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Metal–Organic Frameworks (MOFs) as Versatile Detoxifiers for Chemical Warfare Agents (CWAs)

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Metal-Organic Frameworks (MOFs) as Catalysts

Abstract

Chemical warfare agents (CWAs) are considered as one of the most fatal weapons potentially strong to cause extreme toxicity and disastrous effects to a large population. They were used as weapons for the first time in 1915 during World War I (WWI) when Ypres, a Belgian city, was attacked by the German military. Sulfur mustard, a dreadful chemical warfare agent, which was used in the subsequent battles became the major cause of chemical casualties in WWI. These chemicals imposed harsh after-effects even years after they were deployed. Nerve agents and vesicants are particularly known to be extremely harmful, among the various classes of CWAs; even short-term exposure to these chemicals can lead to severe after-effects. Above all, CWAs also release various volatile organic compounds (VOCs), which comprise an important group of air pollutants, which can potentially cause serious health effects to mankind including mutagenesis and carcinogenesis. In view of these consequences, capture and subsequent degradation of these agents to less or completely non-toxic by-products are of paramount importance. Being highly toxic, degradation of hazardous CWAs through catalytic reactions such as hydrolysis, methanolysis, and oxidation has been proved to be one of the best methods that can eventually transform them into less-toxic products. Research communities throughout the globe have been making relentless attempts on developing novel catalytic materials in this field. Metal-organic frameworks (MOFs), being specifically designed making use of organic linkers and inorganic nodes, offer scope for fabrication of a versatile range of materials with great diversity in structural and chemical properties, characterized by their high stability, crystalline, and ordered nature with significantly large surface areas, high porosity, and free volume. The presence of freely available metal sites and/or numerous functional moieties on the surface of the MOFs allows adsorption or capture of certain toxic CWAs with high selectivity and efficiency via various interactions which may be either H-bonds, ionic or Coulombic interactions, coordination bonds, Π-Π* interactions, etc. or a combination of these. Moreover, further functionalization with coordinating or conjugating agents also imparts them good catalytic properties. The pore properties along with the specificity of the functional groups in the MOFs together ascribe to the subsequent catalytic degradation of highly toxic CWAs and their simulants.

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Abbreviations

4-MAP:

Methylaminopyridine

ACh:

Acetyl choline

AchE:

Acetyl cholinesterase

ALD:

Atomic layer deposition

CEES:

2-Chloroethyl ethyl sulfide

CEESO:

2-Chloroethyl ethyl sulfoxide

CEESO2:

2-Chloroethyl ethyl sulfone

CN:

2-Chloroacetophenone

CR:

Dibenz (b,f)-1,43-oxazepine

CS:

2-(2-Chlorobenzylidene) malononitrile

CWAs:

Chemical Warfare Agents

DCP:

Diethyl chloro phosphonate

DESH:

Diisopropylamino ethyl mercaptan

DIFP:

Diisopropylfluorophosphate

DMNP:

Dimethyl 4-nitrophenyl phosphate

EA-2192:

S-[2(diisopropyla mino) ethyl]methyl phosphonic acid

EMPA:

Ethyl methyl phosphonic acid

GB:

Sarin

GD:

Soman

H4TBAPy:

4,4′,4″,4′′′-(Pyrene-1,3,6,8-tetrayl) tetrabenzoic acid

HD:

Sulfur mustard

HN1:

Bis-(2-chloroethyl)-ethyl-amine

HN2:

2-Chloroethyl)-methyl-amine

HN3:

Tris-(2-chloroethyl)-amine

ID50:

Lethal Dose 50

LED:

Light-emitting diode

LSD:

Lysergic acid diethylamide

MOFs:

Metal-organic Frameworks

NADH:

Nicotinamide adenine dinucleotide hydrogenase

OMS:

Open metal sites

OP:

Organophosphorus

PA-6:

Polyamide-6 nanofiber

PAN:

Polyacrylonitrile

PCN:

Porous coordination networks

PEI:

Polyethyleneimine

PFIB:

Perfluoro isobutylene

PIM:

Polymers of intrinsic microporosity

PMPA:

Pinacolyl methyl phosphonic acid

PNPDPP:

P-nitrophenyl diphenyl phosphate

POPs:

Porous organic polymers

SBUs:

Secondary building units

TA:

Tabun

THC:

Tetrahydrocannabinol

TOF:

Turn Over Frequency

VOCs:

Volatile Organic Compounds

VX:

S-{2-[Di(propan-2-yl) amino] ethyl} O-ethyl methylphosphonothioate

WW I:

World War I

WW II:

World War II

Zr-MOFs:

Zirconium-based Metal–Organic Frameworks

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Acknowledgements

The authors are thankful to Principal, Sir Venkateshwara College, University of Delhi and Principal, Acharya Narendra Dev College, University of Delhi for their valuable cooperation and guidance.

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Authors and Affiliations

  1. Department of Chemistry, Sri Venkateswara College (University of Delhi), Dhaula Kuan, New Delhi, 110021, India

    Laishram Saya

  2. Department of Chemistry, Acharya Narendra Dev College (University of Delhi), Govindpuri, Kalkaji, New Delhi, 110019, India

    Sunita Hooda

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  1. Department of Chemistry, Sri Venkateswara College, University of Delhi, New Delhi, India

    Shikha Gulati

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Saya, L., Hooda, S. (2022). Metal–Organic Frameworks (MOFs) as Versatile Detoxifiers for Chemical Warfare Agents (CWAs). In: Gulati, S. (eds) Metal-Organic Frameworks (MOFs) as Catalysts. Springer, Singapore. https://doi.org/10.1007/978-981-16-7959-9_18

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