Determination of benzoate in cranberry and lingonberry by using a solid-contact benzoate-selective electrode.

Benzoic acid is used as a preservative in processed food, and occasionally in cosmetics and pharmaceuticals, while benzoic acid occurs naturally in, e.g., cranberry and lingonberry. Therefore, the determination of benzoate is of interest for product quality assurance, food safety, and personal health. In this work, a solid-contact benzoate-selective electrode (benzoate-ISE) was developed by utilising poly(3,4-ethylenedioxythiophene) (PEDOT) as solid contact and a solvent polymeric membrane containing a 1,3-bis(carbazolyl)urea derivative as ionophore. The benzoate-ISE was characterised in parallel with an ionophore-free control-ISE by electrochemical impedance spectroscopy and potentiometry. The presence of the ionophore in the membrane improved the selectivity to benzoate. Benzoate-ISEs and control-ISEs were used further to determine the benzoate concentration in cranberry and lingonberry by standard addition. The results obtained with both types of ISEs were compared with those obtained by ion chromatography. The results obtained with benzoate-ISEs were consistent with those obtained with ion chromatography. On the contrary, the control-ISE (without ionophore) gave significantly higher benzoate concentrations, especially in the case of cranberry where the benzoate concentration was low (ca 0.2 g kg-1) compared to lingonberry (ca 1 g kg-1). Hence, the benzoate-selectivity of the ionophore was crucial to obtain a benzoate-ISE that was practically applicable for determination of benzoate concentrations in cranberry and lingonberry.

Aqueous Processable One-Dimensional Polypyrrole Nanostructured by Lignocellulose Nanofibril: A Conductive Interfacing Biomaterial.

One-dimensional (1D) nanomaterials of conductive polypyrrole (PPy) are competitive biomaterials for constructing bioelectronics to interface with biological systems. Synergistic synthesis using lignocellulose nanofibrils (LCNF) as a structural template in chemical oxidation of pyrrole with Fe(III) ions facilitates surface-confined polymerization of pyrrole on the nanofibril surface within a submicrometer- and micrometer-scale fibril length. It yields a core-shell nanocomposite of PPy@LCNF, wherein the surface of each individual fibril is coated with a thin nanoscale layer of PPy. A highly positive surface charge originating from protonated PPy gives this 1D nanomaterial a durable aqueous dispersity. The fibril-fibril entanglement in the PPy@LCNFs facilely supported versatile downstream processing, e.g., spray thin-coating on glass, flexible membranes with robust mechanics, or three-dimensional cryogels. A high electrical conductivity in the magnitude of several to 12 S·cm-1 was confirmed for the solid-form PPy@LCNFs. The PPy@LCNFs are electroactive and show potential cycling capacity, encompassing a large capacitance. Dynamic control of the doping/undoping process by applying an electric field combines electronic and ionic conductivity through the PPy@LCNFs. The low cytotoxicity of the material is confirmed in noncontact cell culture of human dermal fibroblasts. This study underpins the promises for this nanocomposite PPy@LCNF as a smart platform nanomaterial in constructing interfacing bioelectronics.

Design, synthesis and application of carbazole macrocycles in anion sensors.

Carboxylate sensing solid-contact ion-selective electrodes (ISEs) were created to provide a proof-of-concept ISE development process covering all aspects from in silico ionophore design to functional sensor characterization. The biscarbazolylurea moiety was used to synthesize methylene-bridged macrocycles of different ring size aiming to fine tune selectivity towards different carboxylates. Cyclization was achieved with two separate strategies, using either amide synthesis to access up to -[CH2]10- macrocycles or acyl halides to access up to -[CH2]14- macrocycles. Seventy-five receptor-anion complexes were modelled and studied with COSMO-RS, in addition to all free host molecules. In order to predict initial selectivity towards carboxylates, 1H NMR relative titrations were used to quantify binding in DMSO-d 6/H2O solvent systems of two proportions - 99.5%:0.5% m/m and 90.0%:10.0% m/m, suggesting initial selectivity towards acetate. Three ionophores were selected for successful sensor prototype development and characterization. The constructed ion-selective electrodes showed higher selectivity towards benzoate than acetate, i.e., the selectivity patterns of the final sensors deviated from that predicted by the classic titration experiments. While the binding constants obtained by NMR titration in DMSO-d 6/H2O solvent systems provided important guidance for sensor development, the results obtained in this work emphasize the importance of evaluating the binding behavior of receptors in real sensor membranes.

New Signal Readout Principle for Solid-Contact Ion-Selective Electrodes.

A novel approach to signal transduction concerning solid-contact ion-selective electrodes (SC-ISE) with a conducting polymer (CP) as the solid contact is investigated. The method presented here is based on constant potential coulometry, where the potential of the SC-ISE vs the reference electrode is kept constant using a potentiostat. The change in the potential at the interface between the ion-selective membrane (ISM) and the sample solution, due to the change in the activity of the primary ion, is compensated with a corresponding but opposite change in the potential of the CP solid contact. This enforced change in the potential of the solid contact results in a transient reducing/oxidizing current flow through the SC-ISE. By measuring and integrating the current needed to transfer the CP to a new state of equilibrium, the total cumulated charge that is linearly proportional to the change of the logarithm of the primary ion activity is obtained. In this work, different thicknesses of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS) were used as solid contact. Also, coated wire electrodes (CWEs) were included in the study to show the general validity of the new approach. The ISM employed was selective for K(+) ions, and the selectivity of the membrane under implementation of the presented transduction mechanism was confirmed by measurements performed with a constant background concentration of Na(+) ions. A unique feature of this signal readout principle is that it allows amplification of the analytical signal by increasing the capacitance (film thickness) of the solid contact of the SC-ISE.