Fluorinated tripodal receptors for potentiometric chloride detection in biological fluids

• Published in: Biosensors & bioelectronics 2018-01, Vol.99, p.70-76
• Main Authors: Pankratova, Nadezda, Cuartero, Maria, Jowett, Laura A., Howe, Ethan N.W., Gale, Philip A., Bakker, Eric, Crespo, Gastón A.
• Format: Article
• Language: English
• Subjects: Anions - chemistry; Biosensing Techniques; Chloride detection; Chlorides - chemistry; Chlorides - isolation & purification; Halogenation; Human serum; Humans; Hydrogen Bonding; Hydrogen-Ion Concentration; Ionophores - chemistry; Membranes, Artificial; Potentiometry; Receptors; Sensors; Thiocyanates - chemistry
• ISSN: 0956-5663; 1873-4235
• DOI: 10.1016/j.bios.2017.07.001

Fluorinated tripodal compounds were recently reported to be efficient transmembrane transporters for a series of inorganic anions. In particular, this class of receptors has been shown to be suitable for the effective complexation of chloride, nitrate, bicarbonate and sulfate anions via hydrogen bonding. The potentiometric properties of urea and thiourea-based fluorinated tripodal receptors are explored here for the first time, in light of the need for reliable sensors for chloride monitoring in undiluted biological fluids. The ion selective electrode (ISE) membranes with tren-based tris-urea bis(CF3) tripodal compound (ionophore I) were found to exhibit the best selectivity for chloride over major lipophilic anions such as salicylate (logKCl−/Sal−pot=+1.0) and thiocyanate (logKCl−/SCN−pot=+0.1). Ionophore I-based ISEs were successfully applied for chloride determination in undiluted human serum as well as artificial serum sample, the slope of the linear calibration at the relevant background of interfering ions being close to Nernstian (49.8±1.7mV). The results of potentiometric measurements were confirmed by argentometric titration. Moreover, the ionophore I-based ISE membrane was shown to exhibit a very good long-term stability of potentiometric performance over the period of 10 weeks. Nuclear magnetic resonance (NMR) titrations, potentiometric sandwich membrane experiments and density functional theory (DFT) computational studies were performed to determine the binding constants and suggest 1:1 complexation stoichiometry for the ionophore I with chloride as well as salicylate. •Excellent performance of fluorinated tren-based tripodal receptors for chloride detection.•Sufficient potentiometric discrimination of chloride over salicylate and thiocyanate in undiluted human serum.•Outstanding long-term stability (>10 weeks) of fluorinated tren-based tripodal ionophore based membranes.