Emily E. Fenn

Ion–water hydrogen-bond switching observed with 2D IR vibrational echo chemical exchange spectroscopy

The exchange of water hydroxyl hydrogen bonds between anions and water oxygens is observed directly with ultrafast 2D IR vibrational echo chemical exchange spectroscopy (CES). The OD hydroxyl stretch of dilute HOD in H2O in concentrated (5.5 M) aqueous solutions of sodium tetrafluoroborate (NaBF4) displays a spectrum with a broad water-like band (hydroxyl bound to water oxygen) and a resolved, blue shifted band (hydroxyl bound to BF4−). At short time (200 fs), the 2D IR vibrational echo spectrum has 4 peaks, 2 on the diagonal and 2 off-diagonal. The 2 diagonal peaks are the 0–1 transitions of the water-like band and the hydroxyl-anion band. Vibrational echo emissions at the 1–2 transition frequencies give rise to 2 off-diagonal peaks. On a picosecond time scale, additional off-diagonal peaks grow in. These new peaks arise from chemical exchange between water hydroxyls bound to anions and hydroxyls bound to water oxygens. The growth of the chemical exchange peaks yields the time dependence of anion–water hydroxyl hydrogen bond switching under thermal equilibrium conditions as Taw = 7 ± 1 ps. Pump-probe measurements of the orientational relaxation rates and vibrational lifetimes are used in the CES data analysis. The pump-probe measurements are shown to have the correct functional form for a system undergoing exchange.

Water dynamics in large and small reverse micelles: From two ensembles to collective behavior

The dynamics of water in Aerosol-OT reverse micelles are investigated with ultrafast infrared spectroscopy of the hydroxyl stretch. In large reverse micelles, the dynamics of water are separable into two ensembles: slow interfacial water and bulklike core water. As the reverse micelle size decreases, the slowing effect of the interface and the collective nature of water reorientation begin to slow the dynamics of the core water molecules. In the smallest reverse micelles, these effects dominate and all water molecules have the same long time reorientational dynamics. To understand and characterize the transition in the water dynamics from two ensembles to collective reorientation, polarization and frequency selective infrared pump-probe experiments are conducted on the complete range of reverse micelle sizes from a diameter of 1.6-20 nm. The crossover between two ensemble and collective reorientation occurs near a reverse micelle diameter of 4 nm. Below this size, the small number of confined water molecules and structural changes in the reverse micelle interface leads to homogeneous long time reorientation.

Water inertial reorientation: Hydrogen bond strength and the angular potential

The short-time orientational relaxation of water is studied by ultrafast infrared pump-probe spectroscopy of the hydroxyl stretching mode (OD of dilute HOD in H2O). The anisotropy decay displays a sharp drop at very short times caused by inertial orientational motion, followed by a much slower decay that fully randomizes the orientation. Investigation of temperatures from 1°C to 65°C shows that the amplitude of the inertial component (extent of inertial angular displacement) depends strongly on the stretching frequency of the OD oscillator at higher temperatures, although the slow component is frequency-independent. The inertial component becomes frequency-independent at low temperatures. At high temperatures there is a correlation between the amplitude of the inertial decay and the strength of the O-DO hydrogen bond, but at low temperatures the correlation disappears, showing that a single hydrogen bond (ODO) is no longer a significant determinant of the inertial angular motion. It is suggested that the loss of correlation at lower temperatures is caused by the increased importance of collective effects of the extended hydrogen bonding network. By using a new harmonic cone model, the experimentally measured amplitudes of the inertial decays yield estimates of the characteristic frequencies of the intermolecular angular potential for various strengths of hydrogen bonds. The frequencies are in the range of ≈400 cm−1. A comparison with recent molecular dynamics simulations employing the simple point charge-extended water model at room temperature shows that the simulations qualitatively reflect the correlation between the inertial decay and the OD stretching frequency.

Water dynamics at neutral and ionic interfaces

The orientational dynamics of water at a neutral surfactant reverse micelle interface are measured with ultrafast infrared spectroscopy of the hydroxyl stretch, and the results are compared to orientational relaxation of water interacting with an ionic interface. The comparison provides insights into the influence of a neutral vs. ionic interface on hydrogen bond dynamics. Measurements are made and analyzed for large nonionic surfactant Igepal CO-520reverse micelles (water nanopool with a 9-nm diameter). The results are compared with those from a previous study of reverse micelles of the same size formed with the ionic surfactant Aerosol-OT (AOT). The results demonstrate that the orientational relaxation times for interfacial water molecules in the two types of reverse micelles are very similar (13 ps for Igepal and 18 ps for AOT) and are significantly slower than that of bulk water (2.6 ps). The comparison of water orientational relaxation at neutral and ionic interfaces shows that the presence of an interface plays the dominant role in determining the hydrogen bond dynamics, whereas the chemical nature of the interface plays a secondary role.

Water at the surfaces of aligned phospholipid multibilayer model membranes probed with ultrafast vibrational spectroscopy.

The dynamics of water at the surface of artificial membranes composed of aligned multibilayers of the phospholipid dilauroyl phosphatidylcholine (DLPC) are probed with ultrafast polarization selective vibrational pump-probe spectroscopy. The experiments are performed at various hydration levels, x = 2 - 16 water molecules per lipid at 37 degrees C. The water molecules are approximately 1 nm above or below the membrane surface. The experiments are conducted on the OD stretching mode of dilute HOD in H 2O to eliminate vibrational excitation transfer. The FT-IR absorption spectra of the OD stretch in the DLPC bilayer system at low hydration levels shows a red-shift in frequency relative to bulk water, which is in contrast to the blue-shift often observed in systems such as water nanopools in reverse micelles. The spectra for x = 4 - 16 can be reproduced by a superposition of the spectra for x = 2 and bulk water. IR Pump-probe measurements reveal that the vibrational population decays (lifetimes) become longer as the hydration level is decreased. The population decays are fit well by biexponential functions. The population decays, measured as a function of the OD stretch frequency, suggest the existence of two major types of water molecules in the interfacial region of the lipid bilayers. One component may be a clathrate-like water cluster near the hydrophobic choline group and the other may be related to the hydration water molecules mainly associated with the phosphate group. As the hydration level increases, the vibrational lifetimes of these two components decrease, suggesting a continuous evolution of the hydration structures in the two components associated with the swelling of the bilayers. The agreement of the magnitudes of the two components obtained from IR spectra with those from vibrational lifetime measurements further supports the two-component model. The vibrational population decay fitting also gives an estimation of the number of phosphate-associated water molecules and choline-associated water molecules, which range from 1 to 4 and 1 to 12, respectively, as x increases from 2 to 16. Time-dependent anisotropy measurements yield the rate of orientational relaxation as a function of x. The anisotropy decay is biexponential. The fast component is almost independent of x, and is interpreted as small orientational fluctuations that occur without hydrogen-bond rearrangement. The slower component becomes very long as the hydration level decreases. This component is a measure of the rate of complete orientational randomization, which requires H-bond rearrangement and is discussed in terms of a jump reorientation model.

Water Dynamics at the Interface in AOT Reverse Micelles

The orientational dynamics of water molecules at the interface in large Aerosol-OT (AOT) reverse micelles are investigated using ultrafast infrared spectroscopy of the OD stretch of dilute HOD in H(2)O. In large reverse micelles ( approximately 9 nm diameter or larger), a significant amount of the nanoscopic water is sufficiently distant from the interface that it displays bulk-like characteristics. However, some water molecules interact with the interface and have vibrational absorption spectra and dynamics distinct from bulk water. The different characteristics of these interfacial waters allow their contribution to the data to be separated from the bulk. The infrared absorption spectrum of the OD stretch is analyzed to show that the interfacial water molecules have a spectrum that peaks near 2565 cm(-1) in contrast to 2509 cm(-1) in bulk water. A two-component model is developed that simultaneously describes the population relaxation and orientational dynamics of the OD stretch in the spectral region of the interfacial water. The model provides a consistent description of both observables and demonstrates that water interacting with the interface has slower vibrational relaxation and orientational dynamics. The orientational relaxation of interfacial water molecules occurs in 18 +/- 3 ps, in contrast to the bulk water value of 2.6 ps.

Water Dynamics in Water/DMSO Binary Mixtures

The dynamics of dimethyl sulfoxide (DMSO)/water solutions with a wide range of water concentrations are studied using polarization selective infrared pump-probe experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, optical heterodyne detected optical Kerr effect (OHD-OKE) experiments, and IR absorption spectroscopy. Vibrational population relaxation of the OD stretch of dilute HOD in H(2)O displays two vibrational lifetimes even at very low water concentrations that are associated with water-water and water-DMSO hydrogen bonds. The IR absorption spectra also show characteristics of both water-DMSO and water-water hydrogen bonding. Although two populations are observed, water anisotropy decays (orientational relaxation) exhibit single ensemble behavior, indicative of concerted reorientation involving water and DMSO molecules. OHD-OKE experiments, which measure the orientational relaxation of DMSO, reveal that the DMSO orientational relaxation times are the same as orientational relaxation times found for water over a wide range of water concentrations within experimental error. The fact that the reorientation times of water and DMSO are basically the same shows that the reorientation of water is coupled to the reorientation of DMSO itself. These observations are discussed in terms of a jump reorientation model. Frequency-frequency correlation functions determined from the 2D IR experiments on the OD stretch show both fast and slow spectral diffusion. In analogy to bulk water, the fast component is assigned to very local hydrogen bond fluctuations. The slow component, which is similar to the slow water reorientation time at each water concentration, is associated with global hydrogen bond structural randomization.

Geometry and nanolength scales versus interface interactions: water dynamics in AOT lamellar structures and reverse micelles.

To determine the relative importance of the confining geometry and nanoscopic length scale versus water/interface interactions, the dynamic interactions between water and interfaces are studied with ultrafast infrared spectroscopy. Aerosol OT (AOT) is a surfactant that can form two-dimensional lamellar structures with known water layer thickness as well as well-defined monodispersed spherical reverse micelles of known water nanopool diameter. Lamellar structures and reverse micelles are compared based on two criteria: surface-to-surface dimensions to study the effect of confining length scales, and water-to-surfactant ratio to study water/interface interactions. We show that the water-to-surfactant ratio is the dominant factor governing the nature of water interacting with an interface, not the characteristic nanoscopic distance. The detailed structure of the interface and the specific interactions between water and the interface also play a critical role in the fraction of water molecules influenced by the surface. A two-component model in which water is separated into bulk-like water in the center of the lamellar structure or reverse micelle and interfacial water is used to quantitatively extract the interfacial dynamics. A greater number of perturbed water molecules are present in the lamellar structures as compared to the reverse micelles due to the larger surface area per AOT molecule and the greater penetration of water molecules past the sulfonate head groups in the lamellar structures.

Dynamics of water at the interface in reverse micelles: measurements of spectral diffusion with two-dimensional infrared vibrational echoes.

Water dynamics inside of reverse micelles made from the surfactant Aerosol-OT (AOT) were investigated by observing spectral diffusion, orientational relaxation, and population relaxation using two-dimensional infrared (2D IR) vibrational echo spectroscopy and pump-probe experiments. The water pool sizes of the reverse micelles studied ranged in size from 5.8 to 1.7 nm in diameter. It is found that spectral diffusion, characterized by the frequency-frequency correlation function (FFCF), significantly changes as the water pool size decreases. For the larger reverse micelles (diameter 4.6 nm and larger), the 2D IR signal is composed of two spectral components: a signal from bulk-like core water, and a signal from water at the headgroup interface. Each of these signals (core water and interfacial water) is associated with a distinct FFCF. The FFCF of the interfacial water layer can be obtained using a modified center line slope (CLS) method that has been recently developed. The interfacial FFCFs for large reverse micelles have a single exponential decay (∼1.6 ps) to an offset plus a fast homogeneous component and are nearly identical for all large sizes. The observed ∼1.6 ps interfacial decay component is approximately the same as that found for bulk water and may reflect hydrogen bond rearrangement of bulk-like water molecules hydrogen bonded to the interfacial water molecules. The long time offset arises from dynamics that are too slow to be measured on the accessible experimental time scale. The influence of the chemical nature of the interface on spectral diffusion was explored by comparing data for water inside reverse micelles (5.8 nm water pool diameter) made from the surfactants AOT and Igepal CO-520. AOT has charged, sulfonate head groups, while Igepal CO-520 has neutral, hydroxyl head groups. It is found that spectral diffusion on the observable time scales is not overly sensitive to the chemical makeup of the interface. An intermediate-sized AOT reverse micelle (water pool diameter of 3.3 nm) is analyzed as a large reverse micelle because it has distinct core and interface regions, but its core region is more constrained than bulk water. The interfacial FFCF for this intermediate-sized reverse micelle is somewhat slower than those found for the larger reverse micelles. The water nanopools in the smaller reverse micelles cannot be separated into core and interface regions. In the small reverse micelles, the FFCFs are biexponential decays to an offset plus a fast homogeneous component. Each small reverse micelle exhibits an ∼1 ps decay time, which may arise from local hydrogen bond fluctuations and a slower, ∼6-10 ps decay, which is possibly due to slow hydrogen bond rearrangement of noninterfacial water molecules or topography fluctuations at the interface.

Water dynamics and interactions in water-polyether binary mixtures.

Poly(ethylene) oxide (PEO) is a technologically important polymer with a wide range of applications including ion-exchange membranes, protein crystallization, and medical devices. PEOs versatility arises from its special interactions with water. Water molecules may form hydrogen-bond bridges between the ether oxygens of the backbone. While steady-state measurements and theoretical studies of PEOs interactions with water abound, experiments measuring dynamic observables are quite sparse. A major question is the nature of the interactions of water with the ether oxygens as opposed to the highly hydrophilic PEO terminal hydroxyls. Here, we examine a wide range of mixtures of water and tetraethylene glycol dimethyl ether (TEGDE), a methyl-terminated derivative of PEO with 4 repeat units (5 ether oxygens), using ultrafast infrared polarization selective pump-probe measurements on waters hydroxyl stretching mode to determine vibrational relaxation and orientational relaxation dynamics. The experiments focus on the dynamical interactions of water with the ether backbone because TEGDE does not have the PEO terminal hydroxyls. The experiments observe two distinct subensembles of water molecules: those that are hydrogen bonded to other waters and those that are associated with TEGDE molecules. The water orientational relaxation has a fast component of a few picoseconds (water-like) followed by much slower decay of approximately 20 ps (TEGDE associated). The two decay times vary only mildly with the water concentration. The two subensembles are evident even in very low water content samples, indicating pooling of water molecules. Structural change as water content is lowered through either conformational changes in the backbone or increasing hydrophobic interactions is discussed.