Polymeric Sorbent with Controlled Surface Polarity: An Alternate for Solid-Phase Extraction of Nerve Agents and Their Markers from Organic Matrix

Abstract

Extraction and identification of lethal nerve agents and their markers in complex organic background have a prime importance from the forensic and verification viewpoint of the Chemical Weapons Convention (CWC). Liquid-liquid extraction with acetonitrile and commercially available solid phase silica cartridges are extensively used for this purpose. Silica cartridges exhibit limited applicability for relatively polar analytes, and acetonitrile extraction shows limited efficacy toward relatively nonpolar analytes. The present study describes the synthesis of polymeric sorbents with tunable surface polarity, their application as a solid-phase extraction (SPE) material against nerve agents and their polar as well as nonpolar markers from nonpolar organic matrices. In comparison with the acetonitrile extraction and commercial silica cartridges, the new sorbent showed better extraction efficiency toward analytes of varying polarity. The extraction parameters were optimized for the proposed method, which included ethyl acetate as an extraction solvent and n-hexane as a washing solvent. Under optimized conditions, method linearity ranged from 0.10 to 10 μg mL ( r = 0.9327-0.9988) for organophosphorus esters and 0.05-20 μg mL ( r = 0.9976-0.9991) for nerve agents. Limits of detection (S:N = 3:1) in the SIM mode were found in the range of 0.03-0.075 μg mL for organophosphorus esters and 0.015-0.025 μg mL for nerve agents. Limits of quantification (S:N = 10:1) were found in the range of 0.100-0.25 μg mL for organophosphorus esters and 0.05-0.100 μg mL for nerve agents in the SIM mode. The recoveries of the nerve agents and their markers ranged from 90.0 to 98.0% and 75.0 to 95.0% respectively. The repeatability and reproducibility (with relative standard deviations (RSDs) %) for organophosphorus esters were found in the range of 1.35-8.61% and 2.30-9.25% respectively. For nerve agents, the repeatability range from 1.00 to 7.75% and reproducibility were found in the range of 2.17-6.90%.

Materials for Solid-Phase Extraction of Organic Compounds

“…Recently, the performance of different materials prepared from a combination of different monomers, such as MAA, 2-hydroxyethyl methacrylate (HEMA), EDMA, and DVB were compared. The material based on MAA-HEMA ultimately showed the best recoveries (from 75% to 100%) for the extraction of a group of nerve agents from an organic matrix [15].…”

“…MCM41: Mobile Composition of Matter No. 41; 9 SBA: Santa Barbara Amorphous;10 EDCs: endocrine disrupting compounds; 11 KIT-6: KoreaAdvanced Institute of Science and Technology-6; 12 UVM: Universidad Valencia mesoporous;13 NPD: nitrogen-phosphorous detector; 14 MEPS: microextraction by packed syringe;15 MIL: materials of Institute Lavoisier;16 ZIF: zeolite imidazole framework;17 HKUST: Hong Kong University of Science and Technology;18 IMS: ion mobility spectrometry;19 NMA-EDMA: N-methylolacrylamide-ethylenedimethacrylate;20 University of Oslo.…”

Graphene and zeolite as adsorbents in bar-micro-solid phase extraction of pharmaceutical compounds of diverse polarities

“…It was evident extraction using polymeric sorbent (methacrylic acid and ethylene glycol dimethacrylate, 1 : 2) is more efficient than silica sorbent. 20 Zhang and Zhou et al tested several SPE cartridges for simultaneous determination of eleven pharmaceutical compounds using SPE technique. Among the tested cartridges, Oasis HLB-SPE cartridge, the copolymer cartridge was found to produce the best recoveries for the targeted analytes.…”

“…Three-dimensional honeycomb Mg–Al layered double oxide combined with graphitized carbon black was also used as the SPE adsorbent for the simultaneous determination of 15 pesticide residues in green tea coupled with GC-MS. 19 Recovery values of 71.1–119.0% were attained for the tested pesticides. In another study, Roy et al 20 described the synthesis of polymeric adsorbents with tunable surface polarity and their application as SPE for the determination of polar and non-polar chemical warfare agents in non-polar matrices. Through the proper selection of monomer, cross-linker and solvent in the synthesis step, polymeric adsorbents with the required polarity can be obtained.…”

“…It was evident extraction using polymeric sorbent (methacrylic acid and ethylene glycol dimethacrylate, 1 : 2) is more efficient than silica sorbent. 20 …”