Vibrational sum-frequency generation at protein modified air–water interfaces: Effects of molecular structure and surface charging

Protein and surfactant modified air–water interfaces are an important model system for colloid science as many applications for example aqueous foams in food products rely on our knowledge and ability to tune molecular structures at these interfaces. That is because interfaces are a fundamental building block in the hierarchical structure of foam, where in fact the molecular level can determine properties on larger length scales. For that reason it is of great importance to increase our ability to study air–water interfaces with molecular level probes and to obtain not only information on coverage but also direct information on interfacial composition, molecular order, orientations as well as information on the charged state of an interface. Vibrational sum-frequency generation (SFG) is a powerful tool that can help to address these issues and is inherently surface sensitive. In this contribution we will review recent developments in the use of SFG for studies of biomolecules at aqueous interfaces and discuss current issues with the interpretation of SFG spectra from electrified interfaces. In order to guide interpretations from interface spectroscopy we invoke the use of complementary methods such as ellipsometry and zetapotential measurements of bulk molecules.     

Deciphering second harmonic generation signals

Second harmonic generation (SHG) has emerged as one of the most powerful techniques used to selectively monitor surface dynamics and reactions for all types of interfaces as well as for imaging non-centrosymmetric structures, although the molecular origin of the SHG signal is still poorly understood. Here, we present a breakthrough approach to predict and interpret the SHG signal at the atomic level, which is freed from the hyperpolarisability concept and self-consistently considers the non-locality and the coupling with the environment. The direct ab initio method developed here shows that a bulk quadrupole contribution significantly overwhelms the interface dipole term in the purely interfacial induced second-order polarisation for water/air interfaces. The obtained simulated SHG responses are in unprecedented agreement with the experimental signal. This work not only paves the road for the prediction of SHG response from more complex interfaces of all types, but also suggests new insights in the interpretation of the SHG signal at a molecular level. In particular, it highlights the modest influence of the molecular orientation and the high significance of the bulk quadrupole contribution, which does not depend on the interface, in the total experimental response.

Second harmonic generation is one of the most powerful techniques used to selectively probe interfaces of all types. The direct ab initio method developed here allows predicting the signal and highlights the importance of local and non-local effects.     

Increased interfacial thickness of the NaF, NaCl and NaBr salt aqueous solutions probed with non-resonant surface second harmonic generation (SHG)

Specific ion effects on the nonlinear optical response from the water molecules at the air/sodium halide solution interfaces are measured using non-resonant surface second harmonic generation (SHG). Procedures have been developed to monitor and remove the impurities in the salt solution samples to ensure measurement of small changes in the SHG signal. Quantitative polarization analysis of the measured SHG data indicated that the average orientation of the interfacial water molecules changed only slightly around 40 degrees with the increase of the bulk concentration of the three sodium halides, namely NaF, NaCl and NaBr, from that of the neat air/water interface. The observed significant SHG signal increase with the bulk salt concentration is attributed to the overall increase of the thickness of the interfacial water molecular layer, following the order of NaBr > NaCl approximately NaF. The absence of the electric-field-induced SHG (EFISHG) effect indicated that the electric double layer at the salt aqueous solution interface is much weaker than that predicted from the molecular dynamics (MD) simulations. These results provided quantitative data to the specific anion effects on the interfacial water molecules of the electrolyte aqueous solution, not only for the larger and more polarizable Br(-) anion, but also for the smaller and less polarizable F(-) and Cl(-) anions.     

A study of kinetic molecular exchange processes in the medium frequency range by surface SHG on an oscillating bubble

The dilatational properties of fluid surfaces and interfaces have been comprehensively investigated in recent years. For example, an improved oscillating bubble device provided experimental results that allow for critical testing of established surface models, such as the Lucassen/van den Tempel (LvdT) model. The comparison of the LvdT model with the oscillating bubble experiments demonstrates a mismatch between the model parameters. For example, near the CMC or the limit of solubility the calculated parameters of surfactant solutions become unrealistically large. The deviation can be explained by the introduction of more detailed surface models, in particular by the modification of the effective thickness of the surface layer, its internal structure and the molecular exchange processes between these structures. For the verification of such processes an experimental setup was realized which allows for an independent determination of the instantaneous adsorption state at the surface of an oscillating bubble inside a surfactant solution. The setup utilizes the Second Harmonic Generation (SHG)--effect at the air-solution interface generated by the light of a pulsed LASER. The set-up is described in detail, and the results of a first experimental series are presented and discussed in this paper. As system, aqueous solutions of the fluortenside F381 were used.     

有序分子系统的线性与非线性光谱学的简化描述

A simplified formulation for treating the linear and nonlinear spectroscopy of ordered molecular systems is presented,in order to help experimentalists to have an explicit physical picture and quantitative tool on using linear and nonlinear spectroscopy to study molecules in ordered molecular systems. This formulation is expended from our recent quantitative orientational and polarization treatment on second-order nonlinear spectroscopic techniques in interface studies,namely,the Second Harmonic Generation（SHG）and Sum Frequency Generation-Vibrational Polarization Spectroscopy（SFG-VPS）. The key to this formulation is to simplify the effective linear or nonlinear molecular susceptibility and construct the general orientational functional with a clear approach to calculate the orientational and intensity parameters from the experimental parameters,which determines the orientational and polarization behavior of the general orientational functional in a particular experimental configuration. Also discussed are the advantages of coherent spectroscopic techniques over incoherent ones for the accurate measurement of orientation and ordering of ordered molecular system.     

Reconsideration of second-harmonic generation from isotropic liquid interface: broken Kleinman symmetry of neat air/water interface from dipolar contribution

It has been generally accepted that there are significant quadrupolar and bulk contributions to the second-harmonic generation (SHG) reflected from the neat air/water interface, as well as common liquid interfaces. Because there has been no general methodology to determine the quadrupolar and bulk contributions to the SHG signal from a liquid interface, this conclusion was reached based on the following two experimental phenomena: the breaking of the macroscopic Kleinman symmetry and the significant temperature dependence of the SHG signal from the neat air/water interface. However, because the sum frequency generation vibrational spectroscopy (SFG-VS) measurement of the neat air/water interface observed no apparent temperature dependence, the temperature dependence in the SHG measurement has been reexamined and proven to be an experimental artifact. Here we present a complete microscopic analysis of the susceptibility tensors of the air/water interface, and show that dipolar contribution alone can be used to address the issue of the breaking of the macroscopic Kleinman symmetry at the neat air/water interface. Using this analysis, the orientation of the water molecules at the interface can be obtained, and it is consistent with the measurement from SFG-VS. Therefore, the key rationales to conclude significantly quadrupolar and bulk contributions to the SHG signal of the neat air/water interface can no longer be considered as valid as before. This new understanding of the air/water interface can shed light on our understanding of the nonlinear optical responses from other molecular interfaces as well.     

DIFFRACTION AND HOLOGRAPHY WITH PHOTOELECTRONS AND FLUORESCENT X-RAYS

We consider studies of the atomic and magnetic structure near surfaces by photoelectron diffraction and by the holographic inversion of both photoelectron diffraction data and diffraction data involving the emission of fluorescent x-rays. The current status of photoelectron diffraction studies of surfaces, interfaces, and other nanostructures is first briefly reviewed, and then several recent developments and proposals for future areas of application are discussed. The application of full-solid-angle diffraction data, together with simultaneous characterization by low energy electron diffraction and scanning tunneling microscopy, to the epitaxial growth of oxides and metals is considered. Several new avenues that are being opened up by third-generation synchrotron radiation sources are also discussed. These include site-resolved photoelectron diffraction from surface and interface atoms, the possibility of time-resolved measurements of surface reactions with chemical-state resolution, and circular dichroism in photoelectron angular distributions from both non-magnetic and magnetic systems. The addition of spin to the photoelectron diffraction measurement is also considered as a method for studying short-range magnetic order, including the measurement of surface magnetic phase transitions. This spin sensitivity can be achieved through either core-level multiplet splittings or circular-polarized excitation of spin-orbit-split levels. The direct imaging of short-range atomic structure by both photoelectron holography and two distinct types of x-ray holography involving fluorescent emission is also discussed. Both photoelectron and x-ray holography have demonstrated the ability to directly determine at least approximate atomic structures in three dimensions. Photoelectron holography with spin resolution may make it possible also to study short-range magnetic order in a holographic fashion. Although much more recent in its first experimental demonstrations, x-ray fluorescence holography should permit deriving more accurate atomic images for a variety of materials, including both surface and bulk regions.     

以催化功能优化为导向的无机复合结构表界面和电子态调控

本文概述了具有特定表/界面的无机复合结构纳米晶体的可控合成方法,阐述了合成过程中的关键控制参数。以笔者课题组近年来的进展为例,重点讨论了复合结构的设计对纳米催化剂表/界面状态和电子态的调控。纳米结构的表/界面状态和电子态调控赋予了催化剂在反应分子吸附与活化中的独特行为,从而获得了不同于单一组分催化剂的优异催化性能。     

Self‐Assembled Monolayers into the 21st Century: Recent Advances and Applications

The modification of an interface on a molecular level with more than one molecular ‘building block' is essentially an example of the ‘bottom–up' fabrication principle of nanotechnology. The fabrication of such integrated molecular systems in electrochemistry has seen rapid progress in recent years via the development of sensing interfaces fabricated using self‐assembled monolayers (SAMs). This review outlines recent advances and applications of self‐assembled monolayers for modifying electrodes with an emphasis on the development of integrated molecular systems. First, some basic issues regarding fabricating integrated molecular systems, such as the role of the surface topography of the electrode and patterning surfaces, are discussed. Subsequently an overview of recent developments in pH, inorganic and bio sensing involving the use of SAMs is given. Finally emerging trends in using molecular building blocks in the fabrication of integrated molecular systems, such as nanotubes, dendrimers and nanoparticles, are reviewed.     

Behavior of nanocelluloses at interfaces

Despite being non-surface active, nanocelluloses position efficiently at interfaces, already at very low concentration. This behavior has lately triggered a strong interest in the cellulose and colloids communities. This review reports the recent developments on the use of nanocelluloses at interfaces and highlights the fundamental principles governing the high efficiency observed in reinforcing the boundary between two phases. The use of nanocelluloses as emulsifier and emulsion stabilizer is first discussed, and the structural properties of nanocelluloses such as aspect ratio and surface properties are correlated with the high efficiency in forming colloidally-stable multiphase systems. Then, the behavior at the air/water interface is presented and the most recent advances are reviewed with focus on the surface free energy of nanocelluloses and their role in the interfacial self-assembly process.     

Molecular dynamics investigation of the intrinsic structure of water-fluid interfaces via the intrinsic sampling method

Capillary wave fluctuations smooth out the structure of fluid interfaces, making difficult the detailed analysis of the interfacial structure. Most computer simulation investigations performed to date have focused on the computation of average density profiles, ignoring the characterization of the intrinsic structure of the interface. Recent theoretical developments have reversed this situation, making possible the detailed investigation of the interfacial intrinsic structure at an unprecedented level of detail. In this article we investigate via molecular dynamics simulations the intrinsic structure of water-alkane (hexane and dodecane) interfaces. The implementation of the recently introduced, intrinsic sampling method to compute the intrinsic surface of water-fluid interfaces is discussed. We provide quantitative molecular information on the structure, corrugation, and stiffness of the liquid surfaces. The intrinsic structure of water at alkane interfaces is shown to be insensitive to the alkane-chain length, and can be very accurately described by the intrinsic structure of the water free surface.     

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.     

Janus and patchy colloids at fluid interfaces

Understanding the fundamental behavior of chemically anisotropic Janus and patchy particles at fluid interfaces enables utilization of these colloids as solid surfactants for stabilization of emulsions and as building blocks for fabrication of functional and responsive materials. Here, we review recent progress on understanding the combined effects of particle–interface and particle–particle interactions on the surface activity and organization of Janus and patchy particles at fluid interfaces. We also highlight recent developments that harness these fundamental properties for applications in self-assembly and emulsion stabilization, and discuss some of the outstanding questions that warrant future investigation. The progress in the field opens new opportunities to pursue techniques for controlling interfacial rheology, directed motion, and the formulation of novel soft materials.     

Molecular sieving using nanofilters: past, present and future

Filtration of molecules by nanometer-sized structures is ubiquitous in our everyday life, but our understanding of such molecular filtration processes is far less than desired. Until recently, one of the main reasons was the lack of experimental methods that can help provide detailed, microscopic pictures of molecule-nanostructure interactions. Several innovations in experimental methods, such as nuclear track-etched membranes developed in the 70s, and more recent development of nanofluidic molecular filters, played pivotal roles in advancing our understanding. With the ability to make truly molecular-scale filters and pores with well-defined sizes, shapes, and surface properties, now we are well positioned to engineer better functionality in molecular sieving, separation and other membrane applications. Reviewing past theoretical developments (often scattered across different fields) and connecting them to the most recent advances in the field would be essential to get a full, unified view on this important engineering question.     

微生物脂肽在气/液界面上的分子形态*

微生物脂肽是一类具有很强表面活性和生物特性的生物表面活性剂。脂肽分子由亲水的肽链和疏水的脂肪烃链两部分组成,由于其特殊的化学组成和两亲性分子结构,脂肽类生物表面活性剂在医药、食品、化妆品、环境修复和微生物采油等领域具有良好的应用潜力。表面活性素是一类典型的微生物脂肽化合物,这主要是因为它除了具有表面活性外,还具有抗菌、抗病毒等生物活性。表面活性和生物活性主要在界面处发生,并受到活性分子在亲水/疏水界面上的分子形态的影响。本文重点以表面活性素为评述对象,综述了近年来微生物脂肽在气/液界面上分子形态的研究进展。     

Conformation, directed self-assembly and engineered modification: some recent near surface structure determinations by grazing incidence small angle X-ray and neutron scattering

Some recent developments in grazing incidence small angle scattering (GISAS) technique are reviewed. The emphasis is on the application of GISAS to elucidating the effects of geometrical surface constraint on self-assembled systems and the effect of modification of interfaces or molecular subassemblies to direct the formation of more complex structures.     

Surface plasma treatment effects on the molecular structure at polyimide/air and buried polyimide/epoxy interfaces

Polyimides are widely used as chip passivation layers and organic substrates in microelectronic packaging. Plasma treatment has been used to enhance the interfacial properties of polyimides, but its molecularmechanism is not clear. In this research, the effects of polyimide surface plasma treatment on the molecular structures at corresponding polyimide/air and buried polyimide/epoxy interfaces were investigated in situ using sum frequency generation (SFG) vibrational spectroscopy. SFG results show that the polyimide backbone molecular structure was different at polyimide/air and polyimide/epoxy interfaces before and after plasma treatment. The different molecular structures at each interface indicate that structural reordering of the polyimide backbone occurred as a result of plasma treatment and contact with the epoxy adhesive. Furthermore, quantitative orientation analysis indicated that plasma treatment of polyimide surfaces altered the twist angle of the polyimide backbone at corresponding buried polyimide/epoxy interfaces. These SFG results indicate that plasma treatment of polymer surfaces can alter the molecular structure at corresponding polymer/air and buried polymer interfaces.     

Control of carboxylic acid and ester groups on chromium (VI) binding to functionalized silica/water interfaces studied by second harmonic generation

Resonantly enhanced surface second harmonic generation (SHG) measurements carried out at pH 7 and room temperature were performed to study how surface-bound carboxylic acid and methyl ester functional groups control the interaction of chromate ions with fused silica/water interfaces. These functional groups were chosen because of their high abundance in humic and fulvic acids and related biopolymers commonly found in soils. They were anchored to the silica surface using organosilane chemistry to avoid competing complexation processes in the aqueous solution as well as competitive adsorption of the organic compounds and chromate. The SHG experiments were carried out at room temperature and pH 7 while using environmentally representative chromate concentrations ranging from 1 x10(-6) to 2 x 10(-4) M. Chromate is found to bind to the acid- and ester-functionalized silica/water interfaces in a reversible fashion. In contrast to the plain silica/water interface, chromate binding studies performed on the functionalized silica/water interfaces show S-shaped adsorption isotherms that can be modeled using the Frumkin-Fowler-Guggenheim (FFG) model. This model predicts a coverage-dependent binding constant of K(ads) x exp(gtheta). Values for g are found to be 3.2(2), 2.1(2), and 1.3(2) for the carboxylic acid-, the ester-, and the nonfunctionalized silica/water interfaces, respectively, and are consistent with stabilizing lateral adsorbate-adsorbate interactions among the Cr(VI) species adsorbed to the functionalized surfaces. The FFG model allows for the parametrization of the solid-liquid partition coefficient and chromate retardation factors in silica-rich soil particles whose surfaces contain organic adlayers rich in carboxylic acid and methyl ester groups. The straightforward model presented here predicts that chromate retardation increases by up to 200% when carboxylic acid functional groups are present at the silica/water interface. Increases up to 50% are predicted for methyl ester-containing organic adlayers, and the retardation factor remains effectively near unity for the plain silica/water interface (no siloxanes present).     

Electrostatic‐Driven Dynamic Jamming of 2D Nanoparticles at Interfaces for Controlled Molecular Diffusion

Dynamically engineering the interfacial interaction of nanoparticles has emerged as a new approach for bottom‐up fabrication of smart systems to tailor molecular diffusion and controlled release. Janus zwitterionic nanoplates are reported that can be switched between a locked and unlocked state at interfaces upon changing surface charge, allowing manipulation of interfacial properties in a fast, flexible, and switchable manner. Combining experimental and modeling studies, an unambiguous correlation is established among the electrostatic energy, the interface geometry, and the interfacial jamming states. As a proof‐of‐concept, the well‐controlled interfacial jamming of nanoplates enabled the switchable molecular diffusion through liquid–liquid interfaces, confirming the feasibility of using nanoparticle‐based surfactants for advanced controlled release.     

Intelligent control of surface hydrophobicity.

Switchable surfaces are highly useful materials with surface properties that change in response to external stimuli. These surfaces can be employed in both research and industrial applications, where the ability to actively control surface properties can be used to develop smart materials and intelligent surfaces. Herein, we review a range of surfaces in which hydrophobicity can be controlled. We present the principal ideas of surface switching, discuss recent developments, explore experimental issues and examine factors that influence surface switching, including the nature of the stimuli, the underlying material, the morphology of the surface and the surrounding environment. We have categorised switchable surfaces according to the stimuli that trigger changes in surface hydrophobicity. These are electrically, electrochemically, thermally, mechanically, photo- and environmentally inducible surfaces. In addition, we review the use of chemical reactions to modify the properties of switchable surfaces and produce changes in the molecular structure and nanoscale features of the surface.