the Cd2+ cations. It is reasonable that this band near 510 nm should be attributed to the coeffects of the adsorption of metal cations onto the surfaces of silver nanoparticles and the aggregation of silver nanoparticles.     

Protein adsorption to organosiloxane surfaces studied by acoustic wave sensor

Surfaces of the two organosiloxanes, polymercaptopropylmethylsiloxane and octaphenylcyclotetrasiloxane, were prepared on the gold electrodes of thickness-shear mode acoustic wave sensors. Compounds containing the siloxane bond are important in the fabrication of medical implants. The flow-through adsorption of the proteins: human serum albumin, alpha-chymotripsinogen A, cytochrome c, fibrinogen, hemoglobin, immunoglobulin G and apo-transferrin to the two siloxane surfaces and a gold electrode were detected by acoustic network analysis. With the exception of minor wash-off by buffer flow, the adsorption of all proteins to the three surfaces is irreversible. Differences observed for the magnitudes of adsorption for the various cases are ascribed to the role played by molecular interactions at the liquid/solid interface. The results confirm that changes in series resonant frequencies caused by macromolecular adsorption differ significantly from the widely accepted "mass based" model usually employed to characterize the response of this type of acoustic wave device.     

Comparative study of adsorption and heats of adsorption on planar and particulate polymer surfaces

The adsorption and heats of adsorption of Lewis acidic-basicprobes on planar and particulate surfaces of polyimide/siloxane, 6F photoimagable fluorinated polyimide and 6F polyimide have been studied by flow microcalorimetric, ellipsometric, and contact angle techniques. The heats of adsotption obtained by these techniques are in good agreement. It is noted that the ellipsometric method based on an analysis of adsorption kinetics has advantages over the contact angle technique and may be used for the study of the interface on planar polymer surfaces. The acidic-basic properties of polymers were approximately estimated by using the DragoE andC constants.     

Simple density functional approach to adsorption of biomolecules on solid surfaces

A simple density functional approach for modeling the adsorption of biomolecules is considered. The model comprises a three-component mixture consisting of spherical and differently charged ions and chain molecules. Spherical ions can form associative bonds with selected segments of a chain. To enable the formation of bonds between chain segments and spherical ions, the statistical associating fluid theory is applied. The present theory is used to study the structure of adsorbed layers, the excess adsorption isotherms, and the capacitance of the double layer.