Studies On Anion-Selective Electrodes With Macrocyclic And Schiff Base Metallic Complexes As Neutral Carriers

Design, synthsis and application of highly selective and sensitive neutral carriers are main research subjects in the ion-selective electrode studies. Recently, study on ion-selective electrodes with anti-Hofmeister selectivity pattern is an important and interesting project in the fields of electrochemistry and electroanalytical chemistry. This thesis focuses on seeking design and synthsis of novel metallic complex and basic studies on solvent polymeric membrane (SPM) anion-selective electrodes containing the novel metallic complex. The electrodes can be applied to medicine and biological sample analysis.This main contents and some conclusions of the thesis are as follows: 1. Studies on Diazatetraene Metallic Complexes as Neutral Carriers for the Preparation of Salicylate -Selective Ion ElectrodesDiazatetraene Metallic Complexes of 3,3'-[ethenebis(imidogenmethin)]-bis-2,4pentanedione Cobalt(II), Copper(II) and Nickel(II)(M(II)EBIBP) are designed and synthesised. The metallic complexes are prepared for ionophores in solvent polymeric membrane electrodes. The influence of plasticizers: 2-nitrophenyl octyl ether(o-NPOE), dideyl sebacate(DDS) and didecyl phthalate(DDP) on the characteristics of electrodes is studied. The results show that the electrode plasticized by o-NPOE and prepared with Co(II)EBIBP exhibits an anti-Hofmeister seletivity sequence with a preferential poteneiometric response to salicylate(Sal"). The potentiometric selectivity coefficients with respect to some common anions are determined by the separated solution method, the selectivity sequence obtained is: Sal>I>SCN>NO2">SO42>NO3>ClO4>Br>C1. The response mechanism is discussed in view of the ac impedance technique and the uv spectroscopy technique.These deviations result from the direct interaction between the central metal and the analyte ion and steric effect associated with the structure of the carrier. The electrode can be applied to medicine and biologic sample analysis and the result is fair agreement with the result given by precipitation method.2. Studies on Tetraazatetraene Metallic Complexes as Neutral Carriers for the Preparation of Thiocyanate -Selective Ion ElectrodesOn the basis of the synthesised diazatetraene metallic complexes, [6,13-diacetyl -5,14-dimethyl-1,4,8,11 -tetraaza-4,6,11,13-tetraene(2-)]Cobalt(II), Copper(II) and Nickel(II)(M(II)LH2) are designed and synthesised. The metallic complexes are prepared for ionophores in solvent polymeric membrane electrodes. The influence of plasticizers: 2-nitrophenyl octyl ether(o-NPOE), dideyl sebacate(DDS) and didecyl phthalate(DDP) on the characteristics of electrodes is studied. The results show that the electrode plasticized by o-NPOE and prepared with Cu(II)LH2 exhibits an anti-Hofmeister seletivity sequence with a preferential poteneiometric response to thiocyanate(SCN'). The potentiometric selectivity coefficients with respect to some common anions are determined by the separated solution method, the selectivity sequence obtained is: SCN>I>SO42>NO3>Br= C1>NO2>C1O4. The response mechanism is discussed in view of the ac impedance technique and the uv spectroscopy technique. These deviations result from the direct interaction between the central metal and the analyte ion and steric effect associated with the structure of the carrier. The electrode can be applied to waste water analysis of the laboratory and the result is fair agreement with the result given by HLPC method.3. Studies on Novel Schiff Metallic Complexes as Neutral Carriers for the Highly Iodide-Selective Ion ElectrodeAnion-selective electrodes based on synthesised Copper(II), Cobalt(II), Zinc(II) and Manganese(III) of N,N-bis(salicylidene)-1,2-bis(p-aminophenoxy)-ethane macrocyclic complex (M(II,III)BBAP) as the neutral carrier are described. The metallic complexes are prepared for ionophores in solvent polymeric membrane electrodes. The influence of plasticizers: 2-nitrophenyl octyl ether(o-NPOE), dideyl sebacate(DDS) and didecyl phthalate(DDP) on the characteristics of electrodes is...