Potential sensing of toxic chemical warfare agents (CWAs) by twisted nanographenes: A first principle approach

Naila Sattar; Hasnain Sajid; Sobia Tabassum; Khurshid Ayub; Tariq Mahmood; Mazhar Amjad Gilani

doi:10.1016/j.scitotenv.2022.153858

Potential sensing of toxic chemical warfare agents (CWAs) by twisted nanographenes: A first principle approach

Sci Total Environ. 2022 Jun 10:824:153858. doi: 10.1016/j.scitotenv.2022.153858. Epub 2022 Feb 14.

Authors

Naila Sattar¹, Hasnain Sajid², Sobia Tabassum³, Khurshid Ayub⁴, Tariq Mahmood⁵, Mazhar Amjad Gilani⁶

Affiliations

¹ Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Lahore 54600, Pakistan.
² School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS, UK.
³ Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS University Islamabad, Lahore Campus, Lahore 54600, Pakistan.
⁴ Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Abbottabad 22060, Pakistan.
⁵ Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Abbottabad 22060, Pakistan; Department of Chemistry, College of Science, University of Bahrain, P.O. Box 32038, Bahrain.
⁶ Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Lahore 54600, Pakistan. Electronic address: mazhargilani@cuilahore.edu.pk.

PMID: 35176369
DOI: 10.1016/j.scitotenv.2022.153858

Abstract

The toxic chemical warfare agents (CWAs) are extremely harmful to the living organisms. Their efficient detection and removal in a limited time span are essential for the human health and environmental security. Twisted nanographenes have great applications in the fields of energy storage and optoelectronics, but their use as sensors is rarely described. Therefore, we have explored the sensitivity and selectivity of twisted nanographene analogues (C₃₂H₁₆, C₆₄H₃₂) towards selected toxic CWAs, including phosgene, thiophosgene and formaldehyde. The interaction between CWAs and twisted nanographenes is mainly interpreted by considering the optimized geometries, adsorption energies, natural bond orbital (NBO), frontier molecular orbital (FMO), non-covalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analyses. The structural geometries show that the central octagon of twisted nanographenes is the most favorable site of interaction. The interaction energies reveal the physisorption of selected CWAs on tNGs surface. The average energy gap change (%E_H-L^a) and % sensitivity are quantitatively determined to evaluate the sensing capability of the twisted nanographenes. Among the selected CWAs molecules, the sensitivity of tNG analogues (C₃₂H₁₆ and C₆₄H₃₂) is superior towards thiophosgene (ThP), which is revealed by the high interaction energies of -8.19 and - 12.17 kcal/mol, respectively. This theoretical study will help experimentalists to devise novel sensors based on twisted nanographenes for the detection of toxic CWAs which may also work efficiently under the humid conditions.

Keywords: Chemical warfare agents (CWAs); Formaldehyde; Phosgene; Sensor; Thiophosgene; Twisted nanographenes (tNGs).

MeSH terms

Adsorption
Chemical Warfare Agents* / analysis
Chemical Warfare Agents* / toxicity
Humans

Substances

Chemical Warfare Agents