Array formation in evanescent waves.
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Journal Article↗
Biomedical subjects
Colin D Bain
Publications and source records attributed to Colin D Bain.
Sum-frequency spectroscopy of a monolayer of zinc arachidate at the solid-solid interface.
Infrared-visible sum-frequency spectroscopy has been used to record the vibrational spectrum of a zinc arachidate monolayer at the interface between a sapphire prism and a fused silica lens. Spectra have been recorded for the monolayer deposited on the prism before, during, and after contact, and as a function of increasing pressure. Sum-frequency spectra are reported of the monolayer under sliding contact. The monolayer is found to be resistant to pressure- and shear-induced conformational disorder. However, frequency shifts, drops in peak intensities, and changes in peak intensity ratios have been observed as the monolayer is placed in contact between the prism and the lens. Transfer of monolayer material between the two surfaces is observed and is confirmed by spectra obtained with a monolayer deposited on the surface of the lens rather than the prism. On one face of the sapphire prism, the monolayer reconstructs to a low symmetry layer, probably due to epitaxy. The epitaxial structure disappeared in contact. Existing models for calculating sum-frequency spectra have been extended to include unit cells containing two molecules and torsion about the terminal C-C bond. This model can explain some, but not all, of the experimental observations.
Journal Article↗
Effects of chain length and heat treatment on the nanotribology of alkylsilane monolayers self-assembled on a rough aluminum surface.
The conformational order of alkylsilane monolayers self-assembled on a rough aluminum surface is affected by the molecular chain length and the thermal history of the sample. These monolayers have been characterized by grazing angle FTIR spectroscopy. Tribological mechanisms were explored using initial molecular conformation order, sliding distance, normal load, and substrate compliance as experimental variables. Results indicate that the initial conformational disorder of the molecules determines the level of friction at the commencement of sliding. Adverse changes in dynamic friction and monolayer life during sliding are not thermally induced but are related to substrate roughness and local plasticity. Plastic deformation reduces the spatial density of the alkylsilane monolayer and is accentuated by an increase in the normal load.
Journal Article↗
Adsorption kinetics in micellar solutions of nonionic surfactants.
Standard models of the adsorption kinetics of surfactants at the air-water surface assume that micelles break down into monomers in the bulk solution and that only monomers adsorb. We show here that micelles of the nonionic surfactant C14E8 adsorb to the surface of a liquid jet at a diffusion-controlled rate. Micellar adsorption can be switched off by incorporation of a small amount of ionic surfactant into the micelle and switched on again by addition of salt. More sophisticated models of adsorption processes in micellar solutions are required that permit a kinetic flux of micelles to the air-water interface.
Adsorption↗
Total internal reflection Raman spectroscopy of barley leaf epicuticular waxes in vivo.
The use of total internal reflection (TIR)-Raman spectroscopy to examine cuticular wax layers in vivo at the surface of barley leaves (Hordeum vulgare L. cultivar Pastoral) is demonstrated. The limited penetration depth (40 nm) of the evanescent wave compared to the thickness of the wax layer eliminates problems arising from fluorescence from underlying pigments. Epicuticular wax crystals are observed to be more crystalline than the amorphous wax layer, which is analysed after removal of the wax crystals by cellulose acetate stripping. Carotenoids are detected as trace species in the cuticular waxes.
Hordeum↗
Penetration of surfactant solutions into hydrophobic capillaries.
The initial rise velocity of surfactant solutions in hydrophobic capillaries is independent of time (F. Tiberg, B. Zhmud, K. Hallstensson and M. von Bahr, Phys. Chem. Chem. Phys., 2000, 2, 5189). By analogy with the hydrodynamics of an overflowing cylinder, we present a steady-state solution for capillary penetration in which the velocity is determined by the adsorption kinetics at the air-water interface. Good agreement between the model predictions and experimental data of Tiberg and coworkers is obtained for the non-ionic surfactant C10E6 under the assumption of diffusion-controlled adsorption. The longer chain homologue, C14E6, shows evidence of kinetic barriers to adsorption.
Adsorption↗
Raman spectra of planar supported lipid bilayers.
Raman scattering has been used to obtain high quality vibrational spectra of planar supported lipid bilayers (pslb's) at the silica/water interface without the use of resonance or surface enhancement. A total internal reflection geometry was used both to increase the bilayer signal and to suppress the water background. Polarization control permits the determination of four components of the Raman tensor, of which three are independent for a uniaxial film. Spectra are reported of the phospholipids DMPC, DPPC, and POPC, in the C-H stretching region and the fingerprint region. The temperature-dependent polarized spectra of POPC show only small changes over the range 14-41 degrees C. The corresponding spectra of DMPC and DPPC bilayers show large thermal changes consistent with a decreasing tilt angle from the surface normal and increasing chain ordering at lower temperatures. The thermal behavior of DMPC pslb's is similar to that of vesicles of the same lipid in bulk suspension. In contrast to calorimetry, which shows a sharp phase transition (L alpha-L beta') with decreasing temperature, the changes in the Raman spectra occur over a temperature range of ca. 10 degrees C commencing at the calorimetric phase transition temperature.
Androstanes↗
Wetting of surfactant solutions by alkanes.
Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided.
Journal Article↗
Surface freezing of chain molecules at the liquid-liquid and liquid-air interfaces.
Surface freezing (SF) is the formation of a crystalline monolayer at the free surface of a melt at a temperature Ts, a few degrees above the bulk freezing temperature, Tb. This effect, i.e. Ts > Tb, common to many chain molecules, is in a marked contrast with the surface melting effect, i.e. Ts < or = Tb, shown by almost all other materials. Depending on chain length, n, the SF layer shows a variety of phases, in some cases tuneable by bulk additives. The SF behaviour of binary mixtures of different-length alkanes and alcohols is governed by the relative chain length mismatch, /delta n/n/2, yielding a quasi-"universal" behaviour for the freezing of both bulk and surface. While SF at the liquid air interface was studied rather extensively, Lei and Bain (Phys. Rev. Lett., 2004, 94, 176103) have shown only very recently that interfacial freezing (IF) can be induced also at the water: tetradecane interface by adding the ionic surfactant CTAB to the water phase. We present measurements of the interfacial tension of the water: hexadecane interface, as a function of temperature and the ionic surfactant STAB, revealing IF at a STAB-concentration-dependent temperature Ti > Tb. The measurements indicate that a single frozen monolayer is formed, with a temperature-existence range of up to 10 degrees C, much larger than the 1.2 degrees C found for SF at the free surface of the melt. We also find a new effect, where the IF allows tuning of the interfacial tension between the two bulk phases to zero for a range of temperatures, deltaT = Tmix - Tb < or = Ti - Tb by cooling the system below Ti. We discuss qualitatively the factors stabilizing the frozen layer and their variation from the liquid-air to the liquid-liquid interfaces. The surfactant concentration dependence of Ti is also discussed and a tentative theoretical explanation is suggested.
Journal Article↗
External reflection Fourier transform infrared spectroscopy of surfactants at the air-water interface: separation of bulk and adsorbed surfactant signals.
External reflection Fourier transform infrared spectroscopy (ERFTIRS) has been used to obtain spectra of monolayers of the hydrocarbon surfactant octaethylene glycol monodecyl ether (C(10)E(8)) and the fluorocarbon surfactant ammonium perfluorononanoate (APFN) at the expanding liquid surface of an overflowing cylinder. The use of target factor analysis (TFA) to separate out the contributions of water, adsorbed surfactant, and dissolved surfactant is demonstrated. For both surfactants, there is a linear relationship between the component weight of the adsorbed surfactant, obtained by TFA, and the surface excess determined independently by ellipsometry or neutron reflection. This linear relationship suggests that the monolayers behave like isotropic films with a constant density. A sensitivity of less than 10% of a monolayer is demonstrated. The benefits of using a multivariate curve fitting procedure to analyze sets of ER-FTIR spectra are discussed and some potential pitfalls are identified. This technique is also applicable to static interfaces.
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External reflection FTIR spectroscopy of the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) on an overflowing cylinder.
External reflection Fourier transform infrared spectroscopy (ER-FTIRS) has been used to study the adsorption of the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) at the air-water interface under nonequilibrium conditions. An overflowing cylinder (OFC) was used to generate a continually expanding liquid surface with a surface age of 0.1-1 s. ER-FTIR spectra were acquired by a single bounce of p- or s-polarized radiation from the flowing surface of the OFC. The C-H stretching region of CTAB spectra was analyzed both by subtraction of a reference spectrum of pure water and by a chemometric technique known as target factor analysis (TFA). The TFA method is shown to give lower scatter in the weight of the component assignable to the adsorbed CTAB monolayer and to permit analysis of spectra at lower bulk surfactant concentrations. The surface sensitivity of ER-FTIRS is demonstrated both experimentally and by theoretical modeling. Modeling shows that surfactant adsorbed at the surface and dissolved in the bulk solution can be distinguished by reflection spectroscopy but also highlights potential errors that can arise from the neglect of the bulk surfactant contribution to the ER-FTIR spectra. Polarized spectra are consistent with an isotropic distribution of transition dipole moments of the hydrocarbon chains in CTAB. Component weights of the CTAB monolayer determined by TFA are compared with an independent determination of values of the dynamic surface excess, Gammadyn, by neutron reflection and ellipsometry. The relationship between the component weights and Gammadyn shows a small but significant deviation from linearity. Possible explanations for this deviation are discussed. The feasibility of using TFA to deconvolute ER-FTIR spectra of mixtures of hydrocarbon surfactants is demonstrated.
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Adsorption of ionic surfactants at an expanding air-water interface.
A quantitative model for the kinetics of adsorption of ionic surfactants to an expanding liquid surface is presented for surfactant concentrations below and above the critical micelle concentration (cmc). For surfactant concentrations below the cmc, the electrostatic double layer is accounted for explicitly in the adsorption isotherm. An overflowing cylinder (OFC) was used to create nonequilibrium liquid surfaces under steady-state conditions. Experimental measurements of the surface excess for solutions of cationic surfactants CH3(CH2)n-1N+(CH3)3 Br- (CnTAB, n = 12, 14, 16) and the anionic fluorocarbon surfactant sodium bis(1H,1H-nonafluoropentyl)-2-sulfosuccinate (di-CF4) in the OFC are in excellent agreement with the theoretical predictions for diffusion-controlled adsorption for all concentrations studied below the cmc. For surfactant concentrations above cmc, the diffusion ofmicelles and monomers are handled separately under the assumption of fast micellar breakdown. This simplified model gives excellent agreement for the system C14TAB + 0.1 M NaBr above the cmc. Agreement between theory and experiment for C16TAB + 0.1 M NaBr is less good. A plausible explanation for the discrepancy is that micellar breakdown is no longer fast on the time scale of the OFC (ca. 0.1 s).
Journal Article↗
Surfactant-induced surface freezing at the alkane-water interface.
Long-chain alkanes exhibit surface freezing at the alkane-air but not the alkane-water interface. Ellipsometry and surface tensiometry are used to show that a simple cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), can induce surface freezing at the tetradecane-water interface even when present in mole fractions as low as 0.1. The surface-freezing temperature T(s) is a linear function of the interfacial excess of CTAB. The excess surface entropy below T(s), S(sigma)=-0.76+/-0.02 mJ K-1 m(-2), is consistent with a rotator phase. Ellipsometry provides strong evidence for a frozen monolayer in which the chains are oriented near the surface normal.
Journal Article↗
Rapid method for measurement of surface tension in multiwell plates.
We describe an optical method for quantifying surface tension in 96-well microtitre plates. Absorbance and fluorescence measurements in vertical beam systems as in 96-well plate photometers are complicated by the interaction of the light with the curved surface of the liquid. If the samples do not all have the same meniscus, errors in the data proportional to the degree of curvature are produced, which may confound interpretation of the data. We have harnessed this effect by modifying a 96-well plate spectrophotometer, and show that the apparent optical density measurements correlate very closely with surface tension. The method is much quicker than conventional methods for measuring multiple samples and requires considerably less technical skill. We demonstrate the applicability of the method to the study of biomolecules by investigating the surfactant properties of two peptides (Abeta and AChE(586-599)) that form amyloid fibrils in vitro, in one case replicating previously published results, and in the other case highlighting the similarity, and possibly generic nature, of the biophysical properties of these amyloidogenic peptides.
Acetylcholinesterase↗
Surfactant adsorption and Marangoni flow in liquid jets. I. Experiments.
The adsorption of surfactants at an expanding liquid surface has been studied in a gravity-driven laminar water jet with Reynolds numbers in the range from 1000 to 2000. Surface concentrations of hexadecyltrimethylammonium bromide (C(16)TAB) were deduced from ellipsometric measurements, using a calibration made previously with neutron reflection. Simultaneous measurements of the velocity profile within the jet were made with laser Doppler velocimetry. These two noninvasive techniques were able to measure conditions to within 1 mm of the nozzle, where rates of surface expansion were as high as 300 s(-1). For the laminar jet without surfactant, the measurements are in excellent agreement with CFD calculations and with the theoretical result that the surface velocity varies as z(1/3), where z is the distance from the nozzle. Close to the nozzle the high rate of surface expansion drives both rapid diffusional transport to the surface, and rapid convection on the surface, resulting in a low concentration of surfactant. Higher concentrations of surfactant downstream cause a Marangoni stress which decelerates the surface-an effect clearly shown by the velocity data. In the presence of 0.2 M salt, which significantly depresses the cmc, the adsorption of C(16)TAB is greatly reduced, probably because it forms cylindrical micelles, which diffuse much more slowly than free monomers. The apparatus is shown to be a very suitable platform for investigating surfactant adsorption and Marangoni flows under carefully controlled hydrodynamic conditions.
Journal Article↗
Surfaces designed for charge reversal.
We have created surfaces which switch from cationic at pH < 3 to anionic at pH > 5, by attaching aminodicarboxylic acid units to silica and gold substrates. Charge reversal was demonstrated by monitoring the adsorption of cationic dyes (methylene blue and a tetracationic porphyrin) and an anionic sulfonated porphyrin, at a range of pH using UV-vis absorption and reflection spectroscopy. The cationic dyes bind under neutral conditions (pH 5-7) and are released at pH 1-4, whereas the anionic dye binds under acidic conditions (pH 1-4) and is released at pH 5-7. Gold surfaces were functionalized with two different amphoteric disulfides with short (CH(2))(2) and long (CH(2))(10)CONH(CH(2))(6) linkers; the longer disulfide gave surfaces exhibiting charge reversal in a narrower pH range. Adsorption is much faster on the functionalized gold (t(1/2) = 62 s) than on functionalized silica (t(1/2) = 6900 s), but the final extents of coverage on both surface are similar, for a given dye at a given pH, with maximal coverages of around 2 molecules nm(-)(2). These charge-reversal processes are reversible and can be repeatedly cycled by changing the pH. We have also created surfaces which undergo irreversible proton-triggered charge switching, using a carbamate-linked thiol carboxylic acid which cleaves in acid. These surfaces are versatile new tools for controlling electrostatic self-assembly at surfaces.
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