Colin D. Bain

Sum-frequency vibrational spectroscopy of the solid/liquid interface

Sum-frequency spectroscopy (SFS) is a non-linear optical technique that yields vibrational spectra of molecules at interfaces. A brief summary of the theoretical background to SFS is provided and the origin of its unusual selection rules is explained. The application of SFS to the study of organic molecules at the solid/liquid interface is reviewed. Areas covered include liquid structure at solid surfaces, electrochemistry and the adsorption of surfactants at the solid/water interface.

Adsorption of CTAB on Hydrophilic Silica Studied by Linear and Nonlinear Optical Spectroscopy

Vibrational sum-frequency spectroscopy (SFS) and total internal reflection Raman scattering (TIR Raman) have been used to study the adsorption of hexadecyltrimethylammonium bromide (CTAB) to hydrophilic silica. These two complementary techniques permit the determination of the adsorbed amount with a sensitivity of approximately 1% of the maximum surface coverage, changes in the average tilt of the adsorbed molecules, the presence of asymmetric aggregates in the adsorbed film, and the structure and orientation of the water molecules in the interfacial region. The TIR Raman spectra show a monotonic increase with CTAB concentration with no measurable changes in the relative intensities of the different polarization combinations probed, implying that no significant changes occur in the conformational order of the hydrocarbon chain. In the sum-frequency (SF) spectra, no detectable peaks from the surfactant headgroup and hydrophobic chain were observed at any surface coverage. Major changes are observed in the water bands of the SF spectra, as the originally negatively charged silica surface becomes positively charged with an increase in the adsorbed amount, inducing a change in the polar orientation of the water molecules near the surface. The detection limits for hydrocarbons chains in the SF spectra were estimated by comparison with the SF spectrum of a disordered octadecyltrichlorosilane monolayer. The simulations demonstrate that the asymmetry in the adsorbed CTAB layer at any concentration is less than 5% of a monolayer. The results obtained pose severe constraints on the possible structural models, in particular at concentrations below the critical micellar concentration where information is scarce. The formation of hemimicelles, monolayers and other asymmetric aggregates is ruled out, with centrosymmetric aggregates forming from early on in the adsorption process.

SUM-FREQUENCY VIBRATIONAL SPECTROSCOPY OF SOLUBLE SURFACTANTS AT THE AIR/WATER INTERFACE

Vibrational spectra of seven surfactants adsorbed at the surface of aqueous solutions have been obtained by IR–VIS sum-frequency generation. From these spectra the degree of conformational disorder and the angle of the terminal methyl group are inferred. In general, the number of gauche conformations increases as the area per chain increases. The angle of the methyl group, which is an indicator of the tilt of the hydrocarbon chains, is not simply related to the area per chain. Comparison of surfactants with the same chain length and area per molecule shows that the structure of the chain region of the monolayer is sensitive to the nature of the head group and not just to the packing density. Quantitative models to explain peak intensities in sum-frequency spectra of surfactants are discussed critically.

Sum-frequency generation from thiophenol on silver in the mid and far-IR

Sum-frequency (SF) spectra of a monolayer of thiophenol on silver are reported in the mid and far-IR (infrared). The free-electron laser FELIX was used to reach wavelengths up to 54 μm. Molecular vibrations of thiophenol are observed at wavelengths near 10 μm (three modes), 14 μm (1 mode), and 24 μm (1 mode). The appearance of the different vibrational modes in the spectra varies dramatically due to interference between the resonant sum-frequency signal and the nonresonant sum-frequency signal from silver. The standard model used to describe line shapes in SF spectra is shown to be insufficient to explain the different line shapes for the various vibrational modes of thiophenol on silver.

Polarization effects in optically bound particle arrays

Sub-micron polystyrene spheres spontaneously assemble into twodimensional arrays in the evanescent field of counterpropagating laser beams at the silica-water interface. The symmetry and dynamics of these arrays depends on the particle size and the polarization of the two laser beams. Here we describe the polarization effects for particles with diameters of 390-520 nm, which are small enough to form regular 2-D arrays yet large enough to be readily observed with an optical microscope. We report the observation of rectangular arrays, three different types of hexagonal arrays and a defective array in which every third row is missing. The structure of the arrays is determined by both optical trapping and optical binding. Optical binding can overwhelm optical trapping and give rise to an array that is incommensurate with the interference fringes formed by two laser beams of the same polarization.

Hydrated Electrons at the Water/Air Interface

The dynamics of hydrated electrons at the water/air interface are investigated using time-resolved second-harmonic generation spectroscopy. Initial solvation occurs in approximately 1 ps, and the electron remains at the interface for >750 ps. The location of the electron relative to the dividing surface is investigated using surfactants, which show that the electron is hydrated in the interfacial region, below the dividing surface.

Mixtures of n-dodecyl-β-d-maltoside and hexaoxyethylene dodecyl ether — Surface properties, bulk properties, foam films, and foams

Mixtures of the two non-ionic surfactants hexaoxyethylene dodecyl ether (C(12)E(6)) and n-dodecyl-beta-D-maltoside (beta-C(12)G(2)) were studied with regard to surface properties, bulk properties, foam films, and foams. The reason for studying a mixture of an ethylene oxide (C(i)E(j)) and a sugar (C(n)G(m)) based surfactant is that despite being non-ionic, these two surfactants behave quite differently. Firstly, the physico-chemical properties of aqueous solutions of C(n)G(m) surfactants are less temperature-sensitive than those of C(i)E(j) solutions. Secondly, the surface charge density q(0) of foam films stabilized by C(n)G(m) surfactants is pH insensitive down to the so-called isoelectric point, while that of foam films stabilized by C(i)E(j) surfactants changes linearly with the pH. The third difference is related to interaction forces between solid surfaces. Under equilibrium conditions very high forces are needed to expel beta-C(12)G(2) from between thiolated gold surfaces, while for C(12)E(6) low loads are sufficient. Fourthly, the adsorption of C(12)E(6) and beta-C(12)G(2) on hydrophilic silica and titania, respectively, is inverted. While the surface excess of C(12)E(6) is large on silica and negligible on titania, beta-C(12)G(2) adsorbs very little on silica but has a large surface excess on titania. What is the reason for this different behaviour? Under similar conditions and for comparable head group sizes, it was found that the hydration of C(i)E(j) surfactants is one order of magnitude higher but on average much weaker than that of C(n)G(m) surfactants. Moreover, C(n)G(m) surfactants possess a rigid maltoside unit, while C(i)E(j) surfactants have a very flexible hydrophilic part. Indeed, most of the different properties mentioned above can be explained by the different hydration and the head group flexibilities. The intriguing question of how mixtures of C(i)E(j) and C(n)G(m) surfactants would behave arises organically. Thus various properties of C(12)E(6)+beta-C(12)G(2) mixtures in aqueous solution have been studied with a focus on the 1:1 mixture. The results are compared with those of the single surfactants and are discussed accordingly.

A sum-frequency study of the two-dimensional phase transition in a monolayer of undecanol on water

Abstract Sum-frequency (SF) vibrational spectra are presented of monolayers of 1-undecanol on water in the vicinity of the first-order phase transition at 28°C. A combined analysis of SF and ellipsometric data permits the calculation of the molecular tilt and area per molecule in the high-temperature phase. The SF spectra demonstrate that the monolayer remains highly conformationally ordered above the phase transition.

Total internal reflection spectroscopy for studying soft matter

Total internal reflection (TIR) spectroscopy is a widely used technique to study soft matter at interfaces. This tutorial review aims to provide researchers with an overview of the principles, experimental design and applications of TIR spectroscopy to enable them to understand how this class of techniques might be used in their research. It also highlights limitations and pitfalls of TIR techniques, which will assist readers in critically analysing the literature. Techniques covered include attenuated total reflection infrared spectroscopy (ATR-IR), TIR fluorescence, TIR Raman scattering and cavity-enhanced techniques. Other related techniques are briefly described.

Control of the Particle Distribution in Inkjet Printing through an Evaporation-Driven Sol–Gel Transition

A ring stain is often an undesirable consequence of droplet drying. Particles inside evaporating droplets with a pinned contact line are transported toward the periphery by radial flow. In this paper, we demonstrate how suspensions of laponite can be used to control the radial flow inside picoliter droplets and produce uniform deposits. The improvement in homogeneity arises from a sol-gel transition during evaporation. Droplets gel from the contact line inward, reducing the radial motion of particles and thus inhibiting the formation of a ring stain. The internal flows and propagation of the gelling front were followed by high-speed imaging of tracer particles during evaporation of the picoliter droplets of water. In the inkjet nozzle, the laponite network is broken down under high shear. Recovery of the low shear viscosity of laponite suspensions was shown to be fast with respect to the lifetime of the droplet, which was instrumental in controlling the deposit morphology. The radial and vertical particle distributions within dried deposits were measured for water droplets loaded with 1 and 5 wt % polystyrene spheres and various concentrations of laponite. Aggregation of the polystyrene spheres was suppressed by the addition of colloidal silica. The formulation can be tuned to vary the deposit profile from a ring to a pancake or a dome.