Anti-fouling TiO₂‑Coated Polymeric Membrane Ion-Selective Electrodes with Photocatalytic Self-Cleaning Properties

Nowadays, using a polymeric membrane ion-selective electrode (ISE) to achieve reliable ion sensing in complex samples remains challenging because of electrode fouling. To address this challenge, we describe a polymeric membrane ISE with excellent anti-fouling and self-cleaning properties based on surface covalent modification of an anatase TiO2 coating. Under ultraviolet illumination, the reactive oxygen species produced by photocatalytic TiO2 can not only kill microorganisms but also degrade organic foulants into carbon dioxide and water, and a formed superhydrophilic film can effectively prevent the adsorption of foulants, thus inhibiting the occurrence of biofouling and organic fouling of the sensors. More importantly, residual foulants could be fully self-cleaned through the flow of water droplets. By using Ca2+-ISE as a model, an anti-fouling polymeric membrane potentiometric sensor has been developed. Compared to the unmodified electrode, the TiO2-coated Ca2+-ISE exhibits remarkably improved anti-biofouling properties with a low bacterial adhesion rate of 4.74% and a high inhibition rate of 96.62%. In addition, the proposed electrode displays unique properties of anti-organic dye fouling and a superior self-cleaning ability even after soaking in a concentrated bacterial suspension of 109 CFU mL–1 for 60 days. The present approach can be extended to improve the fouling resistance of other electrochemical or optical membrane sensors and is promising for the construction of contamination-free sensors

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<p>Nowadays, it is still difficult for molecularly imprinted polymers (MIPs) to achieve homogeneous recognition since they cannot be easily dissolved in organic or aqueous phase. To address this issue, soluble molecularly imprinted nanorods have been synthesized by using soluble polyaniline doped with a functionalized organic protonic acid as the polymer matrix. By employing 1-naphthoic acid as a model, the proposed imprinted nanorods exhibit an excellent solubility and good homogeneous recognition ability. The imprinting factor for the soluble imprinted nanoroads is 6.8. The equilibrium dissociation constant and the apparent maximum number of the proposed imprinted nanorods are 248.5 μM and 22.1 μmol/g, respectively. We believe that such imprinted nanorods may provide an appealing substitute for natural receptors in homogeneous recognition related fields.</p

Soluble Molecularly Imprinted Polymer-Based Potentiometric Sensor for Determination of Bisphenol AF

Molecularly imprinted polymer (MIP)-based polymeric membrane potentiometric sensors have been successfully developed for determination of organic compounds in their ionic and neutral forms. However, most of the MIP receptors in potentiometric sensors developed so far are insoluble and cannot be well dissolved in the polymeric membranes. The heterogeneous molecular recognitions between the analytes and MIPs in the membranes are inefficient due to the less available binding sites of the MIPs. Herein we describe a novel polymeric membrane potentiometric sensor using a soluble MIP (s-MIP) as a receptor. The s-MIP is synthesized by the swelling of the traditional MIP at a high temperature. The obtained MIP can be dissolved in the plasticized polymeric membrane for homogeneous binding of the imprinted polymer to the target molecules. By using neutral bisphenol AF as a model, the proposed method exhibits an improved sensitivity compared to the conventional MIP-based sensor with a lower detection limit of 60 nM. Moreover, the present sensor exhibits an excellent selectivity over other phenols. We believe that s-MIPs can provide an appealing substitute for the traditional insoluble MIP receptors in the development of polymeric membrane-based electrochemical and optical sensors

Trace-Level Potentiometric Detection in the Presence of a High Electrolyte Background

Polymeric membrane ion-selective electrodes (ISEs) have become attractive tools for trace-level environmental and biological measurements. However, applications of such ISEs are often limited to measurements with low levels of electrolyte background. This paper describes an asymmetric membrane rotating ISE configuration for trace-level potentiometric detection with a high-interfering background. The membrane electrode is conditioned in a solution of interfering ions (e.g., Na⁺) so that no primary ions exist in the ISE membrane, thus avoiding the ion-exchange effect induced by high levels of interfering ones in the sample. When the electrode is in contact with the primary ions, the interfering ions in the membrane surface can be partially displaced by the primary ions due to the favorable ion–ligand interaction with the ionophore in the membrane, thus causing a steady-state potential response. By using the asymmetric membrane with an ion exchanger loaded on the membrane surface, the diffusion of the primary ions from the organic boundary layer into the bulk of the membrane can be effectively blocked; on the other hand, rotation of the membrane electrode dramatically reduces the diffusion layer thickness of the aqueous phase and significantly promotes the mass transfer of the primary ions to the sample–membrane interface. The induced accumulation of the primary ions in the membrane boundary layer largely enhances the nonequilibrium potential response. By using copper as a model, the new concept offers a subnanomolar detection limit for potentiometric measurements of heavy metals with a high electrolyte background of 0.5 M NaCl