title: Single electron transfer-driven multi-dimensional signal read-out function of TCNQ as an "off-the-shelf" detector for cyanide.
abstract: Herein we report the first applications of TCNQ as a rapid and highly sensitive off-the-shelf cyanide detector. As a proof-of-concept, we have applied a kinetically selective single-electron transfer (SET) from cyanide to deep-lying LUMO orbitals of TCNQ to generate a persistently stable radical anion (TCNQ(•-)), under ambient condition. In contrast to the known cyanide sensors that operate with limited signal outputs, TCNQ(•-) offers a unique multiple signaling platform. The signal readability is facilitated through multichannel absorption in the UV-vis-NIR region and scattering-based spectroscopic methods like Raman spectroscopy and hyper Rayleigh scattering techniques. Particularly notable is the application of the intense 840 nm NIR absorption band to detect cyanide. This can be useful for avoiding background interference in the UV-vis region predominant in biological samples. We also demonstrate the fabrication of a practical electronic device with TCNQ as a detector. The device generates multiorder enhancement in current with cyanide because of the formation of the conductive TCNQ(•-).
authors.affiliation: Supramolecular and Material Chemistry Lab, School of Physical Sciences, Jawaharlal Nehru University, New Delhi 110067, India.
authors.forename: M R
authors.initials: MR
authors.lastname: Ajayakumar
authors.forename: Kalyanashis
authors.initials: K
authors.lastname: Mandal
authors.forename: Kamla
authors.initials: K
authors.lastname: Rawat
authors.forename: Deepak
authors.initials: D
authors.lastname: Asthana
authors.forename: Ravindra
authors.initials: R
authors.lastname: Pandey
authors.forename: Akanksha
authors.initials: A
authors.lastname: Sharma
authors.forename: Sarita
authors.initials: S
authors.lastname: Yadav
authors.forename: Subhasis
authors.initials: S
authors.lastname: Ghosh
authors.forename: Pritam
authors.initials: P
authors.lastname: Mukhopadhyay
mesh_terms: D000838:Anions; D003486:Cyanides / Q000032:analysis / Q000302:isolation & purification*; D004563:Electrochemistry / Q000379:methods; D004579:Electron Transport; D004581:Electronics; D004583:Electrons; D007700:Kinetics; D008422:Materials Testing; D009570:Nitriles / Q000032:analysis* / Q000737:chemistry*; D012995:Solubility; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D019265:Spectroscopy, Near-Infrared / Q000379:methods*; D013059:Spectrum Analysis, Raman / Q000379:methods*
chemical_list: D000838:Anions; D003486:Cyanides; D009570:Nitriles; C013703:tetracyanoquinodimethane