An Electrochemical Evaluation of Novel Ferrocene Derivatives for Glutamate and Liver Biomarker Biosensing.

Here, we present an evaluation of two new monosubstituted ferrocene (Fc) derivatives, 3-(1H-pyrrol-1-yl)propanamidoferrocene and 1-hydroxy-2-[2-(thiophen-3-yl)-ethylamino]ethylferrocene, as glutamate oxidase mediators, together with their preparation and characterisation. Taking into consideration the influence of the electronic effects of substituents on the redox potentials of the Fc species, two candidates with pyrrole or thiophene moieties were proposed for investigation. Film studies involved potential sweeping in the presence of pyrrole or 3,4-ethylenedioxythiophene monomers resulting in stable electroactive films with % signal loss upon cycling ranging from 1 to 7.82% and surface coverage (Γ) 0.47-1.15 × 10-9 mol/cm2 for films formed under optimal conditions. Construction of a glutamate oxidase modified electrode resulted in second-generation biosensing with the aid of both cyclic voltammetry and hydrodynamic amperometry, resulting in glutamate sensitivity of 0.86-1.28 µA/mM and Km (app) values over the range 3.67-5.01 mM. A follow-up enzyme assay for liver biomarker γ-glutamyl transpeptidase realised unmediated and mediated measurement establishing reaction and incubation time investigations and a realising response over <100 U/L γ-glutamyl transpeptidase with a sensitivity of 5 nA/UL-1.

Interaction between Langmuir and Langmuir-Blodgett films of two calix[4]arenes with aqueous copper and lithium ions.

The binding interactions between aqueous copper (Cu(2+)) and lithium (Li(+)) ions and Langmuir monolayers and Langmuir-Blodgett (LB) multilayers have been investigated by studying surface pressure-area (Pi-A) isotherms and surface potential-area (DeltaV-A) behavior in order to find the effective dipole moment, mu(perpendicular), of the calixarene molecules in the uncomplexed and complexed states. The orientation of both calix[4]arenes, namely, 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene and 5,17-(9H-fluoren-2-yl)methyleneamino)-11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene, is such that the plane of the calix ring is parallel with the plane of the water surface regardless of the ion content of the subphase. The Gibbs equation was used to interpret the adsorption of ions with both calix[4]arenes as a function of the concentration. Effective dipole moments have been calculated from surface potential values using the Helmholtz equation. In this work, new LB films have been prepared employing two novel amphiphilic calix[4]arene derivatives bearing different upper rim substituents. Thus, the effect of modifiying the upper rim has been observed. The results have shown that these calixarenes may be useful components of ion sensors.