Reported is an electrical transduction platform for real‐time wireless anion sensing using single‐walled carbon nanotubes (SWCNTs) noncovalently functionalized with squaramide‐based anion binding selectors. Systematically studied are anion‐binding properties and efficiency of the electrical transduction of the functionalized SWCNT composites using the squaramide‐based selectors with two similar electron‐withdrawing groups, 3,5‐bis(trifluoromethyl)benzyl (1) and 3,5‐bis(trifluoromethyl)phenyl (2), which induce hydrogen‐bonding interaction with anions and deprotonation of a squaramide N–H proton upon addition of acetate (AcO−), respectively. Charge transduction occurs with AcO− as a result of charge transfer from the deprotonated selector 2, whereas less sensitive transduction is observed with selector 1 via hydrogen‐bonding interaction. These results provide guidelines to efficiently transduce the chemical interaction between selectors and anions to create resistive transduction with functionalized SWCNTs. Electron‐withdrawing groups adjacent to the squaramide as well as proximate cationic pyridyl groups, enhance the anion binding affinity and also lower the selector's pKa. The chemiresistive sensor arrays are readily integrated with a wireless sensing module and demonstrated real‐time sensing of multiple anions with a smartphone readout.
Trace analysis of heavy metals in complex, environmentally relevant matrices remains a significant challenge for electrochemical sensors employing stripping voltammetry-based detection schemes. We present an alternative method capable of selectively preconcentrating Cu 2+ ions at the electrode surface using chelating polymer-wrapped multiwalled carbon nanotubes (MWCNTs). An electrochemical sensor consisting of poly-4vinyl pyridine (P4VP)-wrapped MWCNTs anchored to a poly(ethylene terephthalate) (PET)-modified gold electrode (r = 1.5 mm) was designed, produced, and evaluated. The P4VP is shown to form a strong association with Cu 2+ ions, permitting preconcentration adjacent to the electrode surface for interrogation via cyclic voltammetry. The sensor exhibited a detection limit of 0.5 ppm with a linear range of 1.1−13.8 ppm (16.6−216 μM) and a relative standard deviation (RSD) of 4.9% at the Environmental Protection Agency (EPA) limit of 1.3 ppm. Evaluation in tap water, lake water, ocean water, and deionized water rendered similar results, highlighting the generalizability of the presented preconcentration strategy. The advantages of electrochemical analysis paired with polymeric chelation represent an effective platform for the design and deployment of heavy metal sensors for continuous monitoring of natural waters.
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