A comparative study of the effect of o-nitrophenyl octyl ether and o-nitrophenyl pentyl ether as plasticizers on the response and selectivity of carrier-based liquid membrane ion-selective electrodes.
Lithium, potassium and caesium-selective microelectrodes were prepared by coating the tips of preconditioned silver wires, incorporated in a flow-cell, with PVC membranes containing four different ionophores. A dicarboxamide, a 14-crown-4 carboxylic acid, benzo-18-crown-6 and di-(tert-butylbenzo)-21-crown-7 ionophores were used in the electrode matrix. The first two ionophores were used in lithium ion-selective electrodes, the third in a potassium ion electrode and the fourth in a caesium ion electrode. Two different plasticizers, o-nitrophenyl octyl ether (NPOE) and o-nitrophenyl pentyl ether (NPP'E) were used. Enhancement of the signal and the slope of the calibration curve and improvement of the curve linearity were observed in all cases when NPP'E was used as plasticizer. A general trend of enhanced selectivity of the electrodes incorporating crown ether ionophores was also observed when NPP'E was the plasticizer.
Analytical strategies for the measurement of lithium in biological samples.
Therapeutic lithium levels in the treatment of manic depressive psychosis must be maintained in the range of 0.5-1.5 mM in the blood, which also contains 140 mM sodium. This paper reviews spectrophotometric, fluorometric, and ion-selective electrode (ISE) reagents and methods for achieving high lithium selectivity over sodium and their use in blood lithium measurement. These include aromatic organic reagents, crown ethers and amide ionophores. Crown ethers and cryptands provide the best lithium selectivity. A chromophoric small-cavity cryptand phenol exhibits greater than 4000:1 selectivity due to rigid configuration of a well preorganized binding site for lithium complexation. It is water soluble, making it easy to apply for blood analysis. Crown ethers with bulky groups inhibit formation of the 2:1 crown:sodium complex, while allowing formation of the 1:1 lithium complex. A PTM 14-crown-4 having a bulky pinane and subunits at the ethano bridge exhibits at least 10,000:1 selectivity for lithium in a flow-through optical sensor probe. Bulky crown ethers used in PVC membrane ion-selective electrodes exhibit lithium selectivities of 1-2000:1. Methods of evaluating selectivities are discussed, along with the correlation of solvent extraction of crown ether complexes and solvent membrane ISE selectivities.
Application of ion-selective electrodes in flow analysis
Abstract Continuous flow techniques offer one of the most effective approaches to obtaining analytical data on a large scale and monitoring individual components in biological systems or in industrial effluents. The segmented flow methods developed by Skeggs1 and the continuous flow methods, including liquid chromatography, which have been developed in the last 10 years are especially noteworthy.