Self-assembly and imprinting of macrocyclic molecules in layer-by-layered TiO2 ultrathin films Original Research Article

Alternate TiO2 gel ultrathin films assembled with a macrocyclic carboxylic acids of tetrakis-4-carboxyphenyl porphine (TCPP) or tetra-4-carboxylphthalocyanine cobalt (II) (Co-TCPc) were prepared by the surface sol–gel process. To confirm the film growth and imprinting effect, quartz crystal microbalance (QCM) and UV–vis spectroscopy measurements were employed. The binding of TCPP was 1.2–14.3 times more selective compared to structurally related macrocyclic guest molecules. Among other findings, tetrakis-4-carboxymethyloxyphenyl porphine (TCMOPP) that has a spacer (single bondOsingle bondCH2single bond) between the phenyl rings and carboxylic acid moieties of TCPP showed a significantly lower binding efficiency equal to 0.07, regardless of its similar molecular structure to the template molecule. Structural difference of porphyrin and phthalocyanine analogs could be also selectively discriminated: the TCPP imprinted film showed ca. 13 times higher selectivity for recognition of TCPP itself from the mixture of TCPP and Co-TCPc. Characterization by AFM demonstrated that the TiO2/TCPP film has highly uniform surface and ultrathin thickness, while both TEM and SEM studies confirmed the immobilized structures of TCPP inside the film.