Conjugate Acid-Base Interaction Driven Phase Transition at a 2D Air-Water Interface.

A lattice model is described to explain a recent striking Sum Frequency Generation (SFG) observation of a cooperative surface adsorption effect for an organic acid system at an air-water interface. The reported anomalous pH-dependent enhancement in p-methylbenzoic acid (pmBA) arises from an interaction between the acid (HA) and its conjugate base anion (A-), which competes with strong Coulombic repulsion between the conjugate bases (A--A -). Using a statistical mechanical approach, this lattice gas model reveals an analogy to well-studied magnetic systems in which the attraction between the two different molecular species leads to a phase transition to a two-dimensional checkerboard phase consisting of a network of anion-acid complexes formed at the low-dielectric air-water interface. Cooperative acid-anion interactions that control partitioning at solution and aerosol interfaces are of interest to fields ranging from oceanic and atmospheric chemistry, pharmacology, and chemical engineering.

Anomalous pH-Dependent Enhancement of p-Methyl Benzoic Acid Sum-Frequency Intensities: Cooperative Surface Adsorption Effects.

Vibrational sum-frequency generation (SFG) spectroscopy is used to determine the surface pKa of p-methyl benzoic acid (pMBA) at the air-water interface by monitoring the carbonyl and carboxylate stretching modes over the pH range of 2 to 12. The SFG intensities of pMBA and its conjugate base, p-methyl benzoate (pMBA-), exhibit an anomalously large enhancement over a narrow pH range (∼0.5) centered at pH 6.3 near the SFG-determined surface pKa, 5.9 ± 0.1. The increase in the surface pKa relative to the bulk value of 4.34 is consistent with the trend previously observed for long chain carboxylic acids in which the surface pKa is higher than the bulk solution pKa. SFG polarization studies help distinguish the orientation and number density contributions to this observed anomalous surface phenomenon. The large SFG intensity increase is attributed to an increase in the pMBA and pMBA- surface concentrations in this narrow pH range due to a cooperative adsorption effect between pMBA and pMBA-. This cooperativity is manifested only on the 2D air-water interface, where the interactions between the acid and base are not as dielectrically screened as in the aqueous bulk phase. Surface effects are critical to understanding and controlling the reactivity, solubility, and behavior of organic acids at interfaces and can have an impact on biomedical applications.

Structure Making and Breaking Effects of Cations in Aqueous Solution: Nitrous Oxide Pump-Probe Measurements.

Ultrafast IR pump-probe responses resonant with the ν3 asymmetric stretch of nitrous oxide (N2O) at ∼2230 cm-1 are reported for 2 M aqueous salt solutions of MgCl2, CaCl2, NaCl, KCl, and CsCl at room temperature. The solvated cations of these chloride solutions span the range from strongly to weakly hydrating ions, and correspondingly are often categorized as structure makers and structure breakers, respectively. The observed salt dependent trends of the N2O ν3 vibrational energy relaxation (VER) and rotational reorientation anisotropy (R(t)) decays are consistent with the categorization of these cations as structure breakers or makers, and show evidence of effects on the water hydrogen bonding network beyond the first solvation shell of these ions. This N2O mode is resonant with the H2O bend-libration band region. The corresponding FTIR is fitted well by a two Gaussian plus sloping continuum baseline model that allows a framework for characterizing the salt perturbations of the solvent spectral density in the ν3 resonant region. Both coupling strengths and density of states effects appear to contribute the systematic cation dependent T1 effects reported here. R(t) decays follow bulk viscosity values. These results are contrasted with previous IR pump-probe studies predominantly based on the relaxation dynamics of the OH/OD vibrational stretch of HOD hydrogen bonded to anions in salt solutions.

Dispersed three-pulse infrared photon echoes of nitrous oxide in water and octanol.

Dispersed IR three-pulse photon echoes due to the antisymmetric (ν3) stretch mode of N2O dissolved in H2O and 1-octanol at room temperature are reported and analyzed. The experimentally determined transition frequency-frequency correlation function (FFCF) in these two solvents is explained in terms of inertial solvent contributions, hydrogen bond network fluctuations, and, for octanol, the motions of the alkyl chains. The H2O hydrogen bond fluctuations result in 1.5 ps FFCF decay, in agreement with relaxation rates determined from photon echo based measurements of other aqueous solutions including salt solutions. In octanol, hydrogen bond fluctuations decay on a slower time scale of 3.3 ps and alkyl chain motions result in an inhomogeneous broadening contribution to the ν3 absorption spectrum that decays on a 35 ps time scale. Rotational reorientation of N2O is nearly 3 times faster in octanol as compared to water. Although the vibrational ν3 N2O absorption line shapes in water and octanol are similar, the line widths result from different coherence loss mechanisms. A hot band contribution in the N2O in octanol solution is found to have a significant effect on the echo spectrum due to its correspondingly stronger transition moment than that of the fundamental transition. The dephasing dynamics of the N2O ν3 stretch mode is of interest as a probe in ultrafast studies of complex or nanoconfined systems with both hydrophobic and hydrophilic regions such as phospholipids, nucleic acids, and proteins. These results demonstrate the value of the N2O molecule to act as a reporter of equilibrium fluctuations in such complex systems particularly due to its solubility characteristics and long vibrational lifetime.

Freezing and melting water in lamellar structures.

The manner in which ice forms in lamellar suspensions of dielaidoylphosphatidylethanolamine, dielaidoylphosphatidylcholine, and dioleoylphosphatidylcholine in water depends strongly on the water fraction. For weight fractions between 15 and 9%, the freezing and melting temperatures are significantly depressed below 0 degree C. The ice exhibits a continuous melting transition spanning as much as 20 degrees C. When the water weight fraction is below 9%, ice never forms at temperatures as low as -40 degrees C. We show that when water contained in a lamellar lipid suspension freezes, the ice is not found between the bilayers; it exists as pools of crystalline ice in equilibrium with the bound water associated with the polar lipid headgroups. We have used this effect, together with the known chemical potential of ice, to measure hydration forces between lipid bilayers. We find exponentially decaying hydration repulsion when the bilayers are less than about 7 A apart. For larger separations, we find significant deviations from single exponential decay.

Labyrinthine pattern formation in magnetic fluids.

A quasi two-dimensional drop of a magnetic fluid (ferrofluid) in a magnetic field is one example of the many systems, including amphiphilic monolayers, thin magnetic films, and type I superconductors, that form labyrinthine patterns. The formation of the ferrofluid labyrinth was examined both experimentally and theoretically. Labyrinth formation was found to be sensitively dependent on initial conditions, indicative of a space of configurations having a vast number of local energy minima. Certain geometric characteristics of the labyrinths suggest that these multiple minima have nearly equivalent energies. Kinetic effects on pattern selection were found in studies of fingering in the presence of timedependent magnetic fields. The dynamics of this pattern formation was studied within a simple model that yields shape evolutions in qualitative agreement with experiment.