Air/Water Interface Rheology Probed by Thermal Capillary Waves.

Atomic force microscopy (AFM) was used to study the interfacial rheology of air/water interfaces by investigating the thermal capillary fluctuations of surfactant-loaded interfaces. These interfaces are formed by depositing an air bubble on a solid substrate immersed in a surfactant (Triton X-100) solution. An AFM cantilever, in contact with the north pole of the bubble, probes its thermal fluctuations (amplitude of the vibration versus the frequency). The measured power spectral density of the nanoscale thermal fluctuations presents several resonance peaks corresponding to the different vibration modes of the bubble. The measured damping versus the surfactant concentration of each mode presents a maximum and then decreases to a saturation value. The measurements are in good agreement with the model developed by Levich for the damping of capillary waves in the presence of surfactants. Our results show that the AFM cantilever in contact with a bubble is a powerful tool to probe the rheological properties of air/water interfaces.

Electroviscous drag on squeezing motion in sphere-plane geometry.

Theoretically and experimentally, we study electroviscous phenomena resulting from charge-flow coupling in a nanoscale capillary. Our theoretical approach relies on Poisson-Boltzmann mean-field theory and on coupled linear relations for charge and hydrodynamic flows, including electro-osmosis and charge advection. With respect to the unperturbed Poiseuille flow, we define an electroviscous coupling parameter ξ, which turns out to be maximum where the film height h_{0} is comparable to the Debye screening length λ. We also present dynamic atomic force microscopy data for the viscoelastic response of a confined water film in sphere-plane geometry; our theory provides a quantitative description for the electroviscous drag coefficient and the electrostatic repulsion as a function of the film height, with the surface charge density as the only free parameter. Charge regulation sets in at even smaller distances.

Cross-linked polymer microparticles with tunable surface properties by the combination of suspension free radical copolymerization and Click chemistry.

We propose a general, versatile and broad in scope two-steps approach for the elaboration of cross-linked polymer microparticles (µPs) with tunable functionalities and surface properties. Surface-functionalized cross-linked polymer µPs with diameter in the 80 µm range are prepared by the combination of: 1) suspension free radical copolymerization of styrene, propargyl methacrylate and 1,6-hexanediol dimethacrylate, 2) subsequent covalent tethering of a variety of azide-functionalized moieties (i.e. rhodamine B fluorescent dye or poly(ethylene glycol) (PEG) brush precursor) by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and, 3) optional N-alkylation of the 1,2,3-triazole groups followed by anion exchange reaction to afford covalently-tethered 1,2,3-triazolium ionic liquids with iodide or cresol red counter-anions. The resulting µPs are characterized by laser diffraction, differential scanning calorimetry, as well as by optical, confocal fluorescence, scanning electron and atomic force microscopies. Finally, the rheological properties of concentrated suspensions (volume fractions of 0.40 and 0.44) of the different synthesized µPs dispersed in a 1:1 (vol/vol) mixture of polyalkylene glycol and water are studied. The modification of µPs surface properties contributes not only to change the stability of the suspensions against flocculation, but also to significantly modify their rheological behavior at high shear stresses. This represents a clear experimental evidence of the importance of non-hydrodynamic contact forces in the rheology of non-Brownian suspensions (NBSs).

An experimental study on the role of inter-particle friction in the shear-thinning behavior of non-Brownian suspensions.

This paper focuses on shear-thinning in non-Brownian suspensions. In particular, it proposes a quantitative experimental validation of the model proposed by Lobry et al. [J. Fluid Mech., 2019, 860, 682-710] that links viscosity to microscopic friction between particles and, in particular, shear-thinning to load-dependent friction coefficient. To this aim, Atomic Force Microscopy (AFM) is used to measure the pairwise friction coefficient of polystyrene particles (40 µm in diameter), immersed in a Newtonian liquid, for different normal loads ranging from 10 to 1000 nN. It is shown that the inter-particle friction coefficient decreases with the load, contrarily to what is expected for macroscopic contacting bodies. The experimental friction law is then introduced into the viscosity model proposed by Lobry et al. and the results are compared to the viscosity of suspensions made of the same particles dispersed in the same liquid as those used for AFM measurements. The very good agreement between the measured viscosity values and those predicted by the model of Lobry et al. with the friction coefficient measured by AFM as input data shows the relevance of the scenario proposed by Lobry et al. and highlights the close links between the microscopic friction properties of the particles and the macroscopic rheological behavior of suspensions.

Direct Measurement of the Elastohydrodynamic Lift Force at the Nanoscale.

We present the first direct measurement of the elastohydrodynamic lift force acting on a sphere moving within a viscous liquid, near and along a soft substrate under nanometric confinement. Using atomic force microscopy, the lift force is probed as a function of the gap size, for various driving velocities, viscosities, and stiffnesses. The force increases as the gap is reduced and shows a saturation at small gap. The results are in excellent agreement with scaling arguments and a quantitative model developed from the soft lubrication theory, in linear elasticity, and for small compliances. For larger compliances, or equivalently for smaller confinement length scales, an empirical scaling law for the observed saturation of the lift force is given and discussed.

Viscocapillary Response of Gas Bubbles Probed by Thermal Noise Atomic Force Measurement.

We present thermal noise measurements of a vibrating sphere close to microsized air bubbles in water with an atomic force microscope. The sphere was glued at the end of a cantilever with a resonance frequency of few kHz. The subangstrom thermal motion of the microsphere reveals an elastohydrodynamic coupling between the sphere and the air bubble. The results are in perfect agreement with a model incorporating macroscopic capillarity and fluid flow on the bubble surface with full slip boundary conditions.

Slip length measurement of gas flow.

In this paper, we present a review of the most important techniques used to measure the slip length of gas flow on isothermal surfaces. First, we present the famous Millikan experiment and then the rotating cylinder and spinning rotor gauge methods. Then, we describe the gas flow rate experiment, which is the most widely used technique to probe a confined gas and measure the slip. Finally, we present a promising technique using an atomic force microscope introduced recently to study the behavior of nanoscale confined gas.

Nanobubbles and their role in slip and drag.

Atomic force microscope images of flat solid surfaces in water reveal that very soft objects can be formed on the surfaces. These objects are nanobubbles of gas with sizes ranging from 10 nm to several micrometers. The bubbles are stable to dissolution, lasting for several hours. In this paper we review some of the methods that allow their generation and observation using the atomic force microscope. Next, we describe the influence of the bubbles on liquid slip close to a hydrophobic surface. The influence of liquid-gas menisci, formed as a result of nanobubbles being present on the surface, on drag reduction is also discussed. Finally, data of liquid flow probed on bubbles entrapped on microstructured surfaces are presented.

Slip length measurement of confined air flow on three smooth surfaces.

An experimental measurement of the slip length of air flow close to three different solid surfaces is presented. The substrate was driven by a nanopositioner moving toward an oscillating glass sphere glued to an atomic force microscopy (AFM) cantilever. A large separation distance was used to get more effective data. The slip length value was obtained by analyzing the amplitude and phase data of the cantilever. The measurements show that the slip length does not depend on the oscillation amplitude of the cantilever. Because of the small difference among the slip lengths of the three surfaces, a simplified analysis method was used. The results show that on glass, graphite, and mica surfaces the slip lengths are 98, 234, and 110 nm, respectively.

Hydrogenated and fluorinated surfactants derived from Tris(hydroxymethyl)-acrylamidomethane allow the purification of a highly active yeast F1-F0 ATP-synthase with an enhanced stability.

Loss of stability and integrity of large membrane protein complexes as well as their aggregation in a non-lipidic environment are the major bottlenecks to their structural studies. We have tested C(12)H(25)-S-poly-Tris-(hydroxymethyl)acrylamidomethane (H(12)-TAC) among many other detergents for extracting the yeast F(1)F(0) ATP-synthase. H(12)-TAC was found to be a very efficient detergent for removing the enzyme from mitochondrial membranes without altering its sensitivity towards specific ATP-synthase inhibitors. This extracted enzyme was then solubilized by either dodecyl maltoside (DDM), H(12)-TAC or fluorinated surfactants such as C(2)H(5)-C(6)F(12)-C(2)H(4)-S-poly-Tris-(hydroxymethyl)acrylamidomethane (H(2)F(6)-TAC) or C(6)F(13)-C(2)H(4)-S-poly-Tris-(hydroxymethyl)acrylamidomethane (F(6)-TAC), two surfactants exhibiting a comparable polar head to H(12)-TAC but bearing a fluorinated hydrophobic tail. Preparations from enzymes purified in the presence of H(12)-TAC were found to be more adapted for AFM imaging than ATP-synthase purified with DDM. Keeping H(12)-TAC during the Ni-NTA IMAC purification step or replacing it by DDM at low concentrations did not however allow preserving enzyme activity, while fluorinated surfactants H(2)F(6)-TAC and F(6)-TAC were found to enhance enzyme stability and integrity as indicated by sensitivity towards inhibitors. ATPase specific activity was higher with F(6)-TAC than with H(2)F(6)-TAC. When enzymes were mixed with egg phosphatidylcholine, ATP-synthases purified in the presence of H(2)F(6)-TAC or F(6)-TAC were more stable upon time than the DDM purified enzyme. Furthermore, in the presence of lipids, an activation of ATP-synthases was observed that was transitory for enzymes purified with DDM, but lasted for weeks for ATP-synthases isolated in the presence of molecules with Tris polyalcoholic moieties. Relipidated enzymes prepared with fluorinated surfactants remained highly sensitive towards inhibitors, even after 6 weeks.

Evidence of the no-slip boundary condition of water flow between hydrophilic surfaces using atomic force microscopy.

In this study we present measurements of the hydrodynamic force exerted on a glass sphere glued to an atomic force microscopy (AFM) cantilever approaching a mica surface in water. A large sphere was used to reduce the impact of the cantilever beam on the measurement. An AFM cantilever with large stiffness was used to accurately determine the actual contact position between the sphere and the sample surface. The measured hydrodynamic force with different approach velocities is in good agreement with the Taylor force calculated in the lubrication theory with the no-slip boundary conditions, which verifies that there is no boundary slip on the glass and mica surfaces. Moreover, a detailed procedure of how to subtract the electrostatic double-layer force is presented.

Boundary slip study on hydrophilic, hydrophobic, and superhydrophobic surfaces with dynamic atomic force microscopy.

Slip length has been measured using the dynamic atomic force microscopy (AFM) method. Unlike the contact AFM method, the sample surface approaches an oscillating sphere with a very low velocity in the dynamic AFM method. During this process, the amplitude and phase shift data are recorded to calculate the hydrodynamic damping coefficient, which is then used to obtain slip length. In this study, a glass sphere with a large radius was glued to the end of an AFM cantilever to measure the slip length on rough surfaces. Experimental results for hydrophilic, hydrophobic, and superhydrophobic surfaces show that the hydrodynamic damping coefficient decreases from the hydrophilic surface to the hydrophobic surface and from the hydrophobic one to the superhydrophobic one. The slip lengths obtained on the hydrophobic and superhydrophobic surfaces are 43 and 236 nm, respectively, which indicates increasing boundary slip from the hydrophobic surface to the superhydrophobic one.

Slip-length measurement of confined air flow using dynamic atomic force microscopy.

We present an experimental measurement of the slip length of air flow close to solid surfaces using an atomic force microscope (AFM) in dynamic mode. The air was confined between a glass surface and a spherical glass particle glued to an AFM cantilever. The Knudsen number was varied continuously over three decades by varying the distance between the two surfaces. Our results show that the effect of confining the air is purely dissipative. The data are described by an isothermal Maxwell slip-boundary condition, and the measured slip-length value was 118 nm .

Enzymatic activity of immobilized yeast phosphoglycerate kinase.

This work reports the first evidence that recombinant yeast phosphoglycerate kinase (PGK) is still significantly active when immobilized on glass and muscovite mica. Using previous work to improve the sensitivity of the existing setup, Tapping Mode atomic force microscopy (AFM) was used in a liquid environment to determine the surface enzyme coverage of derivatized mica and glass slides. When associated to spectrophotometric measurements, the AFM data allows assessing the catalytic constant of surface enzymes and comparing it to bulk values. The validity of the Michaelis-Menten model for surface reactions is discussed, supported by spectroscopic measurements of the surface consumption of 1,3-bis-phosphoglycerate (1,3-BPG). Only a few percent of the enzyme material maintains its initial bulk activity. This value could constitute a guideline for biosensors made with the method used here whenever a rapid assessment of the remaining surface activity is needed.

Oscillatory dissipation of a simple confined liquid.

We present a sensitive measurement of the dissipation and the effective viscosity of a simple confined liquid (octamethylcyclotetrasiloxane) using an atomic force microscope. The experimental data show that the damping and the effective viscosity increase and present oscillations as the gap between the cantilever tip and the surface is diminished. To our knowledge, the damping and the viscosity modulation are reported here with such good accuracy for the first time. Such an experimental result is different from what has been reported earlier where only a continuous increase of the damping and the viscosity are observed.

Photothermal imaging of nanometer-sized metal particles among scatterers.

Ambient optical detection of labeled molecules is limited for fluorescent dyes by photobleaching and for semiconducting nanoparticles by "blinking" effects. Because nanometer-sized metal particles do not optically bleach, they may be useful optical labels if suitable detection signals can be found. We demonstrate far-field optical detection of gold colloids down to diameters of 2.5 nanometers with a photothermal method that combines high-frequency modulation and polarization interference contrast. The photothermal image is immune to the effects of scattering background, which limits particle imaging through Rayleigh scattering to diameters larger than 40 nanometers.