Multimode binding and stimuli responsive displacement of acridine orange dye complexed with p-sulfonatocalix[4/6]arene macrocycles

Abstract

Interaction of acridine orange (AOH⁺) dye with water soluble anionic p-sulfonatocalix[n]arene (SCXn) hosts, SCX4 and SCX6, having different cavity dimensions, has been investigated using multispectroscopic techniques. Intriguing modulation in the photophysical properties of AOH⁺ upon interaction with SCXn hosts indicate the formation of different host–guest complexes at different regions of the host concentrations. At lower host concentrations, AOH⁺ undergoes SCXn assisted aggregation, causing a drastic reduction in fluorescence intensity. At higher host concentrations, aggregated-AOH⁺–SCXn complexes disintegrate and monomeric-AOH⁺–SCXn exo and inclusion complexes are eventually formed, leading to a huge fluorescence enhancement finally. Observed effects are more pronounced with SCX6 as compared to SCX4 host. Time-resolved fluorescence studies indicate that at very high host concentrations, there is also a diffusion-controlled dynamic quenching for both monomeric-AOH⁺–SCXn exo and inclusion complexes, caused by the free SCXn present in the solution, a phenomenon not reported before for such host–guest systems. The aggregated-AOH⁺–SCXn complexes at lower host concentration were employed to investigate displacement study using an antiviral drug, 1-adamantanamine (AD) and a neurotransmitter, acetylcholine (AcCh), as the competitive binders cum external stimuli, which resulted in a drastic recovery of the fluorescence reduced initially due to aggregation process. Though both the AOH⁺–SCXn systems act as efficient supramolecular assemblies in sensing AD and AcCh as the analytes through fluorescence “OFF–ON” mechanism, the effect is more pronounced for AOH⁺–SCX4 system as compared to AOH⁺–SCX6. SCXn induced interesting modulation in the photophysical properties of AOH⁺ and the stimulus responsive dye displacement observed for aggregated-AOH⁺–SCXn systems can expectedly find applications in fluorescence OFF–ON sensing, supramolecular functional materials and similar others.