Broadband Deep UV Spectra of Interfacial Aqueous Iodide.

The behavior of ions at aqueous interfaces influences vital processes in many fields but has long remained a subject of controversy. Over the past decade, counterintuitive surface concentration enhancement of several ions in aqueous solution has been demonstrated via nonlinear laser spectroscopy and mass spectrometry. While the evidence for significant ion enhancement at the air-water interface is convincing, the mechanism remains incompletely understood. Toward this end, we present the full broadband DUV-SFG spectrum of the charge-transfer-to-solvent (CTTS) band of interfacial aqueous iodide measured in a single laser shot with a newly developed broadband deep UV-SFG technique, clearly revealing a ∼8 nm redshift and a significant linewidth narrowing relative to bulk solution spectra. KI and NaI solutions yield indistinguishable results. Additionally, we observe a dramatic change in the relative intensities of the J = 3/2 and 1/2 CTTS transitions.

Structure of water at charged interfaces: a molecular dynamics study.

The properties of water molecules located close to an interface deviate significantly from those observed in the homogeneous bulk liquid. The length scale over which this structural perturbation persists (the so-called interfacial depth) is the object of extensive investigations. The situation is particularly complicated in the presence of surface charges that can induce long-range orientational ordering of water molecules, which in turn dictate diverse processes, such as mineral dissolution, heterogeneous catalysis, and membrane chemistry. To characterize the fundamental properties of interfacial water, we performed molecular dynamics (MD) simulations on alkali chloride solutions in the presence of two types of idealized charged surfaces: one with the charge density localized at discrete sites and the other with a homogeneously distributed charge density. We find that, in addition to a diffuse region where water orientation shows no layering, the interface region consists of a "compact layer" of solvent next to the surface that is not described in classical electric double layer theories. The depth of the diffuse solvent layer is sensitive to the type of charge distributions on the surface and the ionic strength. Simulations of the aqueous interface of a realistic model of negatively charged amorphous silica show that the water orientation and the distribution of ions strongly depend on the identity of the cations (Na(+) vs Cs(+)) and are not well represented by a simplistic homogeneous charge distribution model. While the compact layer shows different solvent net orientation and depth for Na(+) vs Cs(+), the depth (~1 nm) of the diffuse layer of oriented waters is independent of the identity of the cation screening the charge. The details of interfacial water orientation revealed here go beyond the traditionally used double and triple layer models and provide a microscopic picture of the aqueous/mineral interface that complements recent surface specific experimental studies.

Ultrafast vibrational dynamics and spectroscopy of a siloxane self-assembled monolayer.

Time and frequency domain sum-frequency generation (SFG) were combined to study the dynamics and structure of self-assembled monolayers (SAMs) on a fused silica surface. SFG-free induction decay (SFG-FID) of octadecylsilane SAM in the CH stretching region shows a relatively long time scale oscillation that reveals that six vibrational modes are involved in the response of the system. Five of the modes have commonly been used for the fitting of SFG spectra in the CH stretching region, namely the symmetric stretch and Fermi resonance of the methyl group, the antisymmetric stretch of the methyl, as well as the symmetric and antisymmetric stretches of the methylene group. The assignment of the sixth mode to the terminal CH(2) group was confirmed by performing a density function theory calculation. The SFG-FID measures the vibrational dephasing time (T(2)) of each of the modes, including a specific CH(2) group within the SAM, the terminal CH(2), which had never been measured before. The relatively long (∼1.3 ps) dephasing of the terminal CH(2) suggests that alkyl monolayer structure is close to that of the liquid condensed phase of Langmuir Blodgett films.

Neuronal adhesion and differentiation driven by nanoscale surface free-energy gradients.

Recent results indicate that, in addition to chemical, spatial and mechanical cues, substrate physical cues such as gradients in surface energy may also impact cell functions, such as neuronal differentiation of PC12 cells. However, it remains to be determined what surface effect is the most critical in triggering PC12 cell differentiation. Here we show that, beyond continuously probing the surface energy landscape of their environment, PC12 cells are highly sensitive to nanoscale chemical heterogeneities. Self-assembled monolayers of alkylsiloxanes on glass were used as a culture substrate. By changing the structure, ordering and chemical nature of the monolayer, the surface energy distribution is altered. While both well-ordered CH(3) terminated substrates and bare glass (OH terminated) substrates did not favor PC12 cell adhesion, PC12 cells seeded on highly disordered CH(3)/OH substrates underwent enhanced adhesion and prompt neuritogenesis by 48 h of culture, without nerve growth factor treatment. These data illustrate that surface free-energy gradients, generated by nanoscale chemical heterogeneities, are critical to biological processes such as nerve regeneration on biomaterials.

Effect of hydrogen-bond strength on the vibrational relaxation of interfacial water.

Time-resolved sum frequency generation (tr-SFG) reveals that the vibrational energy relaxation rate of O-H stretching of dilute HDO in D(2)O at the silica interface is markedly different from that of bulk water. As compared to the bulk liquid, the vibrational lifetime (T(1)) of HDO is shorter at the charged surface than in the bulk, but longer at the neutral surface. The vibrational decoupling of the O-H of the HDO species leads to the observation of a frequency-dependent T(1) of the O-H stretch, which is shorter at the red than the blue side of the hydrogen-bonded OH spectral region. This correlates with the red-shift of the SFG spectra with increasing surface charge and is consistent with a theoretical model that relates the vibrational lifetime to the strength of the hydrogen-bond network.

Effect of surface charge on the vibrational dynamics of interfacial water.

The effect of the structuring of interfacial water, induced by surface charge, on the ultrafast vibrational dynamics of the O-H stretch in the hydrogen bonded spectral region was studied at the H(2)O/fused silica interface. At high pH, where the electric field resulting from deprotonation of silanol groups polarizes several layers of water molecules, fast vibrational dynamics similar to the dynamics of bulk water is observed. At the neutral surface, where the structural ordering of interfacial water and the thickness of interfacial water are smaller than those at the charged surface, the vibrational lifetime of the O-H stretch becomes more than two times longer (T(1) approximately 570 fs). The longer vibrational lifetime is a result of reduced intermolecular coupling resulting from incomplete solvation of the interfacial water species.

Self-assembled monolayer compatible with metal surface acoustic wave devices on lithium niobate.

The formation of a siloxane self-assembled monolayer (SAM) film on a lithium niobate substrate was investigated for surface acoustic wave (SAW) sensor devices for the detection of hydrogen. The most widely used SAM coupling reagent, octadecyltrichlorosilane, etches aluminum metal features that are integral to sensor devices, due to the formation of high local concentrations of hydrochloric acid. An alternative coupling reagent, octadecyltrimethoxysilane (OTMS), does not show any etching of metal parts. OTMS and related molecules are compatible with conventional SAW device manufacturing techniques and other devices that contain metal features susceptible to etching by acid released in the SAM formation process.