ABSTRACT
Fluorescent conjugated polymers (FCPs) have been explored for selective detection of metal cations with ultra-sensitivity in environmental and biological systems. Herein, a new FCP sensor, tmeda-PPpETE (poly[(pentiptycene ethynylene)-alt-(thienylene ethynylene)] with a N,N,N'-trimethylethylenediamino receptor), has been designed and synthesized via Sonogashira cross-coupling reaction with the goal of improving solid state polymer sensor development. The polymer was found to be emissive at λmax ~ 459 nm under UV radiation with a quantum yield of 0.119 at room temperature in THF solution. By incorporating diamino receptors and pentiptycene groups into the poly[(phenylene ethynylene)-(thiophene ethynylene)] (PPETE) backbone, the polymer showed an improved turn-off response towards copper(II) cation, with more than 99% quenching in fluorescence emission. It is capable of discriminating copper(II) cation from sixteen common cations, with a detection limit of 16.5 nM (1.04 ppb).
ABSTRACT
Fluorescent conjugated polymers have received a great deal of recent interest due to their ability to act as chemosensors to detect various chemical species in both environmental and biological systems with sensitivity and selectivity. Examples from the literature include polymer chemosensors that operate on either fluorescence "turn-on" or "turn-off" as mechanisms of sensor response. These responses can be related to either photoinduced electron transfer or electronic energy transfer mechanisms. Recently, a series of metal-containing polymers or metallopolymers have been explored by various research groups for their use as chemosensors. In many cases, these metallopolymers have been shown to be more sensitive and selective for specific chemical species. This review focuses on fluorescent conjugated polymers as chemosensors, with a specific concentration on recent advances in metallopolymer chemosensors.
ABSTRACT
A functionalized fluorescent conjugated polymer, tolylterpyridine poly(p-phenyleneethynylene-thienyleneethynylene (ttp-PPETE), was designed and synthesized to detect trace amounts of toxic transition metal pollutants in ground water. Photophysical studies in tetrahydrofuran (THF) successfully demonstrated this polymer as a selective and sensitive chemosensor for Ni(2+) and Co(2+) in aqueous solution. Solid state composites of these chemosensors have now been prepared which can be modified to provide for inexpensive and portable field based chemical detection. A solid composite of ttp-PPETE, blended with poly (methyl methacrylate) shows UV-vis absorption and fluorescence emission spectra which are red- shifted when compared to solution phase spectra, suggesting an increase in conjugation in the solid state. An additional absorption peak, not present in solution, is also observed in the solid state. The presence of this new peak provides evidence of interacting FCP chains in the solid state. Concentration dependent experiments were done on the solid composite showing red-shifted emission peaks accompanied by a significant reduction in the fluorescent quantum yield. These observations are consistent with the formation of aggregated polymer species in the solid state. Intermolecular interactions of this type can be manipulated in the design of sensitive and selective solid state fluorescent conjugated polymer sensors.
