Heterodyne-detected Vibrational Sum Frequency Generation 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.

Unified picture of vibrational relaxation of OH stretch at the air/water interface

The elucidation of the energy dissipation process is crucial for understanding various phenomena occurring in nature. Yet, the vibrational relaxation and its timescale at the water interface, where the hydrogen-bonding network is truncated, are not well understood and are still under debate. In the present study, we focus on the OH stretch of interfacial water at the air/water interface and investigate its vibrational relaxation by femtosecond time-resolved, heterodyne-detected vibrational sum-frequency generation (TR-HD-VSFG) spectroscopy. The temporal change of the vibrationally excited hydrogen-bonded (HB) OH stretch band (ν=1→2 transition) is measured, enabling us to determine reliable vibrational relaxation (T1) time. The T1 times obtained with direct excitations of HB OH stretch are 0.2-0.4 ps, which are similar to the T1 time in bulk water and do not noticeably change with the excitation frequency. It suggests that vibrational relaxation of the interfacial HB OH proceeds predominantly with the intramolecular relaxation mechanism as in the case of bulk water. The delayed rise and following decay of the excited-state HB OH band are observed with excitation of free OH stretch, indicating conversion from excited free OH to excited HB OH (~0.9 ps) followed by relaxation to low-frequency vibrations (~0.3 ps). This study provides a complete set of the T1 time of the interfacial OH stretch and presents a unified picture of its vibrational relaxation at the air/water interface.

Observation of Electrostatically Driven Surface Adsorption in Mixed Surfactant Systems.

We employed heterodyne-detected vibrational sum-frequency generation (HD-VSFG) spectroscopy to obtain a molecular-level understanding of the interaction between the anionic surfactant sodium dodecyl ammonium sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). We observed that these surfactants show a strong cooperative effect on their adsorption to the water-air interface. Even at bulk concentrations 1000 times lower than the critical micelle concentrations of SDS and DTAB, a nearly complete surface surfactant layer is observed when both surfactants are present. This strong enhancement of the surface concentrations of DS- and DTA+ can be quantitatively explained from the favorable Coulomb interaction of the oppositely charged headgroups of DS- and DTA+ and the electrostatic interactions with their counterions. The HD-VSFG results are complemented by a modified Langmuir adsorption model in which we include the free energy associated with the electrostatic interactions of the surfactant ions and their counterions.

Surface stratification determines the interfacial water structure of simple electrolyte solutions

The distribution of ions at the air/water interface plays a decisive role in many natural processes. Several studies have reported that larger ions tend to be surface-active, implying ions are located on top of the water surface, thereby inducing electric fields that determine the interfacial water structure. Here we challenge this view by combining surface-specific heterodyne-detected vibrational sum-frequency generation with neural network-assisted ab initio molecular dynamics simulations. Our results show that ions in typical electrolyte solutions are, in fact, located in a subsurface region, leading to a stratification of such interfaces into two distinctive water layers. The outermost surface is ion-depleted, and the subsurface layer is ion-enriched. This surface stratification is a key element in explaining the ion-induced water reorganization at the outermost air/water interface.

Origin of Strong Hydrogen Bonding and Preferred Orientation of Water at Uncharged Polyethylene Glycol Polymer/Water Interface.

Polyethylene glycol (PEG), a water-soluble non-ionic polymer, finds diverse applications from Li-ion batteries to drug delivery. The effectiveness of PEG in these contexts hinges on water's behavior at PEG/water interfaces. Employing heterodyne-detected vibrational sum frequency generation and Raman spectroscopy along with a novel analytical approach, termed difference spectroscopy with simultaneous curve-fitting analysis, we observed that water exhibits both "hydrogen-up" and "hydrogen-down" orientations at PEG(≥400u)/water interfaces. As the molar mass of PEG increases, the contribution of the strongly hydrogen-bonded and H-up-oriented water rises. We propose that the PEG-affected interfacial water originates from the asymmetrical hydration of the surface-adsorbed PEG, as evidenced by the resemblance between the water spectra in the hydration shell of PEG and those at the PEG/water interface. These findings elucidate the molecular mechanism underlying PEG's catalytic role in water splitting at membrane interfaces.

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

Molecular Orientations of Myristic Acid Derivatives with Different Perfluoroalkyl Chain Lengths at the Air/Water Interface Evaluated by Heterodyne-Detected Sum Frequency Generation Spectroscopy

Surface-related properties of perfluoroalkyl compounds such as hydrophobicity and adhesion force can have a close relationship with the orientational order of the molecules at the surface. Myristic acid (MA) derivatives with perfluoroalkyl (Rf) groups have been known to form a well-ordered monolayer at the air/gold substrate interface. In this study, molecular orientations of the MA derivative monolayers at the air/water interface were investigated by heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. We estimated the molecular orientation of MA derivative monolayers with a marker band observed at around 1370 cm–1. The Rf chain length and the surface pressure dependence of the molecular orientation of four MA derivatives were examined. The marker bands were observed except for the derivative with the shortest Rf chain at the higher surface pressure, whereas the marker bands were observed only for the two derivatives with relatively longer Rf chain lengths at the lower surface pressure. The observation indicates that the longer the Rf chain is and the higher the surface pressure is, MA derivatives tend to adopt a standing orientation closer to perpendicular to the interface.

Origin of Solvent Stabilization at Superconcentrated Electrolyte/Electrode Interfaces Revealed by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy

Superconcentrated electrolyte solutions have attracted much attention because of their ability to stabilize solvent molecules for high-voltage rechargeable batteries. However, the stabilization mechanism has not been fully understood because of the lack of an in situ observation of the relevant interface. In the present study, we investigated the interfaces of platinum electrodes and acetonitrile solutions containing dilute and superconcentrated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) using in situ heterodyne-detected vibrational sum frequency generation as well as ex situ vibrational sum frequency generation spectroscopies. The results showed that the structures of the electrode interfaces are remarkably different with these two solutions and indicate that acetonitrile decomposes in the dilute solution, whereas the TFSI– anion decomposes in the superconcentrated solution.

True Origin of Amide I Shifts Observed in Protein Spectra Obtained with Sum Frequency Generation Spectroscopy.

Accurate determination of protein structure at interfaces is critical for understanding protein interactions, which is directly relevant to a molecular-level understanding of interfacial proteins in biology and medicine. Vibrational sum frequency generation (VSFG) spectroscopy is often used for probing the protein amide I mode, which reports protein structures at interfaces. Observed peak shifts are attributed to conformational changes and often form the foundation of hypotheses explaining protein working mechanisms. Here, we investigate structurally diverse proteins using conventional and heterodyne-detected VSFG (HD-VSFG) spectroscopy as a function of solution pH. We reveal that blue-shifts of the amide I peak observed in conventional VSFG spectra upon lowering the pH are governed by the drastic change of the nonresonant contribution. Our results highlight that connecting changes in conventional VSFG spectra to conformational changes of interfacial proteins can be arbitrary, and that HD-VSFG measurements are required to draw unambiguous conclusions about structural changes in biomolecules.

Adsorption of SARS-CoV-2 Spike (N501Y) RBD to Human Angiotensin-Converting Enzyme 2 at a Lipid/Water Interface.

The receptor binding domain (RBD) of spike proteins plays a crucial role in the process of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2) attachment to the human angiotensin-converting enzyme 2 (ACE2). The N501Y mutation and later mutations introduced extra positive charges on the spike RBD and resulted in higher transmissibility, likely due to stronger binding with the highly negatively charged ACE2. Consequently, many studies have been devoted to understanding the molecular mechanism of spike protein binding with the ACE2 receptor. Most of the theoretical studies, however, have been done on isolated proteins. ACE2 is a transmembrane protein; thus, it is important to understand the interaction of spike proteins with ACE2 in a lipid matrix. In this study, the adsorption of ACE2 and spike (N501Y) RBD at a lipid/water interface was studied using the heterodyne-detected vibrational sum frequency generation (HD-VSFG) technique. The technique is a non-linear optical spectroscopy which measures vibrational spectra of molecules at an interface and provides information on their structure and orientation. It is found that ACE2 is effectively adsorbed at the positively charged 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP) lipid monolayer via electrostatic interactions. The adsorption of ACE2 at the DPTAP monolayer causes a reorganization of interfacial water (D2O) from the D-down to the D-up orientation, indicating that the originally positively charged DPTAP interface becomes negatively charged due to ACE2 adsorption. The negatively charged interface (DPTAP/ACE2) allows further adsorption of positively charged spike RBD. HD-VSFG spectra in the amide I region show differences for spike (N501Y) RBD adsorbed at D2O, DPTAP, and DPTAP/ACE2 interfaces. A red shift observed for the spectra of spike RBD/DPTAP suggests that spike RBD oligomers are formed upon contact with DPTAP lipids.

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.

Observation of Strong Synergy in the Interfacial Water Response of Binary Ionic and Nonionic Surfactant Mixtures.

Interfacial vibrational footprints of the binary mixture of sodium dodecyl sulfate (SDS) and hexaethylene glycol monododecyl ether (C12E6) were probed using heterodyne detected vibrational sum frequency generation (HDVSFG). Our results show that in the presence of C12E6 at CMC (70 μM) the effect of SDS on the orientation of interfacial water molecules is enhanced 10 times compared to just pure surfactants. The experimental results contest the traditional Langmuir adsorption model predictions. This is also evidenced by our molecular dynamics simulations that show a remarkable restructuring and enhanced orientation of the interfacial water molecules upon DS- adsorption to the C12E6 surface. The simulations show that the adsorption free energy of DS- ions to a water surface covered with C12E6 is an enthalpy-driven process and more attractive by ∼10 kBT compared to the adsorption energy of DS- to the surface of pure water.

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.

Ultrafast vibrational dynamics of the free OD at the air/water interface: Negligible isotopic dilution effect but large isotope substitution effect.

Vibrational relaxation dynamics of the OH stretch of water at the air/water interface has been a subject of intensive research, facilitated by recent developments in ultrafast interface-selective nonlinear spectroscopy. However, a reliable determination of the vibrational relaxation dynamics in the OD stretch region at the air/D2O interface has not been yet achieved. Here, we report a study of the vibrational relaxation of the free OD carried out by time-resolved heterodyne-detected vibrational sum frequency generation spectroscopy. The results obtained with the aid of singular value decomposition analysis indicate that the vibrational relaxation (T1) time of the free OD at the air/D2O interface and air/isotopically diluted water (HOD-H2O) interfaces show no detectable isotopic dilution effect within the experimental error, as in the case of the free OH in the OH stretch region. Thus, it is concluded that the relaxation of the excited free OH/OD predominantly proceeds with their reorientation, negating a major contribution of the intramolecular energy transfer. It is also shown that the T1 time of the free OD is substantially longer than that of the free OH, further supporting the reorientation relaxation mechanism. The large difference in the T1 time between the free OD and the free OH (factor of ∼2) may indicate the nuclear quantum effect on the diffusive reorientation of the free OD/OH because this difference is significantly larger than the value expected for a classical rotational motion.

DNA-Induced Reorganization of Water at Model Membrane Interfaces Investigated by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

Lipid-DNA complexes are important nonviral vectors to be used in gene therapy, which is one of the promising strategies for the cure of many diseases. Although interfacial water is expected to play a significant role in lipid-DNA complexation, a molecular-level understanding about the role of interfacial water in the DNA-lipid complexation is still sparse. In this study, the structure and orientation of water at cationic and zwitterionic lipid monolayer/water interfaces in the presence of DNA are studied by the use of interface-selective heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. It is found that the adsorption of DNA at a cationic lipid interface drastically decreases the orientation of interfacial water reflecting the neutralization of the positively charged interface, whereas the adsorption of DNA at a zwitterionic lipid interface makes interfacial water become more "H-up", indicating that the originally zwitterionic interface becomes negatively charged due to the DNA adsorption. Furthermore, interfacial water having relatively strong hydrogen bonds is observed at both the cationic and zwitterionic lipid interfaces in the presence of DNA.

Water-Induced Restructuring of the Surface of a Deep Eutectic Solvent.

We study the molecular-scale structure of the surface of Reline, a DES made from urea and choline chloride, using heterodyne-detected vibrational sum frequency generation (HD-VSFG). Reline absorbs water when exposed to the ambient atmosphere, and following structure-specific changes at the Reline/air interface is crucial and difficult. For Reline (dry, 0 wt %, w/w, water) we observe vibrational signatures of both urea and choline ions at the surface. Upon increase of the water content, there is a gradual depletion of urea from the surface, an enhanced alignment, and an enrichment of the surface with choline cations, indicating surface speciation of ChCl. Above 40% w/w water content, choline cations abruptly deplete from the surface, as evidenced by the decrease of the vibrational signal of the −CH2– groups of choline and the rapid rise of a water signal. Above 60% w/w water content, the surface spectrum of aqueous Reline becomes indistinguishable from that of neat water.

Headgroup-Specific Interaction of Biological Lipid Monolayer/Water Interface with Perfluorinated Persistent Organic Pollutant (f-POP): As Observed with Interface-Selective Vibrational Spectroscopy.

Perfluoro compounds are widely used in various manufacturing processes, which leads to their bioaccumulation and subsequent adverse effects on human health. Using interface-selective vibrational spectroscopy (heterodyne-detected vibrational sum frequency generation (HD-VSFG)), we have elucidated the molecular mechanism of the perturbation of lipid monolayers on the water surface using a prototype perfluorinated persistent organic pollutant, perfluoroheptanoic acid (PFHA). PFHA disrupts the well-ordered all-trans conformation of a cationic lipid (1,2-dipalmitoyl-3-trimethylammonium propane (DPTAP)) monolayer and reduces the interfacial electric field at the lipid/water interface. In contrast, the hydrophobic packing of an anionic lipid (1,2-dipalmitoyl-sn-glycero-3-phospoglycerol (DPPG)) monolayer remains largely unaffected in the presence of PFHA, though the interfacial electric field is reduced. For a zwitterionic lipid (1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC))/water interface, both alkyl chain ordering and interfacial electric field are fairly perturbed by PFHA. Lipid headgroup-specific interaction of PFHA and the repulsive interaction of oleophobic fluoroalkyl chain with the lipid alkyl chains govern these distinct perturbations of the lipid monolayers on the water surface.