We have examined the direct effect of manipulating the number of free surfaces on the measured glass transition temperature T(g) of thin polystyrene films. Thin films in the range 35 nm < h < 114 nm with molecular weights of 592 kg/mol and 1144 kg/mol were studied. Ellipsometry was used to determine the temperature dependence of the thickness and refractive index of freestanding films. By noting the change in slope in each of these quantities, a T(g) value can be assigned in quantitative agreement with previously reported results. For thin freestanding films this value is reduced from that of the bulk. The exact same films are then transferred to a Si substrate and the T(g) of the resulting supported film was determined. The T(g) values of the now supported films are the same as the bulk value and the same as previous reports of similar supported films. These experiments unambiguously show that free interfaces are the dominant cause of the T(g) reductions for the film thicknesses studied.
Hydrodynamic boundary conditions play a crucial role in the flow dynamics of thin films and can be probed by the analysis of liquid front profiles. For long-chained polymer films it was reported that a deviation from a symmetric profile is a result of viscoelastic effects. In this Letter, however, evidence is given that merely a slip-boundary condition at the solid-liquid interface can lead to an asymmetric profile. Variation of molecular weight shows that slippage is directly linked to chain entanglements. We find a reduced entanglement density at the solid-liquid interface (factors 3 to 4), which stresses the importance of considering nonbulk polymer properties in the vicinity of an interface.
Although microbial responses to light have been widely recognized, any influence of light on cell-surface interactions remains elusive. Here, we reveal that the unspecific adhesion of microalgae to surfaces can be reversibly switched on and o by light. Using a micropipette force spectroscopy technique, we measured in vivo single-cell adhesion forces and show that the microalga's flagella provide light-switchable adhesive contacts with the surface. This light-induced adhesion to surfaces is an active and completely reversible process that occurs on a timescale of seconds. Our results suggest that light-switchable adhesiveness is a natural functionality of microalgae to regulate the transition between the planktonic and the surface-associated state, which yields an adhesive adaptation to optimize the photosynthetic e ciency in conjunction with phototaxis.
Organosilane self-assembled monolayers (SAMs) are commonly used for modifying a wide range of substrates. Depending on the end group, highly hydrophobic or hydrophilic surfaces can be achieved. Silanization bases on the adsorption, self-assembly and covalent binding of silane molecules onto surfaces and results in a densely packed, SAM. Following wet chemical routines, the quality of the monolayer is often variable and, therefore, unsatisfactory. The process of self-assembly is not only affected by the chemicals involved and their purity but is also extremely sensitive to ambient parameters such as humidity or temperature and to contaminants. Here, a reliable and efficient wet-chemical recipe is presented for the preparation of ultra-smooth, highly ordered alkyl-terminated silane SAMs on Si wafers. The resulting surfaces are characterized by means of atomic force microscopy, X-ray reflectometry and contact angle measurements.
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