History of Cobaltabis(dicarbollide) in Potentiometry, No Need for Ionophores to Get an Excellent Selectivity

Abstract

This work is a mini-review highlighting the relevance of the θ metallabis(dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− with its peculiar and differentiating characteristics, among them the capacity to generate hydrogen and dihydrogen bonds, to generate micelles and vesicles, to be able to be dissolved in water or benzene, to have a wide range of redox reversible couples and many more, and to use these properties, in this case, for producing potentiometric membrane sensors to monitor amine-containing drugs or other nitrogen-containing molecules. Sensors have been produced with this monoanionic cluster [3,3′-Co(1,2-C2B9H11)2]−. Other monoanionic boron clusters are also discussed, but they are much fewer. It is noteworthy that most of the electrochemical sensor species incorporate an ammonium cation and that this cation is the species to be detected. Alternatively, the detection of the borate anion itself has also been studied, but with significantly fewer examples. The functions of the borate anion in the membrane are different, even as a doping agent for polypyrrole which was the conductive ground on which the PVC membrane was deposited. Apart from these cases related to closo borates, the bulk of the work has been devoted to sensors in which the θ metallabis (dicarbollide) [3,3′-Co(1,2-C2B9H11)2]− is the key element. The metallabis (dicarbollide) anion, [3,3′-Co(1,2-C2B9H11)2]−, has many applications; one of these is as new material used to prepare an ion-pair complex with bioactive protonable nitrogen containing compounds, [YH]x[3,3′-Co(1,2-C2B9H11)2]y as an active part of PVC membrane potentiometric sensors. The developed electrodes have Nernstian responses for target analytes, i.e., antibiotics, amino acids, neurotransmitters, analgesics, for some decades of concentrations, with a short response time, around 5 s, a good stability of membrane over 45 days, and an optimal selectivity, even for optical isomers, to be used also for real sample analysis and environmental, clinical, pharmaceutical and food analysis.

Chemistry of Carbon-Substituted Derivatives of Cobalt Bis(dicarbollide)(1−) Ion and Recent Progress in Boron Substitution

“…Growing attention to the use of the cobalt bis(dicarbollide) anion in biological applications led to the first attempts of electrochemistry in the aqueous milieu [11,12,14,153]. The authors report not only the reversible redox signal of the Co(III) central atom (as was reported previously in non-aqueous media [240]) but also the irreversible signal of the core boron cage (Figure 34) [63,82,244].…”

“…Sensors with bonded ligands were found to be suitable for multisensor systems for the simultaneous determination of several cations [146]. Further information on the significance of metallacarboranes for producing potentiometric membrane sensors, to monitor amine-containing drugs and other nitrogencontaining molecules, is reported in a mini-review from Stoica et al published in 2022 [14].…”

“…The ion is marked by its ionic negative charge, diamagnetic character, low nucleophilicity, and very high thermal, chemical, and radiolytic stability. Its versatility is evident in various applications, including nuclear waste treatment [9,10], conducting polymers and coordination polymers [11], electrochemistry, ion-selective electrodes [11][12][13][14], catalysts, photocatalysts [15,16], and more. The ion (1 − ) also exhibits hydrogen and dihydrogen bonding capabilities, which facilitate self-assembly [17][18][19], water solubility [20], and the formation of micelles and vesicles [21][22][23].…”

Single stop analysis of a protein surface using molecular probe electrochemistry

“…The preparation of the electroactive component in potentiometric membranes for the detection of amino acids was based on the high insolubility of the [YH] [3,3 0 -Co(1,2-C 2 B 9 H 11 ) 2 ] salt in water, with Y being the amino acid under consideration. 42,48 The same concept was applied to stabilize magnetic nanoparticles decorated with amine groups incorporating [3,3 0 -Co(1,2-C 2 B 9 H 11 ) 2 ] À anions. 49 However, these studies offered a vague and general overview of the possible interactions.…”

Employment of chiral columns with superficially porous particles in chiral separations of cobalt bis (dicarbollide) and nido‐7,8‐C2B9H12(1‐) derivatives

“…The high thermal and chemical stability of COSAN and its derivatives led to their employment in materials chemistry, 4–6 electrochemistry, 7,8 and analytical chemistry 9,10 . The growing knowledge of COSAN chemistry led to the investigation of its derivatives in medicinal chemistry 11–20 .…”