Second harmonic generation-based coherent vibrational spectroscopy for a liquid interface under the nonresonant pump condition

The molecular dynamics in the low-frequency region (0-500 cm(-1)) sensitively reflects the intermolecular interactions in a liquid. The second harmonic generation-based coherent vibrational spectroscopy (SHG-CVS) was developed to monitor the low-frequency dynamics of molecules at a liquid interface, which was difficult to access by using the present spectroscopic techniques such as sum frequency generation or attenuated total reflection (ATR)-IR. Background-free detection with the transient grating (TG) optical configuration was adopted to obtain the weak signal under the electronically nonresonant pump condition. It was demonstrated that the S/N ratio of the SHG-CVS with the TG configuration was remarkably superior to that with the conventional time-resolved SHG configuration, and the improved detection limit enabled us to detect the low-frequency dynamics of coumarin 314 molecules at the air/water interface under the electronically nonresonant pump condition.     

Deduction of structural information of interfacial proteins by combined vibrational spectroscopic methods

We demonstrate both theoretically and experimentally that the combination of vibrational spectroscopic techniques on samples can be used to deduce more detailed structural information of interfacial proteins and peptides. Such an approach can be used to elucidate structures of proteins or peptides at interfaces, such as at the solid/liquid interface or in cell membranes. We also discuss that the controlled perturbations may provide more measured parameters for structural studies on such proteins and peptides. In this paper, we will demonstrate that optical spectroscopic techniques such as polarized Fourier transform infrared spectroscopy (FTIR), sum frequency generation (SFG) vibrational spectroscopy, and higher order nonlinear vibrational spectroscopies can be used to deduce different and complementary structural information of molecules at interfaces (e.g., orientation information of certain functional groups and secondary structures of interfacial proteins). Also, we believe that controlled perturbations on samples, such as variation of sample temperature, application of electrical fields, and alternation of substrate roughness, can provide more detailed information regarding the interfacial structures of proteins and peptides. The development of nonlinear vibrational spectroscopies, such as SFG and four-wave mixing vibrational spectroscopy, to examine interfacial protein and peptide structures, and introduction of external perturbations on samples should be able to substantially advance our knowledge in understanding structures and thus functions of proteins and peptides at interfaces.     

Microscopic inhomogeneity and ultrafast orientational motion in an organic photovoltaic bulk heterojunction thin film studied with 2D IR vibrational spectroscopy

Two-dimensional infrared vibrational spectroscopy is used to examine conformational inhomogeneity and ultrafast orientational motion within local environments of an organic photovoltaic bulk heterojunction thin film. The bulk heterojunction material consists of a mixture of the electron donor poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-(1-cyanovinylene)phenylene] (CN-MEH-PPV) and the electron acceptor [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM). PCBM species reside in a distribution of environments within large domains of the molecules that cause their C=O stretch modes to be inhomogeneously broadened. The molecular inhomogeneity also results in frequency dependent vibrational relaxation dynamics. The butyric acid methyl ester group of PCBM undergoes ultrafast wobbling-in-the-cone orientational motion on the 110 fs time scale within a cone semiangle of 29 degrees . The vibrational dynamics are sensitive metrics of molecular order in the material and have implications for charge mobility and degradation phenomena in organic photovoltaic devices. This report represents the first study of organic photovoltaic materials using ultrafast two-dimensional infrared vibrational spectroscopy.     

隐藏高分子界面及生物界面分子结构的和频振动光谱研究

界面的分子结构决定界面的性质.为了以优化界面的结构来改进材料的性质,原位实时地研究界面的分子结构是很重要的.近年来和频振动光谱已发展成为一个很有效及独特的手段来研究隐藏界面的分子结构,例如液/液界面、固/液界面及固/固界面等.这篇综述讨论了和频振动光谱在研究高分子界面及生物界面等复杂界面的分子结构上的应用.具体说来,本文论述了高分子表面在水里的分子结构变化,高分子及模型粘合促进剂硅烷在界面相互作用的分子机理和隐藏的高分子/高分子及高分子/金属界面的结构.另外,此文还将介绍不同二级结构的多肽及几个有代表性的蛋白分子在界面的结构.界面在诸如化学、生物、物理、材料科学及工程和纳米技术等许多领域都很重要.发展一个独特的能原位研究隐藏界面的分子结构的技术会有力地促进这些领域的研究及跨学科研究的发展.     

Water at surfaces and interfaces: From molecules to ice and bulk liquid

The structure and growth of water films on surfaces is reviewed, starting from single molecules to two-dimensional wetting layers, and liquid interfaces. This progression follows the increase in temperature and vapor pressure from a few degrees Kelvin in ultra-high vacuum, where Scanning Tunneling and Atomic Force Microscopies (STM and AFM) provide crystallographic information at the molecular level, to ambient conditions where surface sensitive spectroscopic techniques provide electronic structure information. We show how single molecules bind to metal and non-metal surfaces, their diffusion and aggregation. We examine how water molecules can be manipulated by the STM tip via excitation of vibrational and electronic modes, which trigger molecular diffusion and dissociation. We review also the adsorption and structure of water on non-metal substrates including mica, alkali halides, and others under ambient humid conditions. We finally discuss recent progress in the exploration of the molecular level structure of solid-liquid interfaces, which impact our fundamental understanding of corrosion and electrochemical processes.     

Excited-state dynamics of organic dyes at liquid/liquid interfaces

Liquid/liquid interfaces play a crucial role in numerous areas of science. However, direct spectroscopic access to this thin (～1 nm) region is not possible with conventional optical methods. After a brief review of the most used techniques to perform interfacial optical spectroscopy, we will focus on time-resolved surface second harmonic generation, which allows the measurement of the excited-state dynamics of probe molecules at interfaces. By comparing these dynamics with those measured in bulk solutions, precious information on the properties of the interfacial region can be obtained. To illustrate this, several studies performed in our group will be presented.     

C-H stretching vibrations of methyl, methylene and methine groups at the vapor/alcohol (N = 1-8) interfaces

In IR and Raman spectral studies, the congestion of the vibrational modes in the C-H stretching region between 2800 and 3000 cm(-1) has complicated spectral assignment, conformational analysis, and structural and dynamics studies, even with quite a few of the simplest molecules. To resolve these issues, polarized spectra measurement on a well aligned sample is generally required. Because the liquid interface is generally ordered and molecularly thin, and sum frequency generation vibrational spectroscopy (SFG-VS) is an intrinsically coherent polarization spectroscopy, SFG-VS can be used for discerning details in vibrational spectra of the interfacial molecules. Here we show that, from systematic molecular symmetry and SFG-VS polarization analysis, a set of polarization selection rules could be developed for explicit assignment of the SFG vibrational spectra of the C-H stretching modes. These polarization selection rules helped assignment of the SFG-VS spectra of vapor/alcohol (n = 1-8) interfaces with unprecedented details. Previous approach on assignment of these spectra relied on IR and Raman spectral assignment, and they were not able to give such detailed assignment of the SFG vibrational spectra. Sometimes inappropriate assignment was made, and consequently misleading conclusions on interfacial structure, conformation and even dynamics were reached. With these polarization rules in addition to knowledge from IR and Raman studies, new structural information and understanding of the molecular interactions at these interfaces were obtained, and some new spectral features for the C-H stretching modes were also identified. Generally speaking, these new features can be applied to IR and Raman spectroscopic studies in the condensed phase. Therefore, the advancement on vibrational spectra assignment may find broad applications in the related fields using IR and Raman as vibrational spectroscopic tools.     

Protein adsorption at the electrified air-water interface: implications on foam stability

The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams.     

Biomedical applications of X-ray absorption and vibrational spectroscopic microscopies in obtaining structural information from complex systems

Protein crystallography and NMR spectroscopy took decades to emerge as routine techniques in structural biology. X-ray absorption spectroscopy now has reached a similar stage of maturity for obtaining complementary local structural information around metals in metalloproteins. However, the relatively recent emergence of X-ray and vibrational spectroscopic microprobes that build on these techniques has enabled the structural information obtained from the “mature” techniques on isolated biomolecules to be translated into in situ structural information from inhomogeneous complex systems, such as whole cells and tissues.     

Ultrafast structural dynamics of water induced by dissipation of vibrational energy

In the liquid phase, water molecules form a disordered fluctuating network of intermolecular hydrogen bonds. Using both inter- and intramolecular vibrations as structural probes in ultrafast infrared spectroscopy, we demonstrate a two-stage structural response of this network to energy disposal: vibrational energy from individually excited water molecules is transferred to intermolecular modes, resulting in a sub-100 fs nuclear rearrangement that leaves the local hydrogen bonds weakened but unbroken. Subsequent energy delocalization over many molecules occurs on an approximately 1 ps time scale and is connected with the breaking of hydrogen bonds, resulting in a macroscopically heated liquid.     

Interfacial shear rheology of protein-surfactant layers

The shear rheology of adsorbed or spread layers at air/liquid and liquid/liquid phase boundaries is relevant in a wide range of technical applications such as mass transfer, monolayers, foaming, emulsification, oil recovery, or high speed coating. Interfacial shear rheological properties can provide important information about interactions and molecular structure in the interfacial layer. A variety of measuring techniques have been proposed in the literature to measure interfacial shear rheological properties and have been applied to pure protein or mixed protein adsorption layers at air/water or oil/water interfaces. Such systems play for example an important role as stabilizers in foams and emulsions. The aim of this contribution is to give a literature overview of interfacial shear rheological studies of pure protein and protein/surfactant mixtures at liquid interfaces measured with different techniques. Techniques which utilize the damping of waves, spectroscopic or AFM techniques and all micro-rheological techniques will not discuss here.     

Ultrafast energy transfer in water-AOT reverse micelles

A spectroscopic investigation of the vibrational dynamics of water in a geometrically confined environment is presented. Reverse micelles of the ternary microemulsion H2O/AOT/n-octane (AOT = bis-2-ethylhexyl sulfosuccinate or aerosol-OT) with diameters ranging from 1 to 10 nm are used as a model system for nanoscopic water droplets surrounded by a soft-matter boundary. Femtosecond nonlinear infrared spectroscopy in the OH-stretching region of H2O fully confirms the core/shell model, in which the entrapped water molecules partition onto two molecular subensembles: a bulk-like water core and a hydration layer near the ionic surfactant headgroups. These two distinct water species display different relaxation kinetics, as they do not exchange vibrational energy. The observed spectrotemporal ultrafast response exhibits a local character, indicating that the spatial confinement influences approximately one molecular layer located near the water-amphiphile boundary. The core of the encapsulated water droplet is similar in its spectroscopic properties to the bulk phase of liquid water, i.e., it does not display any true confinement effects such as droplet-size-dependent vibrational lifetimes or rotational correlation times. Unlike in bulk water, no intermolecular transfer of OH-stretching quanta occurs among the interfacial water molecules or from the hydration shell to the bulk-like core, indicating that the hydrogen bond network near the H2O/AOT interface is strongly disrupted.     

Two-dimensional nonlinear optical activity spectroscopy of coupled multi-chromophore system

Most biomolecules are chiral. A variety of optical activity measurement techniques have been extensively used to study chiral natures of complicated biological molecules such as proteins and nucleic acids. Recently, coherent two-dimensional (2D) spectroscopic techniques have been developed and widely used to study structures and dynamics of biomolecules via measuring couplings between chromophores. However, such 2D optical spectroscopic methods utilizing linearly polarized beams do not provide information on the molecular chirality. Thus, we have theoretically shown that novel 2D optical activity measurement techniques based on three- and four-wave-mixing schemes are of use to obtain the 2D spectrum of a chiral molecule. Particularly, we carried out numerical simulations of 2D optical activity spectra of polypeptides and a light-harvesting complex. These methods utilizing circularly polarized beams and related spectroscopic techniques will be of great use in understanding and elucidating the underlying mechanisms of ultrafast chemical and conformational changes of chiral biomolecules in the future.     

Ultrafast dynamics of a solution in spatially restricted environments studied by photothermal spectroscopies

The ultrafast dynamics of a solution in spatially restricted environments was studied by using the ultrafast transient lens (UTL) method. The UTL method is used to monitor the molecular dynamics of a solution by means of a change in the refractive index, which is advantageous for investigating the molecular dynamics of restricted systems. We investigated the photoisomerization of azobenzene derivatives in cyclodextrin nanocavities and revealed how the confinement affects the photoisomerization dynamics and yields. We also studied the relaxation dynamics of photo-excited auramine O (AuO) in a water/aerosol-OT/n-heptane reversed micelle. Both the perturbed properties of the included water and the interactions between AuO and the interface of the reversed micelle strongly appeared to affect the relaxation dynamics. At the same time, we observed a change in the refractive index suggesting a structural change of the micelles in the picosecond region that could not be detected by transient absorption spectroscopy. In addition, we developed the total internal reflection UTL (TIR-UTL) method to monitor the ultrafast molecular dynamics at the liquid interface. The relaxation dynamics of photoexcited AuO at the silica/water interface were observed with subpicosecond time resolution, and it was revealed that the interaction with the interface strongly inhibited the relaxation process. These results demonstrated the advantages of the UTL method for investigating the molecular dynamics of a solution in spatially restricted environments.     

Ultrafast intermolecular dynamics of liquid water: a theoretical study on two-dimensional infrared spectroscopy

Physical and chemical properties of liquid water are dominated by hydrogen bond structure and dynamics. Recent studies on nonlinear vibrational spectroscopy of intramolecular motion provided new insight into ultrafast hydrogen bond dynamics. However, our understanding of intermolecular dynamics of water is still limited. We theoretically investigated the intermolecular dynamics of liquid water in terms of two-dimensional infrared (2D IR) spectroscopy. The 2D IR spectrum of intermolecular frequency region (<1000 cm(-1)) is calculated by using the equilibrium and nonequilibrium hybrid molecular dynamics method. We find the ultrafast loss of the correlation of the libration motion with the time scale of approximately 110 fs. It is also found that the energy relaxation from the libration motion to the low frequency motion takes place with the time scale of about 180 fs. We analyze the effect of the hindered translation motion on these ultrafast dynamics. It is shown that both the frequency modulation of libration motion and the energy relaxation from the libration to the low frequency motion significantly slow down in the absence of the hindered translation motion. The present result reveals that the anharmonic coupling between the hindered translation and libration motions is essential for the ultrafast relaxation dynamics in liquid water.     

Ultrafast Vibrational Dynamics and Local Interactions of Hydrated DNA

Biochemical processes occur mainly in aqueous environments, where interactions with water molecules play a key role for both the structure and function of biomolecules. Deoxyribonucleic acid (DNA), the basic carrier of genetic information, is characterized by an equilibrium double helix structure which is held together by intermolecular hydrogen bonds between base pairs and hydrated by an environment of water molecules with fluctuating hydrogen bonds. Basic vibrational motions of hydrated DNA and the fastest changes in the DNA–water interactions and hydration geometries occur in less than 1 ps. These processes can be accessed by mapping the vibrational dynamics of DNA and water in a time‐resolved way by nonlinear ultrafast vibrational spectroscopy. Recent studies provide a detailed understanding of DNA vibrations and their dynamics, and give insight into nonequilibrium properties and structures of hydrated DNA.     

Spectroscopic techniques to characterize the spin state: Vibrational,optical, Mössbauer,NMR, and X-ray spectroscopy

Basic principles and recent work using probes including Mössbauer, optical, X-ray, and vibrational spectroscopies to follow the transitions in spin crossover complexes are reviewed. X-ray spectroscopy, being a relatively lesser-known probe, is discussed in more detail. X-ray spectroscopic methods have been used in the spin crossover field mostly to elucidate surface phenomena, ultrafast dynamics, and high pressure effects, but recent technical developments provide perspectives for a more widespread use of these powerful techniques in home laboratories.     

Liquid interfacial nanoarchitectonics: Molecular machines,organic semiconductors,nanocarbons, stem cells,and others

The concept of nanoarchitectonics has been proposed as an extensional development of nanotechnology through fusions with material science and the other fields. In nanoarchitectonics, nano-units of atoms, molecules, and nanomaterials are architected into construction of functional material systems. In order to assemble intended structures or hierarchical structures from nano-units, it is more useful to confine nano-units at the interface. In addition, nanoarchitectonics is expected to output functions by harmonizing many units in dynamic environments. However, the liquid interfaces still have lots of unexplored matters in nanoscale because supports by advanced apparatus and techniques in nanotechnology are not always available. Specifically, this review paper summarizes examples of research on molecular manipulation, molecular arrangement and assembly, materials synthesis, and life manipulation at the liquid interface. These examples demonstrate that the liquid interface enables the control of dynamic functions of various size regions, from molecular-level phenomena such as the control of molecular machines to techniques of living creature size such as the control of stem cell differentiation. Liquid interfaces are very useful environments for controlling dynamic functions for a wide range of targets and would have tremendous potential in terms of functional exploration. The great potential of nanoarchitectonics at the liquid interface and the challenges to be solved in the future are also discussed.     

Quantifying the ordering of adsorbed proteins in situ

We have investigated the orientation and conformation of protein molecules at the polystyrene (PS)/protein solution interface using sum frequency generation (SFG) vibrational spectroscopy, supplemented by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). In this research, we studied fibrinogen as a model protein. SFG studies indicate that fibrinogen adopts a bent structure after adsorbing to the PS surface. A broad orientation distribution of fibrinogen coiled-coils at the interface has been quantified by combining SFG and ATR-FTIR measurements. Error analysis for such a deduced distribution was carried out. This research demonstrates that quantitative structural information such as orientational and conformational ordering of proteins at interfaces can be studied using SFG supplemented by other spectroscopic techniques.