Characterization of the thermal and photoinduced reactions of photochromic spiropyrans in aqueous solution

Six water-soluble spiropyran derivatives have been characterized with respect to the thermal and photoinduced reactions over a broad pH-interval. A comprehensive kinetic model was formulated including the spiro- and the merocyanine isomers, the respective protonated forms, and the hydrolysis products. The experimental studies on the hydrolysis reaction mechanism were supplemented by calculations using quantum mechanical (QM) models employing density functional theory. The results show that (1) the substitution pattern dramatically influences the pKa-values of the protonated forms as well as the rates of the thermal isomerization reactions, (2) water is the nucleophile in the hydrolysis reaction around neutral pH, (3) the phenolate oxygen of the merocyanine form plays a key role in the hydrolysis reaction. Hence, the nonprotonated merocyanine isomer is susceptible to hydrolysis, whereas the corresponding protonated form is stable toward hydrolytic degradation

Thermal hydrosilylation of undecylenic acid with porous silicon

The thermal reaction of undecylenic acid with a hydrogen-terminated porous silicon surface takes place at 95\ub0C to yield an organic monolayer covalently attached to the surface through Si-C bonds. The acid terminal group remains intact and is not affected by the chemical process. Under the same conditions, alcohols break the Si-Si back bonds of the PSi matrix. In contrast, the acid function does not react with either the Si-H or the Si-Si bonds of the PSi surface and the reaction takes place at the terminal Formula double bond of the molecule. When the reaction was carried out with decanoic acid, under the same conditions, the reaction was not complete. The functionalized surfaces were characterized using transmission infrared and X-ray photoelectron spectroscopies. The effect of the chemical process on the photoluminescence has been studied, and the stability against corrosion in 100% humidity was verified using chemography. We have demonstrated that the derivatized surface with undecylenic acid can be activated by a simple chemical route using N-hydroxysuccimide in the presence of N-ethyl-N \u2032-(3-dimethylaminopropyl) carbodiimide hydrochloride.NRC publication: Ye