Amorphous iron-(hydr) oxide networks at liquid/vapor interfaces: in situ X-ray scattering and spectroscopy studies.

Surface sensitive X-ray reflectivity (XR), fluorescence (XF), and grazing incidence X-ray diffraction (GIXD) experiments were conducted to determine the accumulation of ferric iron Fe (III) or ferrous iron Fe (II) under dihexadecyl phosphate (DHDP) or arachidic acid (AA) Langmuir monolayers at liquid/vapor interfaces. Analysis of the X-ray reflectivity and fluorescence data of monolayers on the aqueous subphases containing FeCl(3) indicates remarkably high levels of surface-bound Fe (III) in number of Fe(3+) ions per molecule (DHDP or AA) that exceed the amount necessary to neutralize a hypothetically completely deprotonated monolayer (DHDP or AA). These results suggest that nano-scale iron (hydr) oxide complexes (oxides, hydroxides or oxyhydroxides) bind to the headgroups and effectively overcompensate the maximum possible charges at the interface. The lack of evidence of in-plane ordering in GIXD measurements and strong effects on the surface-pressure versus molecular area isotherms indicate that an amorphous network of iron (hydr) oxide complexes contiguous to the headgroups is formed. Similar experiments with FeCl(2) generally resulted with the oxidation of Fe (II)-Fe (III) which consequently leads to ferric Fe (III) complexes binding albeit with less iron at the interface. Controlling the oxidation of Fe (II) changes the nature and amount of binding significantly. The implications to biomineralization of iron (hydr) oxides are briefly discussed.

Ionic specificity in pH regulated charged interfaces: Fe3+ versus La3+.

We determine the distribution of two trivalent ions Fe(3+) and La(3+) next to two different amphiphilic charged interfaces as ions or complexes, consisting of the phosphate lipid dihexadecyl phosphate (DHDP) and the fatty acid arachidic acid (AA). These amphiphiles provide a wide range of pK(a) values, from 2.1 (DHDP) to 5.1 (AA), thus allowing manipulation of the surface charge over extremely low pH (pH ∼1 or larger), and the two ions provide two limiting cases of specificity for the amphiphiles. We find that La(3+) distribution is mostly sensitive to the surface charge, whereas the Fe(3+) binding depends on its character in the solution and is highly specific, as indicated by the crucial role played by iron complexes (Fe(OH)(3) or Fe(OH)(2+)) forming covalent bonds even for an uncharged interface. The implications of the results to other ions and/or amphiphilic interfaces are also discussed.

Ion-specific induced charges at aqueous soft interfaces.

Ionic specificity effects, i.e., ions of the same valence leading to different macroscopic effects, are studied by considering a Langmuir monolayer of arachidic acid over a solution containing either Fe(3+) or La(3+). We systematically vary pH levels as a way to control the interfacial surface charge and characterize the system by surface-sensitive x-ray scattering and spectroscopic techniques. We show that the critical surface pressure at the tilted (L2) to untilted (LS) transition is ionic specific and varies with pH. While the maximum density of surface bound La(3+) per head group of arachidic acid is ∼0.3, the amount necessary to neutralize the surface charge, for Fe(3+) it is nearly 0.6 and it is accompanied with a significant accumulation of the coions Cl(-) as revealed by surface x-ray spectroscopy. We account for the experimental observations by a statistical mechanical model including ion specificity.