Light and Electric Potential Induced Reversible Wetting on Structured Surfaces

Derivatised 2,4-diketopyrimidine groups have been anchored to planar gold surfaces as self¬-assembled monolayers (SAMs) for chemical and photochemical studies. Three derivatives, 5-methyluracil (thymine), 5-trifluoromethyluracil and 5-nitrouracil, were chosen for the specific moiety present at position C-5, which can exert strong or weak inductive effects on the adjacent aromatic ring. The measured acidity constants decrease from 5-methyluracil to 5-nitrouracil as the inductive properties of the group at C-5 position increase. When grafted to the surface the acidity constants increase, albeit still adhering to the expected inductive trend. The functionality also exerts an influence on the surface wetting properties. Surface wettabilities indicate that the orientation of the pyrimidine groups at the surface occurs so that the C-5 position has a direct effect upon the surface chemistry. Upon dimerisation the surface contact angles increase signifi¬cantly. At pH 11 the contact angle changes reflect that the dimer has a higher pKa than the monomer. The monomer surface is deprotonated at this pH while the dimer surface is partially deprotonated, leading to changes in contact angle of up to 22 degrees. Large changes in contact angle were observed for 5-nitrouracil which were independent of surface charge and were appar¬ently due to conformational changes alone. Electrowetting of three fluoropolymer surfaces by electrolyte solutions was studied with the sessile drop method. The electrowetting curve (contact angle/potential) is analogous to the elec¬trocapillary curve (surface tension/potential) and may be described by a combination of the Young and Lippmann equations. We demonstrate that for some specific surfaces a systematic deviation occurs at positive potentials. This departure is attributed to double layer effects, namely the adsorption of hydroxide and halide anions. pH, ionic strength and polymer composi¬tion can all influence electrowetting behaviour.