Decontamination of Chemical Warfare Agents by Novel Oximated Acrylate Copolymer

Abstract

A novel acrylate copolymer, polymethylacrylate-β-(bromoacetyl ethyl)ester-co-N,N-dimethylacrylamide [P(MABE-co-DMAA)] was synthesized by the copolymerization of N,N-dimethylacrylamide and methylacrylate-β-(bromoacetyl ethyl)ester. Subsequently, the copolymer was oximated by 4-pyridinium aldoxime(4-PAM), and was abbreviated as PAM-P(MABE-co-DMAA). A maximum oxime conversion of 53.7% was obtained. The as-prepared oximated copolymer PAM-P(MABE-co-DMAA) effectively decontaminated chemical warfare agents(CWAs) including methylphosphonofluoridate(sarin or GB), S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate (VX), and 2,2′-dichloroethyl sulfide(sulfur mustard, or HD). The detoxification rates were 90.6% for GB, 85.7% for VX, and 90.5% for HD. Chromogenic analysis, high performance liquid chromatography-mass spectrometry (HPLC/MS) and gas chromatography-mass spectrometry(GC/MS) were used to identify the decontamination products, and the decontamination mechanism was concluded to be a combination of nucleophilic substitution and a second order Beckmann rearrangement. Furthermore, the active decontamination materials, such as decontamination cloths and covers could be made from the oximated copolymer by virtue of its processability, as well as its strong ability to degrade CWA.

Keywords

Oximated copolymer / Chemical warfare agent / Decontamination material / Broad-spectrum decontaminating / Detoxification rate

References

[1] Elias S, Saphier S, Columbus I, Zafrani Y. Environ. Sci. Technol., 2014, 48: 2893.

[2] Wagner G W. Environ. Sci. Technol., 2015, 49: 3755.

[3] Columbus I, Waysbort D, Marcovitch I, Yehezkel L, Mizrahi D M. Environ. Sci. Technol., 2012, 46: 3921.

[4] Osovsky R, Kaplan D, Nir I, Rotter H, Elisha S, Columbus I. Environ. Sci. Technol., 2014, 48: 10912.

[5] Fang Y, Kim E, Strathmann T J. Environ. Sci. Technol., 2018, 52: 1997.

[6] Giannakoudakis D A, Arcibar-Orozco J A, Bandosz T J. Appl. Catal. B: Environ., 2015, 174/175: 96.

[7] Alvaroa M, Cojocarub B, Ismailc A A, Petread N, Ferrera B, Harrazc F A, Parvulescub V I, Garcia H. Appl. Catal. B: En-viron., 2010, 99: 191.

[8] Holdren S, Tsyshevsky R, Fears K, Owrutsky J, Wu T, Wang X, Eichhorn B W, Kuklja M M, Zachariah M R. ACS Catal., 2019, 9: 902.

[9] Islamoglu T, Ortuno M A, Proussaloglou E, Howarth A J, Vermerlen N A, Atilgan A, Asiri A M, Cramer C J, Farha O K. Angew. Chem. Int. Ed., 2018, 57: 1949.

[10] Dong J, Lv H J, Sun X R, Wang Y, Ni Y M, Zou B, Zhang N, Yin A X, Chi Y N, Hu C W. Chem. Eur. J., 2018, 24: 19208.

[11] Yan X R, Li X H, Song K X, Zhao H T, Chen X Z. Chem. J. Chinese Universities, 2001, 22(4): 610.

[12] Singh N, Karpichev Y, Tiwari A K, Kuca K, Ghosh K K. J. Mol. Liq., 2015, 208: 237.

[13] Gainullina E T, Gulikova D K, Korneev D O, Oreshkin D V, Ryzhikov S B, Fateenkov V N. J. Anal. Chem., 2015, 70: 771.

[14] Bajgar J, Cabal J, Kassa J, Pavlík M. Acta Medica, 2015, 58: 128.

[15] Gupta B, Sharma R, Singh N, Karpichev Y, Satnami N L, Ghosh K K. J. Phys. Org. Chem., 2013, 26: 632.

[16] Singh N, Ghosh K K, Marek J, Kuca K. Int. J. Chem. Kinet., 2011, 43: 569.

[17] Amitai G, Murata H, Andersen J D, Koepsel R, Russell A J. Biomaterials, 2010, 31: 4417.

[18] Bigley A N, Desormeaux E, Xiang D F, Bae S Y, Harvey S P, Raushe F M. Biochem., 2019, 58: 2039.

[19] Tiwari S, Ghosh K K, Marek J, Kuca K. J. Phy. Org. Chem., 2010, 23: 519.

[20] Bromberg L, Schreuder-Gibson H, Creasy W R, McGarvey D J, Fry R A, Hatton T A. Ind. Eng. Chem. Res., 2009, 48: 1650.

[21] Louise-Leriche L, Paunescu E, Saint-Andre G, Baati R, Romieu A, Wagner A, Renard P Y. Chem. Eur. J., 2010, 16: 3510.

[22] Oh K A, Park N J, Park N, Kuca K, Jun D, Jung Y S. Chem-Biol. Interact., 2008, 175: 365.

[23] Bjarnason S, Mikler J, Hill I, Tenn C, Garrett M, Caddy N, Sawyer T W. Hum. Exp. Toxicol., 2008, 27: 253.

[24] Bromberg L, Hatton T A. Ind. Eng. Chem. Res., 2007, 46: 3296.

[25] Becker G, Kawan A, Gutzeit D, Worek F, Szinicz L. Arch. Toxicol., 2007, 81: 415.

[26] Taysse L, Daulon S, Dekamanche S, Bellier B, Breton P. Hum. Exp. Toxicol., 2007, 26: 135.

[27] Terrier F, Rodriguez-Dafonte P, Guevel E L, Moutiers G. Org. Biomol. Chem., 2006, 4: 4352.

[28] Bromberg L, Hatton T A. Ind. Eng. Chem. Res., 2005, 44: 7991.

[29] Tang S Z, Wong P T, Cannon J, Yang K, Bowden S, Bhattacharjee S, O’Konek J J, Choi S K. Chem-Biol. Interact., 2019, 297: 67.

[30] Ding Y Y, Wang C Z, Wen X F, Zhang X P, Ye L, Zhang A Y, Feng Z G. Chem. J. Chinese Universities, 2013, 347: 1758.

[31] Matar H, Price S C, Chilcott R P. Toxicol. in Vitro, 2019, 54: 263.

[32] Zou Y, Xi H L, Zhang S. J. Chem. Defense, 2010, 4: 1.

[33] Walters T J, Kauvar D S, Reeder J, Baer D G. Mil. Med., 2007, 1713: 318.

[34] Kong T, Lin J, Ye L, Zhang A Y, Feng Z G. Polym. Chem., 2015, 6: 5832.

[35] Zhang Z L, Xu L, Zang C Y, Toyoji K, Shen X D. Acta Polym. Sin., 2019, 50: 384.

[36] Shao Z Q, Zhang Y D, Wu M L, Wang W J. Chin. J. Energ. Mat., 2009, 17: 330.

[37] Zhao X Z. Preparation of Novel Modified Chitosan Microspheres and Preliminary Application, 2017, Hangzhou: Zhejiang Gongshan University.

[38] Xie Y, Chen J, Xu B, Yan L, Tang J J, Xie J W. Chem. J. Chinese Universities, 2017, 385: 758.

[39] Ellman G L, Courtney K D, Andres V, Feathersotne R M. Biochem. Pharmacol., 1961, 7: 88.

[40] Zhao S P, Xi H L, Zuo Y J, Han S T, Zhu Y B, Li Z G, Yuan L, Wang Z C, Liu C C. J. Hazard. Mater., 2019, 367: 91.

[41] Zhao J, Shi J, Xu C. Tech. Develop. Chem. Ind., 2009, 384: 28.

[42] Yang Y C, Szafraniec L L, Beaudry W T, Rohrbaugh D K, Procell L R, Samuel J B. J. Org. Chem., 1996, 61: 8407.

[43] Wagner G W, O’Connor R J, Edwards J L, Brevett C A S. Langmuir, 2004, 20: 7146.