Heterodyne-detected Vibrational Sum-frequency Generation Spectroscopy Research Articles

Working on a dream: bringing up the level of interface spectroscopy to the bulk level

Abstract Liquid interfaces are unique environments in which a variety of fundamental phenomena occur. Therefore, it is important to obtain a molecular-level understanding of liquid interfaces for both basic science and industrial applications. However, it is not an easy task to investigate molecules in the interface region that only has nanometer thicknesses. Second-order nonlinear spectroscopy, or even-order nonlinear spectroscopy more generally, is intrinsically interface-selective because the relevant nonlinear signal is generated only in the region in which the inversion symmetry is broken under the dipole approximation. In the past 2 decades, we have been developing and applying new interface nonlinear spectroscopic methods, aiming to bring up the level of knowledge on interfacial molecules to that on molecules in solution. During this attempt, we developed electronic sum-frequency generation spectroscopy, heterodyne-detected electronic sum-frequency generation spectroscopy, and heterodyne-detected vibrational sum-frequency generation spectroscopy, as well as fourth-order Raman spectroscopy. We also extended the methods to femtosecond time-resolved measurements. Using these methods, we are now able to study the structure and dynamics at liquid interfaces, in particular exposed interfaces such as air/liquid interfaces, at a similar level to the study for solution. I overview our interface research while describing thoughts we had at each turning point.

Orientational Behavior and Vibrational Response of Glycine at Aqueous Interfaces.

Aqueous glycine plays many different roles in living systems, from being a building block for proteins to being a neurotransmitter. To better understand its fundamental behavior, we study glycine's orientational behavior near model aqueous interfaces, in the absence and presence of electric fields and biorelevant ions. To this purpose, we use a surface-specific technique called heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). Using HD-VSFG, we directly probe the symmetric and antisymmetric stretching vibrations of the carboxylate group of zwitterionic glycine. From their relative amplitudes, we infer the zwitterion's orientation near surfactant-covered interfaces and find that it is governed by both electrostatic and surfactant-specific interactions. By introducing additional ions, we observe that the net orientation is altered by the enhanced ionic strength, indicating a change in the balance of the electrostatic and surfactant-specific interactions.

Observation of a Two-Dimensional Hydrophobic Collapse at the Surface of Water Using Heterodyne-Detected Surface Sum-Frequency Generation.

We study the effect of sodium chloride (NaCl) on the properties of the interface of water and the surfactant dodecyl sulfate (DS-) using heterodyne-detected vibrational sum-frequency generation spectroscopy. We find that the signal of the O-H stretch vibrations of oriented water molecules at the interface is highly nonlinearly dependent on the NaCl concentration. This nonlinear dependence is explained by a combination of screening of the electric field of surface-bound DS- ions pointing into the bulk and screening of the Coulomb repulsion between the headgroups of the DS- ions in the surface plane. The latter effect strongly increases the oriented water signal within a limited NaCl concentration range of 10-100 mM, indicating a two-dimensional hydrophobic collapse of the surfactant layer. The occurrence of collapse is supported by model calculations of the surface potential and surface surfactant density.

Structural Anomality of the Adsorbed Water on Al-Doped Silica Revealed by Heterodyne-Detected Vibrational Sum-Frequency Generation Spectroscopy

Structural Anomality of the Adsorbed Water on Al-Doped Silica Revealed by Heterodyne-Detected Vibrational Sum-Frequency Generation Spectroscopy

Elucidation of the pH-Dependent Electric Double Layer Structure at the Silica/Water Interface Using Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy

The silica/water interface is one of the most abundant charged interfaces in natural environments, and the elucidation of the water structure at the silica/water interface is essential. In the present study, we measured the interface-selective vibrational (χ(2)) spectra in the OH stretch region of the silica/water interface in a wide pH range of pH 2.0-12.0 while changing the salt concentration by heterodyne-detected vibrational sum-frequency generation spectroscopy. With the help of singular value decomposition analysis, it is shown that the imaginary part of the χ(2) (Imχ(2)) spectra can be decomposed into the spectra of the diffuse Gouy-Chapman layer (DL) and the compact Stern layer (SL), which enables us to quantitatively analyze the spectra of DL and SL separately. The salt-concentration dependence of the DL spectra at different pH values is analyzed using the modified Gouy-Chapman theory, and the pH-dependent surface charge density and the pKa value (4.8 ± 0.2) of the silica/water interface are evaluated. Furthermore, it is found that the pH-dependent change of the SL spectra is quantitatively explained by three spectral components that represent the three characteristic water species appearing in different pH regions in SL. The quantitative understanding obtained from the analysis of each spectral component in the Imχ(2) spectra provides a clear molecular-level picture of the electric double layer at the silica/water interface.

Molecular Orientation of Carboxylate Anions at the Water-Air Interface Studied with Heterodyne-Detected Vibrational Sum-Frequency Generation.

The carboxylate anion group plays an important role in many (bio)chemical systems and polymeric materials. In this work, we study the orientation of carboxylate anions with various aliphatic and aromatic substituents at the water-air interface by probing the carboxylate stretch vibrations with heterodyne-detected vibrational sum-frequency generation spectroscopy in different polarization configurations. We find that carboxylate groups with small aliphatic substituents show a large tilt angle with respect to the surface normal and that this angle decreases with increasing size of the substituent. We further use the information about the orientation of the carboxylate group to determine the hyperpolarizability components of this group.

Proton Configuration in Water Chain on Pt(533).

In this paper, a wetting behavior of Pt(533) is studied by using heterodyne-detected vibrational sum-frequency generation spectroscopy under an ultrahigh-vacuum condition at 145 K. The imaginary parts of the surface nonlinear susceptibility (Imχ(2)) of the H-bonded OH stretching region are successfully obtained for submonolayer water coverage that show negative bands indicating H-down (proton pointing to the substrate) configurations both for the water at the step and at the terrace. The growth manner of the Imχ(2) signal with coverage and the results of an isotopic dilution are consistent with a model in which a one-dimensional (1D) chain at the step forms a "zigzag" structure that contains H-down orientations. This finding resolves the previous controversy in the literature concerning the proton configuration in the 1D water chain at the step.

Bulk Response of Carboxylic Acid Solutions Observed with Surface Sum-Frequency Generation Spectroscopy.

We study the molecular properties of aqueous acetic acid and formic acid solutions with heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). For acid concentrations up to ∼5 M, we observe a strong increase of the responses of the acid hydroxyl and carbonyl stretch vibrations with increasing acid concentration due to an increase of the surface coverage by the acid molecules. At acid concentrations >5 M we observe first a saturation of these responses and then a decrease. For pure carboxylic acids we even observe a change of sign of the Im[χ(2)] response of the carbonyl vibration. The decrease of the response of the hydroxyl vibration and the decrease and sign change of the response of the carbonyl vibration indicate the formation of cyclic dimers, which only show a quadrupolar bulk response in the HD-VSFG spectrum because of their antiparallel conformation. We also find evidence for the presence of a quadrupolar response of the CH vibrations of the acid molecules.

Molecular Structure and Surface Accumulation Dynamics of Hyaluronan at the Water-Air Interface.

Hyaluronan is a biopolymer that is essential for many biological processes in the human body, like the regulation of tissue lubrication and inflammatory responses. Here, we study the behavior of hyaluronan at aqueous surfaces using heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). Low-molecular-weight hyaluronan (∼150 kDa) gradually covers the water–air interface within hours, leading to a negatively charged surface and a reorientation of interfacial water molecules. The rate of surface accumulation strongly increases when the bulk concentration of low-molecular-weight hyaluronan is increased. In contrast, high-molecular-weight hyaluronan (>1 MDa) cannot be detected at the surface, even hours after the addition of the polymer to the aqueous solution. The strong dependence on the polymer molecular weight can be explained by entanglements of the hyaluronan polymers. We also find that for low-molecular-weight hyaluronan the migration kinetics of hyaluronan in aqueous media shows an anomalous dependence on the pH of the solution, which can be explained from the interplay of hydrogen bonding and electrostatic interactions of hyaluronan polymers.

Direct Evidence for a Surface and Bulk Specific Response in the Sum-Frequency Generation Spectrum of the Water Bend Vibration.

We study the bending mode of pure water and charged aqueous surfaces using heterodyne-detected vibrational sum-frequency generation spectroscopy. We observe a low (1626 cm^{-1}) and a high (1656 cm^{-1}) frequency component that can be unambiguously assigned to an interfacial dipole and a bulk quadrupolar response, respectively. We thus demonstrate that probing the bending mode provides structural and quantitative information on both the surface and the bulk.

Freezing of Aqueous Carboxylic Acid Solutions on Ice.

We study the properties of acetic acid and propionic acid solutions at the surface of monocrystalline ice with surface-specific vibrational sum-frequency generation (VSFG) and heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). When we decrease the temperature toward the eutectic point of the acid solutions, we observe the formation of a freeze concentrated solution (FCS) of the carboxylic acids that is brought about by a freeze-induced phase separation (FIPS). The freeze concentrated solution freezes on top of the ice surface as we cool the system below the eutectic point. We find that for freeze concentrated acetic acid solutions the freezing causes a strong decrease of the VSFG signal, while for propionic acid an increase and a blue-shift are observed. This different behavior points at a distinct difference in molecular-scale behavior when cooling below the eutectic point. We find that cooling of the propionic acid solution below the eutectic point leads to the formation of hydrogen-bonded dimers with an opposite alignment of the carboxylic acid O–H groups.

Molecular structure of a hyperactive antifreeze protein adsorbed to ice.

Antifreeze proteins (AFPs) are a unique class of proteins that bind to ice crystal surfaces and arrest their growth. The working mechanism of AFPs is not well understood because, as of yet, it was not possible to perform molecular-scale studies of AFPs adsorbed to the surface of ice. Here, we study the structural properties of an AFP from the insect Rhagium mordax (RmAFP) adsorbed to ice with surface specific heterodyne-detected vibrational sum-frequency generation spectroscopy and molecular dynamic simulations. We find that RmAFP, unlike other proteins, retains its hydrating water molecules upon adsorption to the ice surface. This hydration water has an orientation and hydrogen-bond structure different from the ice surface, thereby inhibiting the insertion of water layers in between the protein and the ice surface.

Surface Structure of Solutions of Poly(vinyl alcohol) in Water.

We use surface-specific heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG) and surface tension measurements to investigate the molecular structure of the surface of aqueous solutions of poly(vinyl alcohol) (PVA) polymers with average molecular weights of 10000 and 125000 g/mol. We find that the interfacial water molecules have a preferred orientation with their hydrogen-bonded O-H groups pointing away from the bulk, for both PVA10000 and PVA125000. This observation is explained from the ongoing hydrolysis of the acetyl impurities on the PVA polymer chains. This hydrolysis yields negatively charged acetate ions that have a relatively high surface propensity. For both PVA10000 and PVA125000 the strong positive signal vanishes when the pH is decreased, due to the neutralization of the acetate ions. For solutions with a high concentration of PVA10000 the interfacial water signal becomes very small, indicating that the surface gets completely covered with a disordered PVA polymer film. In contrast, for high concentrations of PVA125000, the strong positive water signal persists at high pH, which shows that the water surface does not get completely covered. The HD-VSFG data combined with surface tension data indicate that concentrated PVA125000 solutions form a structured surface layer with pores containing a high density of interfacial water.

Water Orientation at Ceramide/Water Interfaces Studied by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy and Molecular Dynamics Simulation

Lipid/water interaction is essential for many biological processes. The water structure at the nonionic lipid interface remains little known, and there is no scope of a priori prediction of water orientation at nonionic interfaces, either. Here, we report our study combining advanced nonlinear spectroscopy and molecular dynamics simulation on the water orientation at the ceramide/water interface. We measured χ(2) spectrum in the OH stretch region of ceramide/isotopically diluted water interface using heterodyne-detected vibrational sum-frequency generation spectroscopy and found that the interfacial water prefers an overall hydrogen-up orientation. Molecular dynamics simulation indicates that this preferred hydrogen-up orientation of water is determined by a delicate balance between hydrogen-up and hydrogen-down orientation induced by lipid–water and intralipid hydrogen bonds. This mechanism also suggests that water orientation at neutral lipid interfaces depends highly on the chemical structure of the lipid headgroup, in contrast to the charged lipid interfaces where the net water orientation is determined solely by the charge of the lipid headgroup.

Direct Measurement of the Absolute Orientation of N3 Dye at Gold and Titanium Dioxide Surfaces with Heterodyne-Detected Vibrational SFG Spectroscopy

Light-harvesting dyes in dye-sensitized solar cells (DSSCs) must be designed not only to effectively harvest visible light but also to maintain an adsorption geometry at the solvent/TiO2 interface that encourages electron injection. Electron injection is encouraged when the dye is adsorbed to the TiO2 surface such that the LUMO of the dye is spatially near the surface. Furthermore, deleterious recombination pathways between the surface and dye are suppressed if the HOMO of the dye is spatially well-separated from the surface. Thus, measuring the configuration of dyes at these interfaces is important for understanding why some dyes perform better than others as well as providing insight into designing more ideal dyes. We investigate the adsorption geometry of N3 dye on gold and TiO2 using heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). Incorporating heterodyne detection into our VSFG experiment provides both enhanced SFG signal and phase sensitivity, which enables the measu...

Counterion effect on interfacial water at charged interfaces and its relevance to the Hofmeister series.

Specific counterion effects represented by Hofmeister series are important for a variety of phenomena such as protein precipitations, surface tensions of electrolytes solutions, phase transitions of surfactants, etc. We applied heterodyne-detected vibrational sum-frequency generation spectroscopy to study the counterion effect on the interfacial water at charged interfaces and discussed the observed effect with relevance to the Hofmeister series. Experiments were carried out for model systems of positively charged cetyltrimethylammonium monolayer/electrolyte solution interface and negatively charged dodecylsulfate monolayer/electrolyte interface. At the positively charged interface, the intensity of the OH band of the interfacial water decreases in the order of the Hofmeister series, suggesting that the adsorbability of halide anions onto the interface determines the Hofmeister order as previously proposed by Zhang and Cremer (Curr. Opin. Chem. Biol. 2006, 10, 658-663). At the negatively charged interfaces, on the other hand, the OH band intensity does not depend significantly on the countercation, whereas variation in the hydrogen-bond strength of the interfacial water is well correlated with the Hofmeister order of the cation effect. These results provide new insights into the molecular level mechanisms of anionic and cationic Hofmeister effects.

Structure and Dynamics of Interfacial Water Studied by Heterodyne-Detected Vibrational Sum-Frequency Generation

Vibrational sum-frequency generation (VSFG) spectroscopy is a powerful tool to study interfaces. Recently, multiplex heterodyne-detected VSFG (HD-VSFG) has been developed, which enables the direct measurement of complex second-order nonlinear susceptibility [χ((2))]. HD-VSFG has remarkable advantages over conventional VSFG. For example, the imaginary part of χ((2)) [Imχ((2))] obtained with this interferometric technique is the direct counterpart to the infrared [Imχ((1))] and Raman [Imχ((3))] spectra in the bulk, and it is free from the spectral deformation inevitable in conventional VSFG [|χ((2))|(2)] spectra. The Imχ((2)) signal is obtained with a sign that contains unambiguous information about the up/down orientation of interfacial molecules. Furthermore, HD-VSFG can be straightforwardly extended to time-resolved measurements when combined with photoexcitation. In this review, we describe the present status of experiments and applications of multiplex HD-VSFG spectroscopy, in particular with regard to the orientation and structure of interfacial water at charged, neutral, and biorelevant water interfaces.