A study of photothermal laser ablation of various polymers on microsecond time scales.

To analyze the photothermal ablation of polymers, we designed a temperature measurement setup based on spectral pyrometry. The setup allows to acquire 2D temperature distributions with 1 µm size and 1 µs time resolution and therefore the determination of the center temperature of a laser heating process. Finite element simulations were used to verify and understand the heat conversion and heat flow in the process. With this setup, the photothermal ablation of polystyrene, poly(α-methylstyrene), a polyimide and a triazene polymer was investigated. The thermal stability, the glass transition temperature Tg and the viscosity above Tg were governing the ablation process. Thermal decomposition for the applied laser pulse of about 10 µs started at temperatures similar to the start of decomposition in thermogravimetry. Furthermore, for polystyrene and poly(α-methylstyrene), both with a Tg in the range between room and decomposition temperature, ablation already occurred at temperatures well below the decomposition temperature, only at 30-40 K above Tg. The mechanism was photomechanical, i.e. a stress due to the thermal expansion of the polymer was responsible for ablation. Low molecular weight polymers showed differences in photomechanical ablation, corresponding to their lower Tg and lower viscosity above the glass transition. However, the difference in ablated volume was only significant at higher temperatures in the temperature regime for thermal decomposition at quasi-equilibrium time scales.

Adsorption, aggregation, and desorption of proteins on smectite particles.

We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

Redox active polymer brushes with phenothiazine moieties.

We have investigated two different concepts to synthesize redox active polymer brushes using surface initiated atomic transfer radical polymerization (SI-ATRP). This polymerization technique allows the synthesis of well-defined grafted polymer brushes. In the initial step the surface was functionalized with a self-assembling monolayer of the SI-ATRP starter. Then, polymer brushes carrying phenothiazine moieties were grafted from the surface via SI-ATRP. The first concept consists of polymerizing monomers with phenothiazine pendant moieties to directly incorporate the redox functionality as side group in the growing polymer brush. The second concept consists of using grafted activated ester brushes which are functionalized with phenothiazine redox moieties in a successive reaction step. The electrochemical properties of the grafted redox active brushes were examined by cyclic voltammetry. Furthermore, the surface morphology and the chemical composition of the polymer brushes were characterized using scanning force microscopy (SFM), X-ray techniques, and UV/vis spectroscopy. Apart from their redox behavior, the synthesized brushes revealed increased mechanical stability on the nanoscale.

Antibacterial strategies from the sea: polymer-bound cl-catechols for prevention of biofilm formation.

Inspired by the amino acid 2-chloro-4,5-dihydroxyphenylalanine (Cl-DOPA), present in the composition of the proteinaceous glue of the sandcastle worm Phragmatopoma californica, a simple strategy is presented to confer antifouling properties to polymer surfaces using (but not releasing) a bioinspired biocide. Cl-Dopamine is used to functionalize polymer materials and hydrogel films easily, to prevent biofilm formation on them.