Structure affinity of the Langmuir monolayer and the corresponding Langmuir–Blodgett film revealed by X-ray techniques†

Abstract

The possibility of reproducing the structural organization and functional abilities of a Langmuir monolayer in a film formed from it is one of the fundamental problems of ultrathin film science. This work is devoted to the comparison of monolayer and Langmuir–Blodgett (LB) film characteristics using the example of 2D systems based on the dithia-aza-crown substituted hemicyanine dye HCS. As was shown earlier, the investigated systems are promising for the preparation of selective sensors and extractors for mercury ions in aqueous solutions with a subnanomolar sensitivity threshold. Therefore, the study of the analyte binding mechanism by such a film is of great importance. The study carried out using an ultra-highly brilliant X-ray source (ESRF) allows the application of highly sensitive techniques such as X-ray reflectometry (XRR) and X-ray standing wave (XSW). Comparison of the electron density depth profile of the HCS Langmuir monolayer at the air/water interface and the HCS film transferred to a silicon substrate shows the preservation of the film structure and its functional features. The XSW measurements in turn reveal the similarities in the fine structure of preorganized Langmuir monolayers and Langmuir–Blodgett films of HCS. The integration of X-ray techniques with molecular modeling methods allowed us to show that the crown-ether groups of HCS molecules in the pre-organized monolayer and in the corresponding LB film lie on the surface of water or silicon, and the bound mercury ion is located above the crown-ether, partially binding to the nitrogen atom. The latter loses conjugation to the chromophore group, thereby altering the UV-vis spectrum and providing a response signal. The revealed mechanism of imprinting preorganization allows the proposed approach to be extended to other crown-substituted amphiphilic dyes to significantly enhance the sensory response.