Graphene Functionalized with Imidazole Derivatives as Nanotransducers for Electrochemically Detecting Isothiazolinone Biocides

Abstract

Isothiazolinones, which are widely used as chemical additives in many industries, may lead to skin irritation and allergies, thereby adversely influencing human health and the environment. Therefore, this paper proposes an efficient strategy for screening nanohybrid transducers to selectively detect 2-octyl-3-isothiazolinone (OIT) as a representative isothiazolinone. Chemical receptor (CR) candidates consisting of two parts: a reactive imidazole unit and side functional group for covalent conjugation with graphene and noncovalent interaction with the target, respectively, were designed. Five CR structures were selected and synthesized based on density-functional-theory calculations. The synthesized CRs were anchored to graphene for electrochemical transduction. The alkyl groups calculated to have the highest chemical affinities toward OIT were introduced in the CR/graphene nanohybrids (CGNHs). The electrochemical responses of the CGNHs toward OIT depended on the CR type, OIT concentration, and applied potential. Therefore, the combination of five CGNHs as a transducer with different potentials enabled the facile and effective detection of OIT (1–200 mg L–1) from the interferences through principal component analyses. The best CR corresponded to the dodecyloxy group, and the optimal measurement conditions included a scan rate of 25 mV s–1 and applied potentials of −0.75, 0.08, and 1.30 V (vs Ag/AgNO3). The proposed strategy can facilitate the efficient development of nanotransducers for identifying different types of chemical species such as biocides.

Two‐Step Sequential Process for Fabricating Graphene Nanosheets Decorated with Copper Halide Nanocrystals and Their Optoelectronic Applications

“…The geometry was optimized using the B3LYP functional combined with the 6-31G(d) split-valence basis set. [31,32]…”

Physically Exfoliating 2D Materials: A Versatile Combination of Different Materials into a Layered Structure

“…To effectively eliminate interlayer interaction, heteroatoms or functional groups have been introduced into 2D materials via various chemical means, such as oxidation/reduction, selective etching, and specific addition reactions (diazonium, nitrene, carbene, etc. ). ,,− In particular, diazonium chemistry has been widely used for graphene, MoS 2 , WS 2 , WSe 2 , Sb 2 S 3 , and Bi 2 S 3 . ,, Strano and co-workers provided a comprehensive summary of studies on the covalent functionalization of graphene with diazonium compounds. , The grafting of diazonium compounds onto graphene was dependent on graphene’s Fermi energy and the density of states of the diazonium reactants, and therefore the resulting reaction rate was highly affected by the number of graphene layers, edge states, defects, and the electrostatic environment. One example is an edge-functional MoS 2 exfoliation method that employs a soft organic compound as an exfoliating agent with no metallic or organometallic components .…”

“…A range of 2D materials with promising properties, such as transition metal dichalcogenides (TMDs), transition metal oxides (TMOs), and transition metal carbides/nitrides (MXenes), has emerged, with a strong potential for widespread application in a variety of fields. Many studies on 2D materials have shown that they have extraordinary catalytic and electronic properties. − TMDs, ,,,, for example, have been utilized as cocatalysts for enhanced photocatalysis due to the highly active chalcogenide atoms at the exposed edges and a suitable band position. In particular, the process of reducing bulk 2D materials into single or a few layers involves inevitably the severing of their two-dimensionally oriented chemical bonds.…”

Heterostructured 2D material-based electro-/photo-catalysts for water splitting

“…125,126 Graphene exhibits extraordinary properties such as a large surface area (B2600 m 2 g À1 ), excellent mechanical strength, high thermal and electrical conductivity (B5000 W m À1 K À1 ), high carrier mobility (2 Â 10 5 cm 2 V À1 s À1 ), and optical transparency. [127][128][129][130] Because of its exceptional electrical conductivity, graphene is an ideal material for high-performance electronic applications, including energy storage and conversion devices as well as sensors that require fast charge transport. [131][132][133] The efficient electron transfer and tunable electronic properties of graphene play an important role in catalyzing various chemical reactions, particularly for water splitting.…”