Prof. Dr. Aránzazu del Campo

The curing time of an adhesive material is determined by the polymerization and cross-linking kinetics of the adhesive formulation and needs to be optimized for the particular application. Here, we explore the possibility of tuning the polymerization kinetics and final mechanical properties of tissue-adhesive PEG gels formed by polymerization of end-functionalized star-PEGs with catecholamines with varying substituents. We show strong differences in cross-linking time and cohesiveness of the final gels among the catecholamine-PEG variants. Installation of an electron-withdrawing but π-electron donating chloro substituent on the catechol ring resulted in faster and more efficient cross-linking, while opposite effects were observed with the strongly electron-withdrawing nitro group. Chain substitution slowed down the kinetics and hindered cross-linking due either to chain breakdown (beta-OH group, in norepinephrine) or intramolecular cyclization (α-carboxyl group, in DOPA). Interesting perspectives derive from use of mixtures of catecholamine-PEG precursors offering further opportunities for fine-tuning of the curing parameters. These are interesting properties for the application of catecholamine-PEG gels as tissue glues or biomaterials for cell encapsulation.

The recent interest in fibrillar biological attachment systems, as found in the gecko, has led to the development of micropatterned elastomer adhesion surfaces. All reported studies have been performed at ambient humidity neglecting its possible influence on adhesion. The present paper investigates, for the first time, the effect of systematic changes in ambient humidity from 2 to 90%. Adhesion measurements were performed on PDMS (Sylgard 184) surfaces possessing micropillars with flat-ended and hemispherical contact shape. The pillar radius was varied between 2.5 and 25 µm; the pillar aspect ratio was kept at 1. While the adhesion of a flat sample was not affected by humidity, we found that pillar size and shape influenced the sensitivity to humidity changes: Thinner pillars, with higher pull-off forces in the dry state, exhibited decreasing adhesion values, by up to 35 %, with increasing humidity. The effect was stronger for the hemispherical tip shape, where the positive effect of finer pillars was even reversed. Possible explanations for these effects, which may lower the reliability of biomimetic adhesion devices in the presence of humidity, are given.

The recently emerging interest in fibrillar biological attachment systems, as those found in the gecko, has led to the fabrication of micropatterned elastomer adhesion surfaces. Reported studies have demonstrated that measurements on micropatterned surfaces are affected by experimental parameters not relevant for flat samples. The present paper investigates the influence on adhesion values of the sample stiffness, the backing layer thickness, the ambient humidity, and of repetitive measurements at the same location. Measurements were performed on PDMS (Sylgard® 184) micropatterned surfaces possessing flat-ended pillars with 10 µm diameter and 10 µm height. We find that adhesion increased with decreasing sample stiffness and decreasing backing layer thickness, whereas it dropped when several tests were carried out at exactly the same location. For ambient humidities between 2 and 90%, no influence on adhesion performance was found.

Molecular architecture affects the properties of surface layers. Photosensitive silanes with branched architectures allow patterning and coupling of proteins and cells on surfaces while maintaining their biofunctional state. Attachment can be directed to the activated regions of irradiated substrates with high selectivity (see image of mouse fibroblasts). Novel photosensitive silanes with a branched molecular architecture combining three end-functionalized oligoethylene glycol (OEG) and alkyl arms are presented. These molecules are synthesized and applied to the modification of silica surfaces. The resulting layers are tested in their ability for the selective, patterned and functional immobilization of proteins and cells. The results demonstrate and accurately quantify the benefits of branched OEG structures against linear analogues for preventing non-specific interactions with the biological material. Linear structures guarantee high selectivity for the attachment of proteins, however, they fail in the case of cells. Branched structures provide good antifouling properties in both cases and allow the formation of protein patterns with higher densities of the target protein, as well as cell patterns. The results demonstrate the careful balance between surface functionality, composition and architecture that is required for maximizing the performance of any surface-based assay in biology.

Two photoremovable protecting groups, namely, nitroveratryloxycarbonyl (NVo) and diethylamino-coumarin-4-yl (DEACM), have been tested for wavelength-selective, independent removal. The chromophores were attached to the amine group of aminopropyltriethoxysilane and used for the modification of silica surfaces. A photolytic experiment on the photosensitive layers allowed us to identify the irradiation conditions for the selective cleavage of the chromophores. UV measurements revealed that the photolabile DEACM group can be cleaved off with UV light at 412 nm without damaging the NVo group. The NVo group could then be removed at 365 nm. Masked irradiation of substrates modified with a I: I molar mixture of both silanes allowed the generation of bifunctional patterns after the selective cleavage of DEACM and NVo in a sequential irradiation process. The deprotection reaction was confirmed by coupling two different fluorescent dyes to the liberated amine groups. The expected two-color pattern could be observed by fluorescence microscopy.