Electrically conducting polymers (ECPs) are one of the most popular types of materials to interface ion-selective membranes (ISMs) with electron conducting substrates to construct solid contact ion-selective electrodes (SCISEs). For optimal ion-to-electron transduction and potential stability, the p-doped ECPs with low oxidation potentials such as PPy need to be generally in their conducting form along with providing a sufficiently hydrophobic interface to counteract the aqueous layer formation. The first criterion requires that the ECPs are in their oxidized state, but the high charge density of this state is detrimental for the prevention of the aqueous layer formation. We offer here a solution to this paradox by implementing a highly hydrophobic perfluorinated anion (perfluorooctane sulfonate, PFOS -) as doping ion by 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 which the oxidized form of the ECP becomes hydrophobic. The proof of concept is shown by using polypyrrole (PPy) films doped with PFOS -(PPy-PFOS) as the solid contact in K + -selective SCISEs (K + -SCISE). Prior to applying the plasticized poly(vinyl chloride) ISM, the oxidation state of the electrodeposited PPy-PFOS was adjusted by polarization to the known open circuit potential of the solid contact in 0.1 M KCl. We show that the pre-polarization results in a hydrophobic PPy-PFOS film with a water contact angle of 97±5º, which effectively prevents the aqueous layer formation under the ISM. Under optimal conditions the K + -SCISEs had a very low standard deviation of E 0 of only 501.0±0.7 mV that is the best E 0 reproducibility reported for ECP-based SCISEs.
In this work, flexible and free-standing composite films of nanofibrillated cellulose/polypyrrole (NFC/PPy) and NFC/PPy-silver nanoparticles (NFC/PPy-Ag) have been synthesized for the first time via in situ one-step chemical polymerization and applied in potential biomedical applications. Incorporation of NFC into PPy significantly improved its film formation ability resulting in composite materials with good mechanical and electrical properties. It is shown that the NFC/PPy-Ag composite films have strong inhibition effect against the growth of Gram-positive bacteria, e.g., Staphylococcus aureus. The electrical conductivity and strong antimicrobial activity makes it possible to use the silver composites in various applications aimed at biomedical treatments and diagnostics. Additionally, we report here the structural and morphological characterization of the composite materials with Fourier-transform infrared spectroscopy, atomic force microscopy, and scanning and transmission electron microscopy techniques.
The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed.
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