TY - JOUR
T1 - Efficient Decontamination of HD by an Electrophilic Iodine/Carboxylate Composite as an Active Sorbent
AU - Smolkin, Boris
AU - Levi, Noam
AU - Chen, Ravit
N1 - Publisher Copyright:
© 2022 The Authors. Published by American Chemical Society.
PY - 2022/7/26
Y1 - 2022/7/26
N2 - The development of new and efficient decontamination methods has become more relevant in recent years, especially with regard to solid-based decontamination and detoxification systems. The majority of powders used today are dealing with the physical adsorption of chemical warfare agents (CWAs) and their removal from sites without actively destroying them. In this work, we have designed and developed an active solid composite matrix combining organic carboxylate salts and N-iodosuccinimide (NIS) for HD decontamination via oxidation. All the reactions and mechanistic studies for the sorption and degradation of CWAs were conducted using direct polarization and cross polarization solid-state magic-angle spinning nuclear magnetic resonance techniques. Performance toward the sorption and detoxification of HD was tested, exhibiting oxidation within minutes in a mild and selective manner to the nontoxic sulfoxide derivative followed by visible formation of iodine. The results indicate that carboxylate moieties in the matrix are important for stabilizing the positively charged sulfonium ion intermediate and for supplying oxygen for hydrolysis in a water-deficient environment. The NaOBz/NIS composite was shown to be the most efficient in sorbing and converting the water-insoluble agent HD to its nontoxic, water-soluble sulfoxide, which could then be removed from the site with mere water, resulting in less environmental damage and quick remediation.
AB - The development of new and efficient decontamination methods has become more relevant in recent years, especially with regard to solid-based decontamination and detoxification systems. The majority of powders used today are dealing with the physical adsorption of chemical warfare agents (CWAs) and their removal from sites without actively destroying them. In this work, we have designed and developed an active solid composite matrix combining organic carboxylate salts and N-iodosuccinimide (NIS) for HD decontamination via oxidation. All the reactions and mechanistic studies for the sorption and degradation of CWAs were conducted using direct polarization and cross polarization solid-state magic-angle spinning nuclear magnetic resonance techniques. Performance toward the sorption and detoxification of HD was tested, exhibiting oxidation within minutes in a mild and selective manner to the nontoxic sulfoxide derivative followed by visible formation of iodine. The results indicate that carboxylate moieties in the matrix are important for stabilizing the positively charged sulfonium ion intermediate and for supplying oxygen for hydrolysis in a water-deficient environment. The NaOBz/NIS composite was shown to be the most efficient in sorbing and converting the water-insoluble agent HD to its nontoxic, water-soluble sulfoxide, which could then be removed from the site with mere water, resulting in less environmental damage and quick remediation.
UR - http://www.scopus.com/inward/record.url?scp=85135627898&partnerID=8YFLogxK
U2 - 10.1021/acsomega.2c02280
DO - 10.1021/acsomega.2c02280
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C2 - 35910097
AN - SCOPUS:85135627898
SN - 2470-1343
VL - 7
SP - 25329
EP - 25336
JO - ACS Omega
JF - ACS Omega
IS - 29
ER -