Highly selective thiocyanate optochemical sensor based on manganese(III)-salophen ionophore

- Preparation of different optodes using different compositions
- Mechanism depends on co-extraction of thiocyanate and protons to membrane.
- Sensor showed excellent selectivity.
- Sensor could be applied for thiocyanate determination in real saliva.

We report on the development of optochemical sensor based on Mn(III)-salophen ionophore. The sensor was prepared by embedding the ionophore in a plasticized poly (vinyl chloride) impregnated with the chromoionophore ETH7075. Optical response to thiocyanate occurred due to thiocyanate extraction into the polymer via formation of strong complex with the ionophore and simultaneous protonation of the indicator dye yielding the optical response at 545 nm. The developed optochemical sensor exhibited high selectivity for thiocyanate over other anions including the most lipophilic species such as salicylate and perchlorate. For instance, the optical selectivity coefficients, logKSCN , anionopt, were as follow: ClO4− = − 5.8; Sal− = − 4.0; NO3− ˂ − 6. Further, the thiocyanate optical selectivity obtained using the present optochemical sensor was greatly enhanced in comparison with that obtained using an anion-exchanger based sensor. Also, the optimized optochemical sensor exhibited micro-molar detection limit with 2 min response time at pH 4.5 using acetate buffer. The reversibility of the optimized sensor was poor due to strong ligation of the thiocyanate to the central Metal ion, log K = 14.1, which can be overcome by soaking the optode in sodium hydroxide followed by soaking in buffer solution. The developed sensor was utilized successfully for the determination of thiocyanate in human saliva and in spiked saliva samples.