Evaluating impacts of bambusuril pocket size and sterics on anion binding trends using ChemFET sensors.

Chemically-sensitive Field Effect Transistors (ChemFETs) are a useful tool to evaluate aqueous anion affinity of hydrophobic supramolecular scaffolds. More specifically, ChemFETs can be used to probe impacts of receptor modification to aqueous anion affinity. In this study, ChemFETs are used to evaluate the anion affinity of both dodeca-n-butyl bambus[6]uril and dodecabenzyl bambus[6]uril to assess steric effects in the chemical selectivity of the sensor membrane. The ChemFETs were evaluated through a series of common anions in the Hofmeister series in order to ascertain the difference in detection limit imparted by the specific functionalization of the bambus[6]uril macrocycles, which are quite sensitive to modest steric effects. Significant improvements to perchlorate and nitrate detection limits were observed via n-butyl bambusuril-containing sensor membranes over detection limits recorded with benzyl bambusuril sensors.

Benchmarking the placement of hydrosulfide in the Hofmeister series using a bambus[6]uril-based ChemFET sensor.

Hydrosulfide (HS-) is the conjugate base of gasotransmitter hydrogen sulfide (H2S) and is a physiologically-relevant small molecule of great interest in the anion sensing community. However, selective sensing and molecular recognition of HS- in water remains difficult because, in addition to the diffuse charge and high solvation energy of anions, HS- is highly nucleophilic and readily oxidizes into other reactive sulfur species. Moreover, the direct placement of HS- in the Hofmeister series remains unclear. Supramolecular host-guest interactions provide a promising platform on which to recognize and bind hydrosulfide, and characterizing the placement of HS- in the Hofmeister series would facilitate the future design of selective receptors for this challenging anion. Few examples of supramolecular HS- binding have been reported, but the Sindelar group reported HS- binding in water using bambus[6]uril macrocycles in 2018. We used this HS- binding platform as a starting point to develop a chemically-sensitive field effect transistor (ChemFET) to facilitate assigning HS- to a specific place in the Hofmeister series. Specifically, we prepared dodeca-n-butyl bambus[6]uril and incorporated it into a ChemFET as the HS- receptor motif. The resultant device provided an amperometric response to HS-, and we used this device to measure the response of other anions, including SO42-, F-, Cl-, Br-, NO3-, ClO4-, and I-. Using this response data, we were able to experimentally determine that HS- lies between Cl- and Br- in the Hofmeister series, which matches recent theoretical computational work that predicted a similar placement. Taken together, these results highlight the potential of using molecular recognition coupled with ChemFET architectures to develop new approaches for direct and reversible HS- detection and measurement in water and further advance our understanding of different recognition approaches for this challenging anion.

Hydrosulfide-selective ChemFETs for aqueous H2S/HS- measurement.

We have prepared and characterized hydrosulfide-selective ChemFET devices based on a nitrile butadiene rubber membrane containing tetraoctylammonium nitrate as a chemical recognition element that is applied to commercially available field-effect transistors. The sensors have fast (120 s) reversible responses, selectivity over other biologically relevant thiol-containing species, detection limits of 8 mM, and a detection range from approximately 5 to 500 mM. Sensitivities are shown to be 53 mV per decade at pH 8. Use of this compact, benchtop sensor platform requires little training - only the ability to measure DC voltage, which can be accomplished with a conventional multimeter or a simple analog data acquisition device paired with a personal computer. To the best of our knowledge, this report describes the first example of direct potentiometric measurement of the hydrosulfide ion in water.