The Barthlott effect.

In 1997, Barthlott and Neinhuis published a groundbreaking article entitled "Purity of the sacred lotus, or escape from contamination in biological surfaces" that caused a true paradigm shift in surface science. In this article, they explained the water-repellent and self-cleaning properties of plants, attributing the superhydrophobicity to nano- and micrometric wax textures on the surface of the leaves. This became known as the "Lotus Effect". In the late 1980s, Barthlott already demonstrated the microtexture of plant surfaces and its effect on wetting. However, this knowledge remained confined to botany until the 1997 article popularized it. The dissemination of this knowledge to the materials science community led to the development of countless synthetic superhydrophobic surfaces and a better understanding of wetting mechanisms. The story of this discovery and its consequences demonstrates the relevance of atypical approaches and emphasizes the urgency of respecting biodiversity.

Size-Dependent Internalization Efficiency of Macrophages from Adsorbed Nanoparticle-Based Monolayers.

Functional coatings based on the assembly of submicrometric or nanoparticles are found in many applications in the biomedical field. However, these nanoparticle-based coatings are particularly fragile since they could be exposed to cells that are able to internalize nanoparticles. Here, we studied the efficiency of RAW 264.7 murine macrophages to internalize physisorbed silica nanoparticles as a function of time and particle size. This cell internalization efficiency was evaluated from the damages induced by the cells in the nanoparticle-based monolayer on the basis of scanning electron microscopy and confocal laser scanning microscopy observations. The internalization efficiency in terms of the percentage of nanoparticles cleared from the substrate is characterized by two size-dependent regimes. Additionally, we highlighted that a delay before internalization occurs, which increases with decreasing adsorbed nanoparticle size. This internalization is characterized by a minimal threshold that corresponds to 35 nm nanoparticles that are not internalized during the 12-h incubation considered in this work.

Role of Trapped Air in the Attachment of Staphylococcus aureus on Superhydrophobic Silicone Elastomer Surfaces Textured by a Femtosecond Laser.

Surface texturing is an easy way to control wettability as well as bacterial adhesion. Air trapped in the surface texture of an immersed sample was often proposed as the origin of the low adhesion of bacteria to surfaces showing superhydrophobic properties. In this work, we identified two sets of femtosecond laser processing parameters that led to extreme superhydrophobic textures on a silicone elastomer but showed opposite behavior against Staphylococcus aureus (S. aureus, ATCC 25923) over a short incubation times (6 h). The main difference from most of the previous studies was that the air trapping was not evaluated from the extrapolation of the results of the classical sessile drop technique but from the drop rebound and Wilhelmy plate method. Additionally, all wetting tests were performed with bacteria culture medium and at 37 °C in the case of the Wilhelmy plate method. Following this approach, we were able to study the formation of the liquid/silicone interface and the associated air trapping for immersed samples that is, by far, most representative of the cell culture conditions than those associated with the sessile drop technique. Finally, the conversion of these superhydrophobic coatings into superhydrophilic ones revealed that air trapping is not a necessary condition to avoid Staphylococcus aureus retention on one of these two textured surfaces at short incubation times.

Versatile transmission/reflection tomographic diffractive microscopy approach.

Tomographic diffractive microscopy (TDM) has gained interest in recent years due to its ability to deliver high-resolution, three-dimensional images of unlabeled samples. It has been applied to transparent samples in transmission mode, as well as to surface studies in reflection mode. Mudry et al. [Opt. Lett.35, 1857 (2010)OPLEDP0146-959210.1364/OL.35.001857] introduced the concept of mirror-assisted TDM (MA-TDM), an elegant approach for achieving quasi-isotropic-resolution microscopic imaging, but which is still to be experimentally applied. In this work, we show that a simplified version of MA-TDM allows for transforming a reflective TDM setup into a more versatile instrument, also capable of observing transparent samples in transmission mode if using specific sample holders made out of a mirror and coated with a low-thickness transparent spacer.

Deep-UV photoinduced chemical patterning at the micro- and nanoscale for directed self-assembly.

Deep-UV (DUV) laser patterning has been widely used in recent years for micro- and nanopatterning, taking advantage of the specific properties of irradiation with high-energy photons. In this paper, we show the usefulness of DUV laser patterning for preparing surfaces with controlled chemical properties at the micro- and nanoscale. Our motivation was to develop a simple and versatile method for chemical patterning at multiscales (from mm to nm) over relatively wide areas (mm2 to cm2). The chemical properties were provided by self-assembled monolayers (SAMs), prepared on glass or silicon wafers. We first investigated their modification under our irradiation conditions (ArF laser) using AFM, XPS and contact angle measurements. Photopatterning was then demonstrated with minimum feature sizes as small as 75 nm, and we showed the possibility to regraft a second SAM on the irradiated regions. Finally, we used these chemically patterned surfaces for directed self-assembly of several types of objects, such as block copolymers, sol-gel materials and liquids by vapor condensation.

Tensiometric Characterization of Superhydrophobic Surfaces As Compared to the Sessile and Bouncing Drop Methods.

We have considered in this work the Wilhelmy plate tensiometer to characterize the wetting properties of two model surface textures: (i) a series of three superhydrophobic micropillared surfaces and (ii) a series of two highly water-repellent surfaces microtextured with a femtosecond laser. The wetting forces obtained on these surfaces with the Wilhelmy plate technique were compared to the contact angles of water droplets measured with the sessile drop technique and to the bouncing behavior of water droplets recorded at a high frame rate. We showed that it is possible with this technique to directly measure triple-line anchoring forces that are not accessible with the commonly used sessile drop technique. In addition, we have demonstrated on the basis of the bouncing drop experiments wetting transitions induced by the specific test conditions associated with the Wilhelmy plate tensiometer for the two series of textured surfaces. Finally, the tensiometer technique is proposed as an alternative test for characterizing the wetting properties of highly liquid-repellent surface, especially under immersion conditions.

Role of Cellulose Nanocrystals on the Microstructure of Maleic Anhydride Plasma Polymer Thin Films.

Recently, it was shown that the microstructure of a maleic anhydride plasma polymer (MAPP) could be tailored ab initio by adjusting the plasma process parameters. In this work, we aim to investigate the ability of cellulose nanocrystals (CNCs) to induce topographical structuration. Thus, a new approach was designed based on the deposition of MAPP on CNCs model surfaces. The nanocellulosic surfaces were produced by spin-coating the CNC suspension on a silicon wafer substrate and on a hydrophobic silicon wafer substrate patterned with circular hydrophilic microsized domains (diameter of 86.9 ± 4.9 µm), resulting in different degrees of CNC aggregation. By depositing the MAPP over these surfaces, it was possible to observe that the surface fraction of nanostructures increased from 20% to 35%. This observation suggests that CNCs can act as nucleation points resulting in more structures, although a critical density of the CNCs is required.

Experimental characterization of the nanoparticle size effect on the mechanical stability of nanoparticle-based coatings.

We present an experimental investigation of the mechanical stability of silica nanoparticle-based coatings as a function of the size of the nanoparticles. The coatings are built following a layer-by-layer procedure, alternating positive and negative surface charges. The mechanical stability of the multilayers is studied in water, on the basis of an ultrasonic cavitation test. The resistance of the coating to cavitation is found to remarkably increase with decreasing the size of the nanoparticles, indicating an increase of the cohesive energy density. The relative contribution of van der Waals and electrical double-layer interactions to the stability of the multilayer is discussed toward their size dependence.

Model experimental study of scale invariant wetting behaviors in Cassie-Baxter and Wenzel regimes.

In this work, we discuss quantitatively two basic relations describing the wetting behavior of microtopographically patterned substrates. Each of them contains scale invariant topographical parameters that can be easily expressed onto substrates decorated with specifically designed micropillars. The first relation discussed in this paper describes the contact angle hysteresis of water droplets in the Cassie-Baxter regime. It is shown that the energy at the origin of the hysteresis, that has to be overcome for moving the triple line, can be invariantly expressed for hexagonal pillars by varying the pillars width and interpillar distance. Identical contact angle hystereses are thus measured on substrates expressing this scale invariance for pillar widths and interpillar distances ranging from 4 to 128 µm. The second relation we discuss concerns the faceting of droplets spreading on microtopographically patterned substrates. It is shown in this case that the condition for pinning of the triple line can be fulfilled by simultaneously varying the height of the pillars and the interpillar distance, leading to faceted droplets of similar morphologies. The invariance of these two wetting phenomena resulting from the simultaneous and homothetic variation of topographical parameters is demonstrated for a wide range of pattern dimensions. Our results show that either of those two wetting behaviors can be simply achieved by the proper choice of a dimensionless ratio of topographical length scales.

Intrusion/Extrusion of water into organic grafted SBA-15 silica materials for energy storage.

Mesoporous SBA-15 silica materials were grafted with trialkylsilyl compounds having short (C1) and long (C8) carbon chain and characterized by XRD, N2 physisorption analysis, 29Si MAS-NMR and contact angle (CA) measurements. A drastic enhancement of the hydrophobic property after grafting was observed by forced intrusion water; it occurred in two steps and with quite high intrusion pressures (mean values - 10 and - 15 MPa). The hydrophobic nature of both internal and external surface area was confirmed by 29Si MAS-NMR and CA measurements, respectively. After contact with water, materials displayed a partial hydrophobic behaviour with uncompleted spontaneous extrusion. The energies absorbed during water intrusion correspond to 4.3 and 6.1 J x g(-1) for C1 and C8 grafted species, respectively.

Spontaneous growth of self-relief wrinkles in freely floating lipid-based nanomembranes, formed on a reactive bath of polyoxometalate aqueous solution.

Wetting and capillarity have appeared over the last decadesas potential tools for the guided actuation, self-assembly and nanostructuration, and most recently as powerful "tool-free" techniques of micro-, and nano-fabrication, in the field of nanotechnology. The present work deals with such a use of wetting, achieving for the first time the spontaneous growth of composite (lipid-capped polyoxometalate) nanomembranes, using the reactive spreading film formed by the droplets of a lipid solution, on an aqueous foundation hosting the polyoxometalate ions. Moreover, we show that the internal stress produced by the reactive wetting, and the resulting self-movements of the drop could be accumulated within the drying spreading film, driving the spontaneous occurrence of wrinkles, in the freely floating nanomembranes that are thus formed. Finally, we showed that gravity-driven scaling relations for buckling instabilities apply to these spontaneously occurring wrinkles, allowing the in situ characterization of the physical properties of the nanomembranes. This approach that allowed producing floating nanomembranes of "lipid-capped Keggin ions" that were collectable as freestanding nanosheets may constitute a potential route for the fabrication of a wide range of functional (copolymers/metal nanoparticles) nanocomposite membranes.

Single-filament dynamics and long-range ordering of semiflexible biopolymers under flow and confinement.

We report the collective and single-filament dynamics of long semiflexible actin filaments flowing in an evaporating droplet adhering on glass and accumulating along the physical barrier constituted by the droplet triple line. The observation of fluorescent reporter filaments embedded in the entangled network enables us to relate the final collective organization of the accumulated filaments to the individual filament dynamics. Three areas corresponding to distinct filament organizations are observed in the region of the initial triple line pinning, after complete evaporation of the droplet. A nematic liquid-crystal-like alignment of the filaments is observed at the edge of the droplet because of the dynamic filament alignment, whereas a less-ordered packing is generated because of the bending and folding of most of the filaments. The latter unconventional dynamics is analyzed in terms of the amplification of undulation modes typical of semiflexible polymers. The receding regime of the droplet triple line leads finally to a remaining film of actin filaments showing random organization.

Protrusion force transmission of amoeboid cells crawling on soft biological tissue.

We applied a colloidal force microscopy technique to measure the spreading and retraction forces generated by protrusions (pseudopodia) of vegetative amoeboid cells (Dictyostelium discoideum) adhering on soft tissue analogues composed of 2-mm thick hydrogels of hyaluronic acid exhibiting Young's moduli between 10 and 200 Pa. Local shear deformations of the polymer films evoked by magnetic tweezers and by cellular protrusions were determined by analyzing the deflections of colloidal beads randomly deposited on the surface of the polymer cushions, which enabled us to measure forces generated by advancing ("pushing" forces) and retracting ("pulling" forces) protrusions in a direct way. We found that the maximum amplitudes generated by the advancing protrusions (pushes) decrease with increasing stiffness of the HA substrate while the amplitudes of the retractions do not show such a dependence. The maximum forces transmitted by the advancing and retracting protrusions increase with increasing stiffness of the HA films (from 0.02 to 1 nN for the case of pushing). The protrusions spread or retract with constant velocities which are higher for retractions (100 nm s(-1)) than for spreadings (50 nm s(-1)) and are not significantly influenced by the substrate rigidity. We provide evidence that elastic equilibrium during protrusion formation and retraction is maintained by local elastic dipole fields generated at the rim of the protrusions. A model of protrusion force transmission by coupling of growing actin gel in the cytoplasm of the protrusions to cell surface receptors through talin clutches is proposed.

Local force induced conical protrusions of phagocytic cells.

Magnetic tweezers were used to study the passive and active response of macrophages to local centripetal nanonewton forces on beta1 integrins. Superparamagnetic beads coated with the beta1-integrin-binding protein invasin were attached to J774 murine macrophages to mimic phagocytosis of bacterial pathogens. Forces exceeding approximately 0.5 nN induce the active formation of trumpet-like protrusions resembling pseudopodia after an initial elastic deflection and a response time of approximately 30 seconds. The speed of advancement of the protrusion is =0.065+/-0.020 micro m second(-1) and is force independent. After saturation (after about 100 seconds) the protrusion stops abruptly and is completely retracted again against forces exceeding 5 nN with an effective relaxation time of approximately 30 seconds. The active protrusion is tentatively attributed to the growth of the actin cortex in the direction of the force, and evidence for the involvement of actin is provided by the finding that Latrunculin A abolishes the activated cone growth. The growth is assumed to be activated by cell signaling mediated by the invasin-specific integrins (exhibiting beta1 chains) and could play a role in phagocytic and protrusive events during immune response by macrophages.