Methanol Adsorption on TiO2 Film Studied by Sum Frequency Generation Vibrational Spectroscopy

A broadband infrared surface sum frequency generation vibrational spectroscopy （SFG-VS） and an in situ UV excitation setup devoted to studying surface photocatalysis have been constructed. With a home-made compact high vacuum cell, organic contaminants on TiO2 thin film surface prepared by RF magnetron sputtering were in situ removed under 266 nm irradiation in 10 kPa 02 atmosphere. We obtained the methanol spectrum in the CH3 stretching vibration region on TiO2 surface with changing the methanol pressure at room temperature. Features of both molecular and dissociative methanol, methoxy, adsorbed on this surface were resolved. The CH3 symmetric stretching vibration frequency and Fermi resonance of molecular methanol is red-shifted by about 6-8 cm-1 from low to high coverage. Moreover, the recombination of dissociative methanol and H on Surfaces in vacuum was also observed. Our results suggest two equilibria exist： between molecular methanol in the gas phase and that on surfaces, and between molecular methanol and dissociative methanol on surfaces.

A Highly Sensitive Femtosecond Time-Resolved Sum Frequency Generation Vibrational Spectroscopy System with Simultaneous Measurement of Multiple Polarization Combinations

Characterization of real-time and ultrafast motions of the complex molecules at surface and interface is critical to understand how interracial molecules function. It requires to develop surface-sensitive, fast-identification, and time-resolved techniques. In this study, we employ several key technical procedures and successfully develop a highly sensitive femtosecond time-resolved sum frequency generation vibrational spectroscopy （SFG-VS） system. This system is able to measure the spectra with two polarization combinations （ssp and ppp, or psp and ssp） simultaneously. It takes less than several seconds to collect one spectrum. To the best of our knowledge, it is the fastest speed of collecting SFG spectra reported by now. Using the time-resolved measurement, ultrafast vibrational dynamics of the N-H mode of α-helical peptide at water interface is determined. It is found that the membrane environment does not affect the N-H vibrational relaxation dynamics. It is expected that the time-resolved SFG system will play a vital role in the deep understanding of the dynamics and interaction of the complex molecules at surface and interface. Our method may also provide an important technical proposal for the people who plan to develop time-resolved SFG systems with simultaneous measurement of multiple polarization combinations.

Vibrational Spectra and Adsorption of Trisiloxane Superspreading Surfactant at Air/Water Interface Studied with Sum Frequency Generation Vibrational Spectroscopy

The C-H stretch vibrational spectra of the trisiloxane superspreading surfactant Silwet L-77 （（CH3）3Si- O-Si（CH3）（C3H6）（OCH2CH2）7-8OCH3）-O-Si（CH3）3） at the air/water interface are measured with the surface Sum Frequency Generation Vibrational Spectroscopy （SFG-VS）. The spectra are dominated with the features from the -Si-CH3 groups around 2905 cm^-1 （symmetric stretch or SS mode） and 2957 ^-1 （mostly the asymmetric stretch or AS mode）, and with the weak but apparent contribution from the -O-CH2- groups around 2880 ^-1 （symmetric stretch or SS mode）. Comparison of the polarization dependent SFG spectra below and above the critical aggregate or micelle concentration （CAC） indicates that the molecular orientation of the C-H related molecular groups remained unchanged at different surface densities of the Silwet L-77 surfactant. The SFG-VS adsorption isotherm suggested that there was no sign of Silwet L-77 bilayer structure formation at the air/water interface. The Gibbs adsorption free energy of the Silwet surfactant to the air/water interface is -42.2±0.8kcal/mol, indicating the unusually strong adsorption ability of the Silwet L-77 superspreading surfactant.

Absolute Orientation of Molecules with Competing Hydrophilic Head Groups at the Air/Water Interface Probed with Sum Frequency Generation Vibrational Spectroscopy

The constructive or destructive spectral interference between the molecular groups oriented up and down at the interface in the sum-frequency generation （SFG） spectra provides a direct measurement of the absolute orientation of these molecular groups. This simple approach can be employed to interrogate absolute molecular orientations other than using the complex absolute phase measurement in the SFG studies. We used the -CN group in the p-cyanophenol （PCP） molecule as the internal phase standard, and we measured the phases of the SFG fields of the -CN groups in the 3,5-dimethyl-4-hydroxy-benzonitrile （35DMHBN） and 2,6-dimethyl-4-hydroxy-benzonitrile （26DMHBN） at the air/water interface by measuring the SFG spectra of the aqueous surfaces of the mixtures of the PCP, 35DMHBN, and 26DMHBN solutions. The results showed that the 35DMHBN had its -CN group pointing into the aqueous phase; while the 26DMHBN, similar to the PCP, had its -CN group pointing away from the aqueous phase. The tilt angles of the -CN group for both the 35DMHBN and 26DMHBN molecules at the air/water interface were around 25°-45° from the interface normal. These results provided insights on the understanding of the detailed balance of the competing factors, such as solvation of the polar head groups, hydrogen bonding and hydrophobic effects, etc., on influencing the absolute molecular orientation at the air/water interface.

Surface of room temperature ionic liquid [bmim][PF_6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.

Sum Frequency Generation Vibrational Spectra of Perovskite Nanocrystals at the Single-Nanocrystal and Ensemble Levels

Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.

Sum Frequency Spectroscopy Studies on Cell Membrane Fusion Induced by Divalent Cations

Cell membrane fusion is a fundamental biological process involved in a number of cellular living functions. Regarding this, divalent cations can induce fusion of the lipid bilayers through binding and bridging of divalent cations to the charged lipids, thus leading to the cell membrane fusion. However, the elaborate mechanism of cell membrane fusion induced by divalent cations is still needed to be elucidated.Here, surface/interface sensitive sum frequency generation vibrational spectroscopy(SFG-VS) and dynamic light scattering(DLS) were applied in this research to study the responses of phospholipid monolayer to the exposure of divalent metal ions i.e.Ca^(2+)and Mg^(2+). According to the particle size distribution results measured by DLS experiments, it was found that Ca^(2+)could induce inter-vesicular fusion while Mg^(2+)could not. An octadecyltrichlorosilane self-assembled monolayer(OTS SAM)-lipid monolayer system was designed to model the cell membrane for the SFG-VS experiment. Ca^(2+)could interact with the lipid POO_(2)^(-)head groups more strongly, resulting in cell membrane fusion more easily, in comparison with Mg^(2+). No specific interaction between the two metal cations and the C=O groups was observed. However, the C=O orientations changed more after Ca^(2+)-PO2-binding than Mg^(2+)mediation on lipid monolayer. Meanwhile, Ca^(2+)could induce dehydration of the lipids(which should be related to the strong Ca^(2+)-PO_(2)^(-)interaction), leading to the reduced hindrance for cell membrane fusion.

Methanol Perturbing Modeling Cell Membranes Investigated using Linear and Nonlinear Vibrational Spectroscopy

Cell membranes play a crucial role in many biological functions of cells. A small change in the composition of cell membranes can strongly influence the functions of membrane-associated proteins, such as ion and water channels, and thus mediate the chemical and physical balance in cells. Such composition change could originate from the introduction of short-chain alcohols, or other anesthetics into membranes. In this work, we have applied sum frequency generation vibrational spectroscopy （SFG-VS）, supplemented by attenuated total reflectance Fourier transform infrared spectroscopy （ATR-FTIR）, to investigate interaction between methanol and 1,2-dimyristoyl-d54-sn-glycero-3-phosphocholine （d54-DMPC） lipid bilayers. Lipid＇s hydrocarbon interior is deuterated while its head group is hydrogenated. At the same time, CH3 symmetric stretch from methanol and lipid head amine group has different frequency, thus we can distinguish the behaviors of methanol, lipid head amine group, and lipid hydrocarbon interior. Based on the spectral feature of the bending mode of the water molecules replaced by methanol, we determined that the methanol molecules are intercalated into the region between amine and phosphate groups at the lipid hydrophilic head. The dipole of CH3 groups of methanol and lipid head, and the water O-H M1 adopt the same orientation directions. The introduction of methanol into the lipid hydrophilic head group can strongly perturb the entire length of the alkyl chains, resulting that the signals of CD2 and CD3 groups from both leaflets can not cancel each other.

Ordering effects of cholesterol on sphingomyelin monolayers investigated by high-resolution broadband sum-frequency generation vibrational spectroscopy

This report investigated the ordering of the alky chain of sphingomyelin （SMs） monolayers induced by cholesterol at the air/water interface using high-resolution broadband sum frequency generation vibrational spectroscopy （HR-BB-SFG-VS）. The SFG spectra of the three nature sphingomyelin/cholesterol mixture monolayers with two concentrations of the cholesterol at the air/water interface are performed under different polarization combination. A new resolved CH2 symmetric stretching （d＋, ~2834 cm-1） and the CH3 symmetric stretching （r＋, ~2874 cm-1） mode are applied to characterize the conformational order in the sphingomyelin/cholesterol mixture monolayers. It was found that the cholesterol make the sphingosine backbones more conformational order. During this process, the conformational order of the N-linked acyl chain remains unaltered. Moreover, the sphingosine backbones of SMs have much larger contributions to gauche defects of SMs than one in the N-linked acyl chain. These results presented here not only shed lights on understanding of the interactions of sphingomyelin molecules with cholesterol molecules at interface but also demonstrates the ability of HR-BB-SFG to probe such complicated molecular systems.