Electrical Detection of Molecular Transformations Associated with Chemical Reactions Using Graphene Devices

This study proposes a method to electrically detect chemical reactions that involve bond changes through reactions on graphene surfaces. To achieve a highly sensitive detection, we focused on the thiol-ene reaction that combines the maleimide and thiol groups. Graphene field-effect transistors (FETs) were used to detect the binding changes of the modified molecules. Graphene has high carrier mobility and is sensitive to changes in the electronic state of its surface. Graphene has been used as a sensor to detect low-concentration targets with high sensitivity. N-(9-Acridinyl)maleimide (NAM) was chosen as the modified molecule to immobilize maleimide on graphene through π-interaction, and methanethiol (MeSH) was set as the target thiol. The modification of NAM to graphene was first confirmed by attenuated total reflection Fourier transform infrared spectroscopy, and the modification density was 0.5 ± 0.1/nm² through cyclic voltammetry. Owing to a bond exchange, the transfer characteristics of the graphene FET shifted by 2 V to the negative direction after being exposed to MeSH at 10 parts per billion (ppb), equivalent to 0.2 ng, under ultraviolet irradiation. With 5000 ppb of acetic acid, it only shifted 0.7 V. With 1000 ppb of ethanol and 10,000 ppb of methanol, it shifted to the positive direction by 0.4 and 0.6 V, respectively. Because the nontarget molecule showed only a slight response, a thiol-ene chemical reaction was detected. The proposed method can detect the bond-change reaction using an ultralow concentration of MeSH, which indicates that at least 10 ppb (or 0.2 ng) of MeSH was detected by the graphene FET.