Single-Polymer Friction Force Microscopy of dsDNA Interacting with a Nanoporous Membrane.

Surface-grafted polymers can reduce friction between solids in liquids by compensating the normal load with osmotic pressure, but they can also contribute to friction when fluctuating polymers entangle with the sliding counter face. We have measured forces acting on a single fluctuating double-stranded DNA polymer, which is attached to the tip of an atomic force microscope and interacts intermittently with nanometer-scale methylated pores of a self-assembled polystyrene-block-poly(4-vinylpyridine) membrane. Rare binding of the polymer into the pores is followed by a stretching of the polymer between the laterally moving tip and the surface and by a force-induced detachment. We present results for the velocity dependence of detachment forces and of attachment frequency and discuss them in terms of rare excursions of the polymer beyond its equilibrium configuration.

Human glabrous skin contains crystallized urea dendriform structures in the stratum corneum which affect the hydration levels.

Glabrous skin is hair-free skin with a high density of sweat glands, which is found on the palms, and soles of mammalians, covered with a thick stratum corneum. Dry hands are often an occupational problem which deserves attention from dermatologists. Urea is found in the skin as a component of the natural moisturizing factor and of sweat. We report the discovery of dendrimer structures of crystalized urea in the stratum corneum of palmar glabrous skin using laser scanning microscopy. The chemical and structural nature of the urea crystallites was investigated in vivo by non-invasive techniques. The relation of crystallization to skin hydration was explored. We analysed the index finger, small finger and tenar palmar area of 18 study participants using non-invasive optical methods, such as laser scanning microscopy, Raman microspectroscopy and two-photon tomography. Skin hydration was measured using corneometry. Crystalline urea structures were found in the stratum corneum of about two-thirds of the participants. Participants with a higher density of crystallized urea structures exhibited a lower skin hydration. The chemical nature and the crystalline structure of the urea were confirmed by Raman microspectroscopy and by second harmonic generated signals in two-photon tomography. The presence of urea dendrimer crystals in the glabrous skin seems to reduce the water binding capacity leading to dry hands. These findings highlight a new direction in understanding the mechanisms leading to dry hands and open opportunities for the development of better moisturizers and hand disinfection products and for diagnostic of dry skin.

Revealing the Meissner Corpuscles in Human Glabrous Skin Using In Vivo Non-Invasive Imaging Techniques.

The presence of mechanoreceptors in glabrous skin allows humans to discriminate textures by touch. The amount and distribution of these receptors defines our tactile sensitivity and can be affected by diseases such as diabetes, HIV-related pathologies, and hereditary neuropathies. The quantification of mechanoreceptors as clinical markers by biopsy is an invasive method of diagnosis. We report the localization and quantification of Meissner corpuscles in glabrous skin using in vivo, non-invasive optical microscopy techniques. Our approach is supported by the discovery of epidermal protrusions which are co-localized with Meissner corpuscles. Index fingers, small fingers, and tenar palm regions of ten participants were imaged by optical coherence tomography (OCT) and laser scan microscopy (LSM) to determine the thickness of the stratum corneum and epidermis and to count the Meissner corpuscles. We discovered that regions containing Meissner corpuscles could be easily identified by LSM with an enhanced optical reflectance above the corpuscles, caused by a protrusion of the strongly reflecting epidermis into the stratum corneum with its weak reflectance. We suggest that this local morphology above Meissner corpuscles has a function in tactile perception.

Molecular kinetics and cooperative effects in friction and adhesion of fast reversible bonds.

Molecular mechanisms of adhesion and friction include the rupture of single and multiple bonds. The strength of adhesion and friction thus depends on the molecular kinetics and cooperative effects in the lifetime of bonds under stress. We measured the rate dependence of friction and adhesion mediated by supramolecular guest-host bonds using atomic force microscopy (AFM). The tip of the AFM and the surface were functionalized with cyclodextrin hosts. The influence of molecular kinetics on adhesion and friction was studied using three different ditopic guest molecules that connected the AFM tip and the surface. Adamantane, ferrocene, and azobenzene were the guest end groups of the connector molecules that formed inclusion complexes with the cyclodextrin hosts. The results confirm the importance of the molecular off-rate and of cooperative effects for the strength of adhesion and friction. Positive cooperativity also shapes the dependence of friction on the concentration of connector molecules, which follows the Hill-Langmuir model. Based on the Hill coefficient of 3.6, reflecting a characteristic rupture of at least 3-4 parallel bonds, a rescaling of the pulling rate is suggested that shifts the rate dependence of adhesion and friction for the three different molecules towards one master curve.

Dynamic shear force microscopy of confined liquids at a gold electrode.

The confinement of liquids in nanometer-scale gaps can lead to changes in their viscous shear properties. For liquids of polar molecules, the charge state of the confining surfaces has a significant influence on the structure in the confined liquid. Here we report on the implementation of dynamic shear force microscopy in an electrochemical cell. Lateral oscillations of the tip of an atomic force microscope were magnetically activated at a frequency of about 50 kHz. The damping of the lateral tip oscillation was recorded as a function of the tip-sample distance and of the electrode potential at the surface of a Au(100) single crystal electrode. The influence of surface charges on the shear response of the nano-confined liquids was demonstrated for the ionic liquid [EMIM][NTf2] and for aqueous Na2SO4 solution.

Single-molecule force spectroscopy of fast reversible bonds.

In single-molecule force spectroscopy, the unbinding force is often used to quantify the interaction strength of single molecular bonds. We analyze force spectroscopy of fast reversible bonds probed in thermodynamic equilibrium by considering the dynamics of force probe and molecular linker. The effect of cantilever and linker dynamics is systematically addressed by measuring the unbinding force of single cyclodextrin inclusion complexes by atomic force spectroscopy for a variety of molecular linkers and varying force probe stiffness. The unbinding force of individual bonds probed in thermodynamic equilibrium is not unique for the molecular system but scales with , the square root of the force probe stiffness, and is largely independent of the molecular linker stiffness. The observations are explained by an effective potential resulting from fast linker fluctuations and fast rebinding kinetics which is probed by an AFM cantilever. The slow cantilever dynamics in the kHz range act as mechanical low pass filter, allowing for fast rebinding kinetics of the molecular complex in the order of 106 kHz. The binding energy of the complex can be estimated from the unbinding force as a function of cantilever stiffness, however with some uncertainty arising from lack of a model in three dimensions.

Interactions between shape-persistent macromolecules as probed by AFM.

Water-soluble shape-persistent cyclodextrin (CD) polymers with amino-functionalized end groups were prepared starting from diacetylene-modified cyclodextrin monomers by a combined Glaser coupling/click chemistry approach. Structural perfection of the neutral CD polymers and inclusion complex formation with ditopic and monotopic guest molecules were proven by MALDI-TOF and UV-vis measurements. Small-angle neutron and X-ray (SANS/SAXS) scattering experiments confirm the stiffness of the polymer chains with an apparent contour length of about 130 Å. Surface modification of planar silicon wafers as well as AFM tips was realized by covalent bound formation between the terminal amino groups of the CD polymer and a reactive isothiocyanate-silane monolayer. Atomic force measurements of CD polymer decorated surfaces show enhanced supramolecular interaction energies which can be attributed to multiple inclusion complexes based on the rigidity of the polymer backbone and the regular configuration of the CD moieties. Depending on the geometrical configuration of attachment anisotropic adhesion characteristics of the polymer system can be distinguished between a peeling and a shearing mechanism.

Atomic scale mechanisms of friction reduction and wear protection by graphene.

We study nanoindentation and scratching of graphene-covered Pt(111) surfaces in computer simulations and experiments. We find elastic response at low load, plastic deformation of Pt below the graphene at intermediate load, and eventual rupture of the graphene at high load. Friction remains low in the first two regimes, but jumps to values also found for bare Pt(111) surfaces upon graphene rupture. While graphene substantially enhances the load carrying capacity of the Pt substrate, the substrate's intrinsic hardness and friction are recovered upon graphene rupture.

Impact of van der Waals interactions on single asperity friction.

Single asperity measurements on Si wafers with variable SiO(2) layer thickness, yet identical roughness, revealed the influence of van der Waals (vdW) interactions on friction: on thin (1 nm) SiO(2) layers, higher friction and jump-off forces were observed as compared to thick (150 nm) SiO(2) layers. The vdW interactions were additionally controlled by a set of silanized Si wafers, exhibiting the same trend. The experimental results demonstrate the influence of the subsurface material and are quantitatively described by combining calculations of interactions of the involved materials and the Derjaguin-Müller-Toporov model.

Nanoscale friction on MoS2/graphene heterostructures.

Stacked hetero-structures of two-dimensional materials allow for a design of interactions with corresponding electronic and mechanical properties. We report structure, work function, and frictional properties of 1 to 4 layers of MoS2 grown by chemical vapor deposition on epitaxial graphene on SiC(0001). Experiments were performed by atomic force microscopy in ultra-high vacuum. Friction is dominated by adhesion which is mediated by a deformation of the layers to adapt the shape of the tip apex. Friction decreases with increasing number of MoS2 layers as the bending rigidity leads to less deformation. The dependence of friction on applied load and bias voltage can be attributed to variations in the atomic potential corrugation of the interface, which is enhanced by both load and applied bias. Minimal friction is obtained when work function differences are compensated.

Control of nanoscale friction on gold in an ionic liquid by a potential-dependent ionic lubricant layer.

The lubricating properties of an ionic liquid on gold surfaces can be controlled through application of an electric potential to the sliding contact. A nanotribology approach has been used to study the frictional behavior of 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py(1,4)]FAP) confined between silica colloid probes or sharp silica tips and a Au(111) substrate using atomic force microscopy. Friction forces vary with potential because the composition of a confined ion layer between the two surfaces changes from cation-enriched (at negative potentials) to anion-enriched (at positive potentials). This offers a new approach to tuning frictional forces reversibly at the molecular level without changing the substrates, employing a self-replenishing boundary lubricant of low vapor pressure.

Relationship between corrosion and nanoscale friction on a metallic glass.

Metallic glasses are promising materials for microdevices, although corrosion and friction limit their effectiveness and durability. We investigated nanoscale friction on a metallic glass in corrosive solutions after different periods of immersion time using atomic force microscopy to elucidate the influence of corrosion on nanoscale friction. The evolution of friction upon repeated scanning cycles on the corroded surfaces reveals a bilayer surface oxide film, of which the outer layer is removed by the scanning tip. The measurement of friction and adhesion allows one to compare the physicochemical processes of surface dissolution at the interface of the two layers. The findings contribute to the understanding of mechanical contacts with metallic glasses under corrosive conditions by exploring the interrelation of microscopic corrosion mechanisms and nanoscale friction.

Molecular stiffness cues of an interpenetrating network hydrogel for cell adhesion.

Understanding cells' response to the macroscopic and nanoscale properties of biomaterials requires studies in model systems with the possibility to tailor their mechanical properties and different length scales. Here, we describe an interpenetrating network (IPN) design based on a stiff PEGDA host network interlaced within a soft 4-arm PEG-Maleimide/thiol (guest) network. We quantify the nano- and bulk mechanical behavior of the IPN and the single network hydrogels by single-molecule force spectroscopy and rheological measurements. The IPN presents different mechanical cues at the molecular scale, depending on which network is linked to the probe, but the same mechanical properties at the macroscopic length scale as the individual host network. Cells attached to the interpenetrating (guest) network of the IPN or to the single network (SN) PEGDA hydrogel modified with RGD adhesive ligands showed comparable attachment and spreading areas, but cells attached to the guest network of the IPN, with lower molecular stiffness, showed a larger number and size of focal adhesion complexes and a higher concentration of the Hippo pathway effector Yes-associated protein (YAP) than cells linked to the PEGDA single network. The observations indicate that cell adhesion to the IPN hydrogel through the network with lower molecular stiffness proceeds effectively as if a higher ligand density is offered. We claim that IPNs can be used to decipher how changes in ECM design and connectivity at the local scale affect the fate of cells cultured on biomaterials.

Ageing of a microscopic sliding gold contact at low temperatures.

Nanometer-scale friction measurements on a Au(111) surface have been performed at temperatures between 30 and 300 K by means of atomic force microscopy. Stable stick slip with atomic periodicity is observed at all temperatures, showing only weak dependence on temperature between 300 and 170 K. Below 170 K, friction increases with time and a distortion of the stick-slip characteristic is observed. Low friction and periodic stick slip can be reestablished by pulling the tip out of contact and subsequently restoring the contact. A comparison with molecular dynamics simulations indicates that plastic deformation within a growing gold junction leads to the observed frictional behavior at low temperatures. The regular stick slip with atomic periodicity observed at room temperature is the result of a dynamic equilibrium shape of the contact, as microscopic wear damage is observed to heal in the sliding contact.

Switching atomic friction by electrochemical oxidation.

Friction between the sliding tip of an atomic force microscope and a gold surface changes dramatically upon electrochemical oxidation of the gold surface. Atomic-scale variations of the lateral force reveal details of the friction mechanisms. Stick-slip motion with atomic periodicity on perfect Au(111) terraces exhibits extremely low friction and almost no dependence on load. Significant friction is observed only above a load threshold at which wear of the surface is initiated. In contrast, irregular stick-slip motion and a linear increase of friction with load are observed on electrochemically oxidized surfaces. The observations are discussed with reference to the amorphous structure of the oxo-hydroxide surface and atomic place exchange mechanisms upon oxidation. Reversible, fast switching between the two states of friction has been achieved in both perchloric and sulfuric acid solutions.

Molecular order and disorder in the frictional response of alkanethiol self-assembled monolayers.

Molecular processes in the frictional response of an alkanethiol monolayer, self-assembled on a Au(111) surface, are studied by means of high-resolution friction force microscopy in ultrahigh vacuum. With increasing load, three regimes are observed on defect-free domains of the monolayer: smooth sliding with negligible friction, regular molecular stick-slip motion with increasing friction, and the onset of wear in the monolayer. Molecular contrast in the lateral force is found for inequivalent molecules within the unit cell of the c(4 × 2) superstructure. Significant differences in the frictional response are found between defect-free domains and areas including a domain boundary. Friction increases by an order of magnitude on domain boundaries in connection with irregular stick-slip motion. This increased friction at domain boundaries is observed at loads below the onset of wear.