Molecularly imprinted polystyrene–titania hybrids with both ionic and π–π interactions: a case study with pyrenebutyric acid

We present hybrid films consisting of a composite prepared from polystyrene (PS) and titanium dioxide (titania; TiO₂) and molecularly imprinted with 1-pyrenebutyric acid (PBA). The interaction of PBA with the polymer is shown to occur via binding of the carboxylic group to TiO₂ and hydrophobic interaction of the pyrene moiety with the PS network. We investigated the effects of the PS fraction on morphology, imprinting properties, and guest binding. The template could be completely removed by incubating the films in an acetonitrile solution of pyrene, which is due to the stronger π–π interaction between PBA and pyrene than the interaction between PBA and its binding site. A guest binding study with pyrene, 1-aminopyrene, pyrenemethanol, and anthracene-9-carboxylic acid showed that the hybrid films possessed selectivity and much higher binding capacity for PBA. This study demonstrates the first case of clear PS-assisted imprinting, where the π–π interaction of the template with a linear (non-crosslinked) polymer creates selective binding sites and enhances the binding capacity. This is a driving force for guest binding in addition to the interaction of the template/analyte with TiO₂. All molecularly imprinted films displayed better binding, repeatability and reversibility compared to the respective non-imprinted films.

Molecularly imprinted polystyrene–titania hybrids with both ionic and π–π interactions: a case study with pyrenebutyric acid

We present hybrid films consisting of a composite prepared from polystyrene (PS) and titanium dioxide (titania; TiO₂) and molecularly imprinted with 1-pyrenebutyric acid (PBA). The interaction of PBA with the polymer is shown to occur via binding of the carboxylic group to TiO₂ and hydrophobic interaction of the pyrene moiety with the PS network. We investigated the effects of the PS fraction on morphology, imprinting properties, and guest binding. The template could be completely removed by incubating the films in an acetonitrile solution of pyrene, which is due to the stronger π–π interaction between PBA and pyrene than the interaction between PBA and its binding site. A guest binding study with pyrene, 1-aminopyrene, pyrenemethanol, and anthracene-9-carboxylic acid showed that the hybrid films possessed selectivity and much higher binding capacity for PBA. This study demonstrates the first case of clear PS-assisted imprinting, where the π–π interaction of the template with a linear (non-crosslinked) polymer creates selective binding sites and enhances the binding capacity. This is a driving force for guest binding in addition to the interaction of the template/analyte with TiO₂. All molecularly imprinted films displayed better binding, repeatability and reversibility compared to the respective non-imprinted films.

Illustration of the fabricated polystyrene/titania hybrids imprinted with 1-pyrenebutyric acid providing the interaction between the organic and inorganic components through the pyrene and carboxylic moieties

     

Remarkable enantioselectivity of molecularly imprinted TiO2 nano-thin films

TiO(2) nano-thin films with imprinted (R)- and (S)-enantiomers of propranolol, 1,1'-bi-naphthol, and 2-(4-isobutylphenyl)-propionic acid were fabricated on quartz plates by spin-coating their solutions with Ti(O-(n)Bu)(4) in a toluene-ethanol mixture (1:1, v/v). After template removal, the imprinted films showed better binding for original templates than to the corresponding enantiomers. The assessment of template incorporation, template removal, and re-binding was conducted through UV-vis measurements. Significant enhancement of enantioselectivity was achieved by optimization of the film thickness and by heat-treatment of the imprinted films. After subtraction of non-specific binding, the optimized films provided chiral recognition with the enantioselectivity of almost 100% for (R)-propranolol and 95% for (S)-propranolol.