For ion-selective electrodes (ISEs) to be employed in wearable and implantable applications, the ion-selective membrane components should be biocompatible, and leaching of components, such as plasticizer or ionophore, out of the sensing membrane should be inhibited. To achieve this, we employed a plasticizer-free silicone as the membrane matrix and synthesized as the ionophore a derivative of the bis-crown ether based potassium ionophore BME-44, incorporating a triethoxysilyl functional group that covalently attaches to condensation-cured silicones during the curing process. Soxhlet extraction of these membranes with dichloromethane shows that up to 96% of the ionophore is attached to the silicone membrane during curing.
View Article and Find Full Text PDFWith a view to potentiometric sensing with minimal calibration requirements and high long-term stability, colloid-imprinted mesoporous (CIM) carbon was functionalized by the covalent attachment of a cobalt redox buffer and used as a new solid contact for ion-selective electrodes (ISEs). The CIM carbon surface was first modified by electroless grafting of a terpyridine ligand (Tpy-ph) using diazonium chemistry, followed by stepwise binding of Co(II) and an additional Tpy ligand to the grafted ligand, forming a bis(terpyridine) Co(II) complex, CIM-ph-Tpy-Co(II)-Tpy. Half a molar equivalent of ferrocenium tetrakis(3-chlorophenyl)borate was then used to partially oxidize the Co(II) complex.
View Article and Find Full Text PDFThe ability to miniaturize ion-selective sensors that enable microsensor arrays and wearable sensor patches for ion detection in environmental or biological samples requires all-solid-state sensors with solid contacts for transduction of an ion activity into an electrical signal. Nanostructured carbon materials function as effective solid contacts for this purpose. They can also contribute to improved potential signal stability, reducing the need for frequent sensor calibration.
View Article and Find Full Text PDFSolid-contact ion-selective electrodes (SC-ISEs) in direct long-term contact with physiological samples must be biocompatible and resistant to biofouling, but most wearable SC-ISEs proposed to date contain plasticized poly(vinyl chloride) (PVC) membranes, which have poor biocompatibility. Silicones are a promising alternative to plasticized PVC because of their excellent biocompatibility, but little work has been done to study the relationship between silicone composition and ISE performance. To address this, we prepared and tested K SC-ISEs with colloid-imprinted mesoporous (CIM) carbon as the solid contact and three different condensation-cured silicones: a custom silicone prepared in-house (), a commercial silicone (Dow 3140, ), and a commercial fluorosilicone (Dow 730, ).
View Article and Find Full Text PDFNanopore-driven sequestration of ionic liquids from a silicone membrane is presented, a phenomenon that has not been reported previously. Reference electrodes with ionic liquid doped polydimethylsiloxane (PDMS) reference membranes and colloid-imprinted mesoporous carbon (CIM) as solid contact are not functional unless special attention is paid to the porosity of the solid contact. In the fabrication of such reference electrodes, a solution of a hydroxyl-terminated silicone oligomer, ionic liquid, cross-linking reagent, and polymerization catalyst is deposited on top of the carbon layer, rapidly filling the pores of the CIM carbon.
View Article and Find Full Text PDFComplexation of the adjacent actinide ions americium(III) and curium(III) by the ligand N,N'-bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2bp18c6) in aqueous solution was studied to quantify and characterize its americium/curium selectivity. Liquid-liquid extraction and spectrophotometric titration indicated the presence of both fully deprotonated and monoprotonated complexes, An(bp18c6)(+) and An(Hbp18c6)(2+) (An = Am or Cm), at the acidities that would be encountered when treating nuclear wastes. The stability constants of the complexes in 1 M NaNO3 determined using competitive complexation were log β101 = 15.
View Article and Find Full Text PDF