We report an evanescent wave based fibre optic absorbance meter that enables the colorimetric detection of waterborne cations with water insoluble chromoionophoric sensitisers. This establishes an alternative to the PVC membrane based transducers that are conventionally used for this purpose. Here, a water insoluble sensitiser is coated as a thin film on an unclad section of a multimode optical fibre to overlap with the evanescent field of a light beam propagating along the fibre core. The colorimetric response of the sensitiser when in contact with waterborne cation leads to increased absorption of virtual photons associated with the evanescent field. The resulting intensity loss of the propagating beam is detected by a bespoke newly designed self-referenced evanescent wave absorbance meter with beam intensity modulation and Lock-in amplification. We validate our transducer with the well characterised water insoluble sensitizer, 1-(2-pyridylazo)-2-naphthol (PAN), for the detection of aqueous Zn 2+ cations. We find a limit of detection (LoD) of 54 nM Zn 2+ , 28 times lower compared to a PVC membrane based sensor using same sensitiser for same cation (Albero et al., Journal of Pharmaceutical and Biomedical Analysis 29 (2002), 779). Our evanescent wave absorbance meter can easily be adapted to other colorimetric sensitisers, including chromoionophoric complex forming macrocycles.

When films of zinc 5-(4-carboxyphenyl),10,15,20-triphenyl porphyrin (ZnTPP) are exposed to waterborne amine in pH- neutral or alkaline media, both Q- band and Soret band respond with a change of absorbance due to the donation of amine 'lone pair' electrons to the metalloprophyrin π orbital. However, this is difficult to reveal with a conventional spectrometer even under high amine concentration. We therefore introduce optical fibres coated with ZnTPP into a bespoke 'light balance' evanescent wave absorbance meter [doi:10.1016/j.snb.2016.05.065]. The light balance makes absorbance changes clearly visible under only 5μM aqueous amine, making PVC membranes redundant. We find sensitivity is higher, and limit- of- detection lower, in the Soret band rather than the Q- band, reflecting the stronger Soret band absorbance. Also, we find that sensitivity is higher, and limit- of- detection approximately two times lower, when rough rather than smooth fibres are used. We believe the rough fibre surface leads to enhanced evanescence, and therefore better overlap of the wave propagating in the fibre with the ZnTPP fibre cladding. We find a limit of detection to waterborne amines below 1μM, which compares well to other sensors for waterborne amines [Korent, S.M. et.al. Anal. Bioanal. Chem. 387 (2007) 2863-2870; Algarni, S. A. et.al. Talanta 153 (2016) 107-110]. We therefore recommend 'rough guide' evanescent wave optrodes, in combination with sensitive 'light balance' detector, to succeed membrane- embedding of colorimetric sensitisers such as metalloporphyrines.

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