Torbjörn Pettersson

Comparison of different methods to calibrate torsional spring constant and photodetector for atomic force microscopy friction measurements in air and liquid

A number of atomic force microscopy cantilevers have been exhaustively calibrated by a number of techniques to obtain both normal and frictional force constants to evaluate the relative accuracy of the different methods. These were of either direct or indirect character-the latter relies on cantilever resonant frequencies. The so-called Sader [Rev. Sci. Instrum. 70, 3967 (1999)] and Cleveland [Rev. Sci. Instrum. 64, 403 (1993)] techniques are compared for the normal force constant calibration and while agreement was good, a systematic difference was observed. For the torsional force constants, all the techniques displayed a certain scatter but the agreement was highly encouraging. By far the simplest technique is that of Sader, and it is suggested in view of this validation that this method should be generally adopted. The issue of the photodetector calibration is also addressed since this is necessary to obtain the cantilever twist from which the torsional force is calculated. Here a technique of obtaining the torsional photodetector sensitivity by combining the direct and indirect methods is proposed. Direct calibration measurements were conducted in liquid as well as air, and a conversion factor was obtained showing that quantitative friction measurements in liquid are equally feasible provided the correct calibration is performed.

Lubrication Properties of Bottle-Brush Polyelectrolytes : An AFM Study on the Effect of Side Chain and Charge Density

The effect of side chain to charge ratio on the frictional properties of adsorbed layers formed by bottle-brush polyelectrolytes with poly(ethylene oxide) side chains has been investigated. The brush polyelectrolytes were preadsorbed from 0.1 mM NaNO(3) solutions onto mica and silica surfaces; the interfacial friction was then measured in polyelectrolyte-free solutions via AFM (with the silica surface acting as the colloidal probe). It was concluded that the decisive factor for achieving favorable lubrication properties is the concentration of nonadsorbing poly(ethylene oxide) side chains in the interfacial region. However, contrary to what may be expected, the results showed that an ideal brush layer structure with the adsorbed polymers adopting comb-like conformation is not necessary for achieving a low coefficient of friction in the asymmetric mica-silica system. In fact, the lowest coefficient of friction (<0.01) under applied pressures as high as 30 MPa was observed for a system with a side chain to charge ratio of 9:1, incapable of forming brush-like layers.

Normal and friction forces between mucin and mucin–chitosan layers in absence and presence of SDS

Employing the colloidal probe AFM technique we have investigated normal and friction forces between flat mica surfaces and silica particles coated with mucin and combined mucin-chitosan layers in presence and absence of anionic surfactant, SDS, in 30 mM NaCl solution. We have shown that the normal interactions between mucin coated mica and silica surfaces are dominated by long-range steric repulsion on both compression and decompression. Friction forces between such mucin layers are characterized by a low effective friction coefficient, mu(eff)=0.03+/-0.02, which is lower than the value of 0.13+/-0.02 observed when chitosan layers were adsorbed. Forces between combined mucin-chitosan layers have also been measured. Adsorption of chitosan on mucin results in considerable compaction of the layer, and development of attractive forces detectable on separation. Friction between mucin-chitosan layers in 30 mM NaCl solution is high, with mu(eff) approximately 0.4. Adsorption of additional mucin to this layer results in no improvement with respect to lubrication as compared to the mucin-chitosan layer, and mu(eff) approximately 0.4 is observed. We argue that the layers containing both mucin and chitosan are not strictly layered but rather strongly entangled. As a result attractive interactions between oppositely charged moieties of sialic acid residues from mucin and amine groups from chitosan residing on the opposing surfaces contribute to the increased friction. The effects of SDS on normal and friction forces between combined mucin-chitosan layers were also investigated. The relation between surface interactions and friction properties is discussed.

Oncogenes induce a vimentin filament collapse mediated by HDAC6 that is linked to cell stiffness

Significance Oncogenes deregulate fundamental cellular functions, which can lead to the development of tumors and metastases. We show that oncogenes change the spatial organization of the vimentin fibers of the intracellular cytoskeleton, induce cell stiffness, and promote the invasive capacity of cells. We further show that this vimentin reorganization and increased cell stiffness requires histone deacetylase 6 (HDAC6). Taken together, these data support the concept that oncogenes can induce cellular stiffness via HDAC6-dependent reorganization of the vimentin filament network. These findings—that key molecules in oncogenic cell transformation, such as oncogenes and HDAC6, can modulate cell stiffness—highlight the importance of the need for further investigation of the mechanical properties of cells to better understand the mechanisms behind tumor and metastasis formation. Oncogenes deregulate fundamental cellular functions, which can lead to development of tumors, tumor-cell invasion, and metastasis. As the mechanical properties of cells govern cell motility, we hypothesized that oncogenes promote cell invasion by inducing cytoskeletal changes that increase cellular stiffness. We show that the oncogenes simian virus 40 large T antigen, c-Myc, and cyclin E induce spatial reorganization of the vimentin intermediate filament network in cells. At the cellular level, this reorganization manifests as increased width of vimentin fibers and the collapse of the vimentin network. At nanoscale resolution, the organization of vimentin fibers in these oncogene-expressing cells was more entangled, with increased width of the fibers compared with control cells. Expression of these oncogenes also resulted in up-regulation of the tubulin deacetylase histone deacetylase 6 (HDAC6) and altered spatial distribution of acetylated microtubules. This oncogene expression also induced increases in cellular stiffness and promoted the invasive capacity of the cells. Importantly, HDAC6 was required and sufficient for the structural collapse of the vimentin filament network, and was required for increased cellular stiffness of the oncogene-expressing cells. Taken together, these data are consistent with the possibility that oncogenes can induce cellular stiffness via an HDAC6-induced reorganization of the vimentin intermediate filament network.

Adhesive Layer-by-Layer Films of Carboxymethylated Cellulose Nanofibril–Dopamine Covalent Bioconjugates Inspired by Marine Mussel Threads

The preparation of multifunctional films and coatings from sustainable, low-cost raw materials has attracted considerable interest during the past decade. In this respect, cellulose-based products possess great promise due not only to the availability of large amounts of cellulose in nature but also to the new classes of nanosized and well-characterized building blocks of cellulose being prepared from trees or annual plants. However, to fully utilize the inherent properties of these nanomaterials, facile and also sustainable preparation routes are needed. In this work, bioinspired hybrid conjugates of carboxymethylated cellulose nanofibrils (CNFC) and dopamine (DOPA) have been prepared and layer-by-layer (LbL) films of these modified nanofibrils have been built up in combination with a branched polyelectrolyte, polyethyleneimine (PEI), to obtain robust, adhesive, and wet-stable nanocoatings on solid surfaces. It is shown that the chemical functionalization of CNFCs with DOPA molecules alters their conventional properties both in liquid dispersion and at the interface and also influences the LbL film formation by reducing the electrostatic interaction. Although the CNFC-DOPA conjugates show a lower colloidal stability in aqueous dispersions due to charge suppression, it was possible to prepare the LbL films through the consecutive deposition of the building blocks. Adhesive forces between multilayer films prepared using chemically functionalized CNFCs and a silica probe are much stronger in the presence of Fe(3+) than those between a multilayer film prepared from unmodified nanofibrils and a silica probe. The present work demonstrates a facile way to prepare chemically functionalized cellulose nanofibrils whereby more extended applications can produce novel cellulose-based materials with different functionalities.

How to measure forces with atomic force microscopy without significant influence from nonlinear optical lever sensitivity

In an atomic force microscope (AFM), the force is normally sensed by measuring the deflection of a cantilever by an optical lever technique. Experimental results show a nonlinear relationship between the detected signal and the actual deflection of the cantilever, which is widely ignored in literature. In this study we have designed experiments to investigate different possible reasons for this nonlinearity and compared the experimental findings with calculations. It is commonly assumed that this nonlinearity only causes problems for extremely large cantilever deflections. However, our results show that the nonlinear detector response might influence many AFM studies where soft or short cantilevers are used. Based on our analysis we draw conclusions of the main reason for the nonlinearity and suggest a rule of thumb for which cantilevers one should use under different experimental conditions.

Mucin-Electrolyte Interactions at the Solid-Liquid Interface Probed by QCM-D

The interaction between mucin and ions has been investigated by employing the quartz crystal microbalance technique with measurement of energy dissipation. The study was partially aimed at understanding the adsorption of mucin on surfaces with different chemistry, and for this purpose, surfaces exposing COOH, OH, and CH(3) groups were prepared. Mucin adsorbed to all three types of functionalized gold surfaces. Adsorption to the hydrophobic surface and to the charged hydrophilic surface (COOH) occured with high affinity despite the fact that in the latter case both mucin and the surface were negatively charged. On the uncharged hydrophilic surface exposing OH groups, the adsorption of mucin was very low. Another aim was to elucidate conformational changes induced by electrolytes on mucin layers adsorbed on hydrophobic surfaces from 30 mM NaNO(3). To this end, we investigated the effect of three electrolytes with increasing cation valance: NaCl, CaCl(2) and LaCl(3). At low NaCl concentrations, the preadsorbed layer expands, whereas at higher concentrations of NaCl the layer becomes more compact. This swelling/compacting of the mucin layer is fully reversible for NaCl. When the mucin layer instead is exposed to CaCl(2) or LaCl(3), compaction is observed at 1 mM. For CaCl(2), this process is only partially reversible, and for LaCl(3), the changes are irreversible within the time frame of the experiment. Finally, mucin interaction with the DTAB cationic surfactant in an aqueous solution of different electrolytes was evaluated with turbidimetry measurements. It is concluded that the electrolytes used in this work screen the association between mucin and DTAB and that the effect increases with increasing cation valency.

Water drop friction on superhydrophobic surfaces.

To investigate water drop friction on superhydrophobic surfaces, the motion of water drops on three different superhydrophobic surfaces has been studied by allowing drops to slide down an incline and capturing their motion using high-speed video. Two surfaces were prepared using crystallization of an alkyl ketene dimer (AKD) wax, and the third surface was the leaf of a Lotus (Nelumbo Nucifera). The acceleration of the water droplets on these superhydrophobic surfaces was measured as a function of droplet size and inclination of the surface. For small capillary numbers, we propose that the energy dissipation is dominated by intermittent pinning-depinning transitions at microscopic pinning sites along the trailing contact line of the drop, while at capillary numbers exceeding a critical value, energy dissipation is dominated by circulatory flow in the vicinity of the contacting disc between the droplet and the surface. By combining the results of the droplet acceleration with a theoretical model based on energy dissipation, we have introduced a material-specific coefficient called the superhydrophobic sliding resistance, b(sh). Once determined, this parameter is sufficient for predicting the motion of water drops on superhydrophobic surfaces of a general macroscopic topography. This theory also infers the existence of an equilibrium sliding angle, β(eq), at which the drop acceleration is zero. This angle is decreasing with the radius of the drop and is in quantitative agreement with the measured tilt angles required for a stationary drop to start sliding down an incline.

Physical Tuning of Cellulose-Polymer Interactions Utilizing Cationic Block Copolymers Based on PCL and Quaternized PDMAEMA

In this work, the objective was to synthesize and evaluate the properties of a compatibilizer based on poly(ε-caprolactone) aimed at tuning the surface properties of cellulose fibers used in fiber-reinforced biocomposites. The compatibilizer is an amphiphilic block copolymer consisting of two different blocks which have different functions. One block is cationic, quaternized poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and can therefore electrostatically attach to anionic reinforcing materials such as cellulose-based fibers/fibrils under mild conditions in water. The other block consists of poly(ε-caprolactone) (PCL) which can decrease the surface energy of a cellulose surface and also has the ability to form physical entanglements with a PCL surface thereby improving the interfacial adhesion. Atom Transfer Radical Polymerization (ATRP) and Ring-Opening Polymerization (ROP) were used to synthesize three block copolymers with the same length of the cationic PDMAEMA block but with different lengths of the PCL blocks. The block copolymers form cationic micelles in water which can adsorb to anionic surfaces such as silicon oxide and cellulose-model surfaces. After heat treatment, the contact angles of water on the treated surfaces increased significantly, and contact angles close to those of pure PCL were obtained for the block copolymers with longer PCL blocks. AFM force measurements showed a clear entangling behavior between the block copolymers and a PCL surface at about 60 °C, which is important for the formation of an adhesive interface in the final biocomposites. This demonstrates that this type of amphiphilic block copolymer can be used to improve interactions in biocomposites between anionic reinforcing materials such as cellulose-based fibers/fibrils and less polar matrices such as PCL.

Probing material properties of polymeric surface layers with tapping mode AFM: Which cantilever spring constant, tapping amplitude and amplitude set point gives good image contrast and minimal surface damage?

A phase shift between the oscillatory motion and drive motion of an AFM-cantilever used for tapping mode AFM imaging can be related to adhesive and elastic properties of surface layers. In this study it was studied how optimal contrast between hard and soft surface layers can be achieved while minimizing the surface damage. This was investigated by performing classical force-distance measurements while driving the cantilever as in tapping mode imaging. The amplitude and phase response as a function of the average tip-surface separation was recorded. Five different cantilevers with a wide range of spring constants and four different tapping amplitudes were investigated and compared. Based on these experiments it is concluded that too stiff cantilever, high free tapping amplitude and low amplitude set point value often lead to surface damage, while too low spring constant and low free tapping amplitude result in poor phase image contrast. Intermediate values where little surface damage and significant image contrast are obtained were identified. In all cases it was observed that the best image contrast was obtained when the amplitude set point was chosen such that the amplitude during imaging was reduced to approximately 50% of the free amplitude.