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Potentiometric Performance of Ion-Selective Electrodes Based on Polyaniline and Chelating Agents: Detection of Fe²⁺ or Fe³⁺ Ions.

ABSTRACT: We constructed a sensor for the determination of Fe²⁺ and/or Fe³⁺ ions that consists of a polyaniline layer as an ion-to-electron transducer; on top of it, chelating molecules are deposited (which can selectively chelate specific ions) and protected with a non-biofouling poly(2-methyl-2-oxazoline)s layer. We have shown that our potentiometric sensing layers show a rapid response to the presence of Fe²⁺ or Fe³⁺ ions, do not experience interference with other ions (such as Cu²⁺), and work in a biological environment in the presence of bovine serum albumin (as a model serum protein). The sensing layers detect iron ions in the concentration range from 5 nM to 50 µM.

SUBMITTER: Ismail R

PROVIDER: S-EPMC9313018 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Calibration-free sensors are generally understood as analytical tools with no need for calibration apart from the initial one (i.e., after its fabrication). However, an "ideal" and therefore "more restricted" definition of the concept considers that no calibration is necessary at all, with the sensor being capable of directly providing the analyte concentration in the sample. In the electroanalysis field, investigations have been directed to charge-based readouts (i.e., coulometry) that allow for concentration calculation via the Faraday Law: The sample volume must be precisely defined and the absoluteness of the electrochemical process in which the analyte is involved must be ensured (i.e., the analyte in the sample is ∼100% converted/transported). Herein, we report on the realization of calibration-free coulometric ISEs based on ultrathin ion-selective membranes, which is demonstrated for the detection of potassium ions (K+). In essence, the K+ transfer at the membrane-sample interface is modulated by the oxidation state of the conducting polymer underlying the membrane. The accumulation/release of K+ to/from the membrane is an absolute process owing to the confinement of the sample to a thin-layer domain (thickness of <100 μm). The capacity of the membrane expressed in charge is fixed to ca. 18 μC, and this dictates the detection of micromolar levels of K+ present in ca. 5 μL sample volume. The system is interrogated with cyclic voltammetry to obtain peaks related to the K+ transfer that can be treated charge-wise. The conceptual and technical innovative steps developed here made the calibration-free detection of K+ possible in artificial and real samples with acceptable accuracy (<10% difference compared with the results obtained from a current-based calibration and ion chromatography). The charge-based analysis does not depend on temperature and appeared to be repetitive, reproducible, and reversible in the concentration range from 1 to 37.5 μM, with an average coulometry efficiency of 96%.

Project description:Inspired by the remarkable electronic and optical properties of single walled carbon nanotubes (SWNTs), various molecular sensing devices with sensitivity down to the single molecule level have been developed. However, most sensing approaches such as field effect transistors or near infrared (NIR) fluorescence require the rigorous debundling and separation of metallic tubes and semiconducting tubes in order to reach the desired high sensitivity. Interestingly, all carbon nanomaterials including carbon nanotubes, graphite, graphene, and even amorphous carbon exhibit extremely strong π-plasmon absorption in the ultraviolet region. This strong absorption has been studied as an undesired optical background for applications based on visible and NIR absorptions. For the first time, we found that the strong π-plasmon absorption of SWNTs in the ultraviolet region is extremely sensitive to ion binding. It is even much more sensitive than the absorption in the visible and NIR regions. Herein, we present our first exploration into using the extremely strong plasmon absorption of SWNTs to develop a new sensing platform for the detection of metallic ions. The detection selectivity is realized by modifying the surface of SWNTs with molecular ligands that have a high specificity for metal ions. As a demonstration, the new method is applied to selectively detect iron ions (Fe3+) by modifying the surface of the SWNTs with deferoxamine (DFO), a natural bacterial siderophore, which has a high specificity and affinity for Fe3+. The selective detection of Fe3+ in both aqueous solution and complex rain water is achieved with a pM level of sensitivity and detection limit. In situ resonant Raman spectroscopy demonstrated that the sensitive detection possibly involves electron transfer between the formed Fe-DFO complexes and the SWNTs. We envisage that it can be used to detect other metal ions when a specific binding chelator is attached to the carbon nanotube surface.

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Potentiometric Performance of Ion-Selective Electrodes Based on Polyaniline and Chelating Agents: Detection of Fe²⁺ or Fe³⁺ Ions.

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Potentiometric Performance of Ion-Selective Electrodes Based on Polyaniline and Chelating Agents: Detection of Fe2+ or Fe3+ Ions.

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OmicsDI is part of the ELIXIR infrastructure

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Potentiometric Performance of Ion-Selective Electrodes Based on Polyaniline and Chelating Agents: Detection of Fe²⁺ or Fe³⁺ Ions.