Imprinting of Chiral Molecular Recognition Sites in Thin TiO2 Films Associated with Field-Effect Transistors: Novel Functionalized Devices for Chiroselective and Chirospecific Analyses

Abstract

(R)‐ or (S)‐2‐Methylferrocene carboxylic acids, (R)‐1 or (S)‐1, (R)‐ or (S)‐2‐phenylbutanoic acid, (R)‐2 or (S)‐2, and (R)‐ or (S)‐2‐propanoic acid, (R)‐3 or (S)‐3, can be imprinted in thin TiO₂ films on the gate surface of ion‐sensitive field‐effect transistor (ISFET) devices. The imprinting is performed by hydrolyzing the respective carboxylate Ti^IV butoxide complex on the gate surface, followed by washing off the acid from the resulting TiO₂ film. The imprinted sites reveal chiroselectivity only towards the sensing of the imprinted enantiomer. The chiral recognition sites reveal not only chiroselectivity but also chirospecificity and, for example, the (R)‐2‐imprinted film is active in the sensing of (R)‐2, but insensitive towards the sensing of (R)‐2‐phenylpropanoic acid, (R)‐3, which exhibits a similar chirality. Similarly, the (R)‐3‐imprinted film is inactive in the analysis of (R)‐2. The chiroselectivity and chirospecificity of the resulting imprinted films are attributed to the need to align and fit the respective substrates in precise molecular contours generated in the cross‐linked TiO₂ films upon the imprinting process.