Dynamics of redox processes in ionic liquids and their interplay for discriminative electrochemical sensing

Details

• Personal Author:
  Rehman A ; Xiao C ; Zeng X
• Description:
  Motivated by the use of ionic liquids (ILs) as green replacers of traditional electrolytes, a mechanistic study has been systematically conducted to comprehend various design principles responsible for electrochemical profiling of redox-active species in ILs. The full spectrum of properties associated with ILs is exploited to assess the viability of this platform, thus revealing the correlation between the redox properties and the physiochemical parameters of the species involved. This includes the evaluation of (1) the variation of redox responses toward analytes with similar molecular structures or functionalities of ILs, (2) the influence in terms of physical criteria of the system such as viscosity and conductivity as well as chemical structure of ILs, and (3) the sustainability in harsh conditions (high temperature or humidity) and interferences. The principle is exemplified via trinitrotoluene (TNT) and dinitrotoluene (DNT) with inherent redox activity as analytes and IL membranes as solvents and electrolytes using glassy carbon (GC) electrodes. A discrete response pattern is generated that is analyzed through linear discriminant analysis (LDA) leading to 100% classification accuracy even for the mixture of analytes. Quantitative analysis through square wave voltammetry (SWV) gave rise to the detection limits in liquid phase of 190 and 230 nM for TNT and DNT, respectively, with a linear range up to 100 uM. Gas-phase analysis shows strong redox signals for the estimated concentrations of 0.27 and 2.05 ppm in the gas phase for TNT and DNT, respectively, highlighting that ILs adopt a role as a preconcentrator to add on sensitivity with enhanced selectivity coming from their physiochemical diversity, thus addressing the major concerns usually referred to most sensor systems. [Description provided by NIOSH]
• Subjects:
  Chemistry Humidity Occupational Health Safety Temperature
• Keywords:
  2,4,6-Trinitrotoluene Chemical Properties Dinitrotoluene Gas Detectors Gases Molecular Structure Physical Properties Sensors Temperature Effects Viscosity
• ISSN:
  0003-2700
• Document Type:
  Text
• Funding:
  Grant
• Genre:
  Journal Article
• Place as Subject:
  Michigan ; OSHA Region 5
• CIO:
  National Institute for Occupational Safety and Health (NIOSH)
• Topic:
  Workplace Safety & Health
• Location:
  North America
• Volume:
  84
• Issue:
  3
• NIOSHTIC Number:
  nn:20048644
• Citation:
  Anal Chem 2012 Feb; 84(3):1416-1424
• Contact Point Address:
  Xiangqun Zeng, The Department of Chemistry, Oakland University, Rochester, Michigan 48309
• Email:
  zeng@oakland.edu
• CAS Registry Number:
  2,4,6-Trinitrotoluene (CAS RN 118-96-7) ; Dinitrotoluene (CAS RN 25321-14-6)
• Federal Fiscal Year:
  2012
• Performing Organization:
  Michigan State University
• Peer Reviewed:
  True
• Start Date:
  20100901
• Source Full Name:
  Analytical Chemistry
• End Date:
  20150831
• Collection(s):
  National Institute for Occupational Safety and Health
• Main Document Checksum:
  urn:sha-512:89f5f41b25f89c4f99c4d327f9191053b5744adda1305462a1680d2a3b9770c81a50f08b16920d5fdf2d08f26ecbab7ada2664dc4d01d55a4f344d6766621632
• Download URL:
  https://stacks.cdc.gov/view/cdc/203352/cdc_203352_DS1.pdf
• File Type:
  [PDF - 3.97 MB ]