Inner Filter Effect and Resonance Energy Transfer Based Attogram Level Detection of Nitroexplosive Picric Acid Using Dual Emitting Cationic Conjugated Polyfluorene.

A novel conjugated cationic polyfluorene (polyelectrolyte) derivative, PFBT, was developed by means of simple and cost-effective oxidative coupling polymerization method. PFBT displayed dual state emission in dimethyl sulfoxide (DMSO) as well as in water, a characteristic phenomenon of polyfluorene homopolymers, and tested for nitroexplosive analytes detection to observe a remarkable fluorescence quenching response for picric acid (PA) in the both solvents. The polymer PFBT demonstrated substantial selectivity and ultrasensitivity toward nitroexplosive PA in both the solvents (DMSO and H2O) with exceptional quenching constant values of 2.69 × 104 and 2.18 × 105 M-1 and a ultralow limit of detection of 92.7 nM (21.23 ppb) and 0.19 nM (43.53 ppt) in respective solvents. Furthermore, economical portable test strip devices were prepared for easy and fast on-site PA sensing, which can detect up to 0.22 ag level of PA. PA sensing in vapor phase was also established, that could detect up to 42.6 ppb level of PA vapors. Interestingly, the mechanism of sensing in DMSO solvent was attributed to substantial inner filter effect and photoinduced electron transfer, while in H2O the sensing occurs via possible resonance energy transfer and photoinduced electron transfer, which is exceptional and not reported earlier for a single probe.

Design, synthesis and DSSC performance of o-fluorine substituted phenylene spacer sensitizers: effect of TiO2 thickness variation.

The influence of TiO2 film thickness on the performance of DSSCs with a new series of dyes having ortho-fluorine substituted phenyl spacers and different donor moieties is reported. Optical, electrochemical, molecular orbital and photovoltaic properties were studied by varying the TiO2 thickness (9 and 12 µm) using these dyes. The thickness variation of TiO2 films had a significant effect on the open circuit voltage (Voc), short circuit current (Jsc) and efficiency. The Jsc and Voc of dye 1b with a TiO2 film thickness of 12 µm (8.91 mA cm-2 and 0.63 V) were larger than those of the 9 µm film thickness device (8.40 mA cm-2 and 0.57 V). This could be due to the variation in the thickness of the TiO2 film. However, at an optimized thickness of the TiO2 film (12 µm), 1b exhibited the highest power conversion efficiency (η) of 4.0% (average 3.6%). This highest efficiency value for 1b from 3.3% to 4.0% without using any co-absorbents was solely based on changing the thickness of the TiO2 film. In addition 1b had a planar structure, whereas dyes 2b and 3b had three and two dimensional structures. The optimized geometry calculation of o-fluoro phenyl π-spacer dyes was ascertained by density functional theory (DFT) using the B3LYP/631G(d,p) basis set. These results reveal that dye 1b has higher efficiency due to the deeper HOMO level and it exhibited better charge transfer from donor to acceptor, compared to the other dyes.

Ultrasensitive detection of nitroexplosive - picric acid via a conjugated polyelectrolyte in aqueous media and solid support.

Picric acid (PA) detection at parts per trillion (ppt) levels is achieved by a conjugated polyelectrolyte (PMI) in 100% aqueous media and on a solid platform using paper strips and chitosan (CS) films. The unprecedented selectivity is accomplished via combination of ground state charge transfer and resonance energy transfer (RET) facilitated by favorable electrostatic interactions.