title: Micelle-induced versatile performance of amphiphilic intramolecular charge-transfer fluorescent molecular sensors.
abstract: A series of amphiphilic intramolecular charge-transfer fluorescent molecular sensors AS1-3, equipped with a rod-shaped hydrophobic 2-phenylbenzoxazole fluorophore and a hydrophilic tetraamide Hg(2+)-ion receptor, have been prepared. These sensor molecules could be incorporated into the hydrophobic sodium dodecyl sulfate (SDS) micelle, which is confirmed by the clear spectral blue shift and emission enhancement observed at the critical micelle concentration of SDS. Systematic examination of the sensor-Hg(2+) complexation, by using both UV/visible and fluorescence spectroscopy, indicates that SDS significantly modulates both the binding event and signal transformation of these sensor molecules. The potential advantages are fourfold: 1) SDS substantially increases the Hg(2+)-ion association constant and results in an amplified sensitivity. 2) SDS initiates spectral features which facilitate Hg(2+)-ion analysis, for example, in addition to the strengthened fluorescence of the free sensors AS1-3, the original "on-off" response of AS2 toward the Hg(2+) ion is transformed into a self-calibrated two-wavelength ratiometric signal, while for AS3, Hg(2+)-ion complexation in the presence of SDS results in a 180 nm blue shift, which is preferred to the 51 nm spectral shift obtained without SDS. 3) Thermoreversible tuning of the dynamic detection range is realized. 4) Highly specific Hg(2+)-ion identification could be achieved by using the SDS-induced fingerprint emission (358 nm) of the AS2-Hg(2+) complex. Altogether, this work demonstrates a convenient and powerful strategy that remarkably elevates the performance of a given fluorescent molecular sensor. It also implies that for a specific utilization, much attention should be paid to the microenvironment in which the sensor resides, as the behavior of the sensor might be different from that in the bulk solution.
authors.affiliation: State Key Laboratory of Bioreactor Engineering, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China.
authors.forename: Jiaobing
authors.initials: J
authors.lastname: Wang
authors.forename: Xuhong
authors.initials: X
authors.lastname: Qian
authors.forename: Junhong
authors.initials: J
authors.lastname: Qian
authors.forename: Yufang
authors.initials: Y
authors.lastname: Xu
mesh_terms: D005456:Fluorescent Dyes / Q000737:chemistry*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008628:Mercury / Q000737:chemistry; D008823:Micelles; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry*; D012997:Solvents; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet; D013501:Surface-Active Agents / Q000737:chemistry*; D013696:Temperature
chemical_list: D005456:Fluorescent Dyes; D007202:Indicators and Reagents; D008823:Micelles; D012997:Solvents; D013501:Surface-Active Agents; D012967:Sodium Dodecyl Sulfate; D008628:Mercury