Assessment of four organophosphorus pesticides as inhibitors of human acetylcholinesterase and butyrylcholinesterase.


Journal

Scientific reports
ISSN: 2045-2322
Titre abrégé: Sci Rep
Pays: England
ID NLM: 101563288

Informations de publication

Date de publication:
02 11 2021
Historique:
received: 15 09 2021
accepted: 20 10 2021
entrez: 3 11 2021
pubmed: 4 11 2021
medline: 27 1 2022
Statut: epublish

Résumé

Toxicity of organophosphorus compounds (OPs) remains a major public health concern due to their widespread use as pesticides and the existence of nerve agents. Their common mechanism of action involves inhibition of enzymes acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) which are crucial for neurotransmission. Both chronic and acute poisoning by OPs can leave long-lasting health effects even when the patients are treated with standard medical therapy. Therefore, an increasing urgency exists to find more effective oxime reactivators for compounds which are resistant to reactivation, especially phosphoramidates. Here, we investigated in silico and in vitro interactions and kinetics of inhibition for human cholinesterases with four organophosphate pesticides-ethoprophos, fenamiphos, methamidophos and phosalone. Overall, ethoprophos and fenamiphos displayed higher potency as inhibitors for tested cholinesterases. Our results show that methamidophos-inhibited hAChE was more susceptible to reactivation than hAChE inhibited by fenamiphos by selected oximes. Molecular modelling enabled an evaluation of interactions important for specificity and selectivity of both inhibition and reactivation of cholinesterases. Two newly developed reactivators-bispyridinium triazole oxime 14A and zwitterionic oxime RS194B possess remarkable potential for further development of antidotes directed against pesticides and related phosphoramidate exposures, such as nerve agents tabun or Novichoks.

Identifiants

pubmed: 34728713
doi: 10.1038/s41598-021-00953-9
pii: 10.1038/s41598-021-00953-9
pmc: PMC8563940
doi:

Substances chimiques

Cholinesterase Inhibitors 0
GPI-Linked Proteins 0
Organophosphorus Compounds 0
Pesticides 0
ACHE protein, human EC 3.1.1.7
Acetylcholinesterase EC 3.1.1.7
BCHE protein, human EC 3.1.1.8
Butyrylcholinesterase EC 3.1.1.8

Types de publication

Journal Article Research Support, Non-U.S. Gov't

Langues

eng

Sous-ensembles de citation

IM

Pagination

21486

Subventions

Organisme : Hrvatska Zaklada za Znanost
ID : IP-2018-01-7683

Informations de copyright

© 2021. The Author(s).

Références

Kwong, T. C. Organophosphate pesticides: Biochemistry and clinical toxicology. Ther. Drug Monit. 24, 144–149 (2002).
pubmed: 11805735 doi: 10.1097/00007691-200202000-00022
Goh, K. T., Yew, F. S., Ong, K. H. & Tan, I. K. Acute organophosphorus food poisoning caused by contaminated green leafy vegetables. Arch. Environ. Health 45, 180–184 (1990).
pubmed: 2386424 doi: 10.1080/00039896.1990.9936713
Wu, M., Deng, J., Tsai, W., Wong, S. & Li, H. Food poisoning due to methamidophos- contaminated vegetables. Clin. Toxicol. 39, 333–336 (2001).
Bolognesi, C. & Merlo, F. D. Pesticides: Human Health Effects. In Encyclopedia of Environmental Health 438–453 (Elsevier, 2011). https://doi.org/10.1016/b978-0-444-52272-6.00592-4 .
doi: 10.1016/b978-0-444-52272-6.00592-4
Lushchak, V. I., Matviishyn, T. M., Husak, V. V., Storey, J. M. & Storey, K. B. Pesticide toxicity: A mechanistic approach. Excli J. 17, 1101–1136 (2018).
pubmed: 30564086 pmcid: 6295629
Aroniadou-Anderjaska, V., Figueiredo, T. H., Apland, J. P., Qashu, F. & Braga, M. F. M. Primary brain targets of nerve agents: The role of the amygdala in comparison to the hippocampus. Neurotoxicology 30, 772–776 (2009).
pubmed: 19591865 pmcid: 2761531 doi: 10.1016/j.neuro.2009.06.011
Pope, C., Karanth, S. & Liu, J. Pharmacology and toxicology of cholinesterase inhibitors: Uses and misuses of a common mechanism of action. Environ. Toxicol. Pharmacol. 19, 433–446 (2005).
pubmed: 21783509 doi: 10.1016/j.etap.2004.12.048
Petreski, T., Kit, B., Strnad, M., Grenc, D. & Svenšek, F. Cholinergic syndrome: A case report of acute organophosphate and carbamate poisoning. Arh. Hig. Rada Toksikol. 71, 163–166 (2020).
pubmed: 32975104 pmcid: 7968493
Yurumez, Y. et al. Acute organophosphate poisoning in university hospital emergency room patients. Intern. Med. 46, 965–969 (2007).
pubmed: 17603234 doi: 10.2169/internalmedicine.46.6304
Joyce, M. R. & Holton, K. F. Neurotoxicity in Gulf War Illness and the potential role of glutamate. Neurotoxicology 80, 60–70 (2020).
pubmed: 32585289 doi: 10.1016/j.neuro.2020.06.008
Aroniadou-Anderjaska, V., Figueiredo, T. H., Apland, J. P. & Braga, M. F. Targeting the glutamatergic system to counteract organophosphate poisoning: A novel therapeutic strategy. Neurobiol. Dis. 133, 2 (2020).
doi: 10.1016/j.nbd.2019.02.017
Richardson, J. R., Fitsanakis, V., Westerink, R. H. S. & Kanthasamy, A. G. Neurotoxicity of pesticides. Acta Neuropathol. 138, 343–362 (2019).
pubmed: 31197504 pmcid: 6826260 doi: 10.1007/s00401-019-02033-9
Sandoval-Herrera, N., Mena, F., Espinoza, M. & Romero, A. Neurotoxicity of organophosphate pesticides could reduce the ability of fish to escape predation under low doses of exposure. Sci. Rep. 9, 1–11 (2019).
doi: 10.1038/s41598-019-46804-6
Worek, F. et al. Kinetic analysis of reactivation and aging of human acetylcholinesterase inhibited by different phosphoramidates. Biochem. Pharmacol. 73, 1807–1817 (2007).
pubmed: 17382909 doi: 10.1016/j.bcp.2007.02.008
Emerick, G. L., DeOliveira, G. H., Oliveira, R. V. & Ehrich, M. Comparative in vitro study of the inhibition of human and hen esterases by methamidophos enantiomers. Toxicology 292, 145–150 (2012).
pubmed: 22198100 doi: 10.1016/j.tox.2011.12.004
Bocquené, G. & Galgani, F. Acetylcholinesterase activity in the common prawn (Palaemon serratus) contaminated by carbaryl and phosalone: Choice of a method for detection of effects. Ecotoxicol. Environ. Saf. 22, 337–344 (1991).
pubmed: 1778118 doi: 10.1016/0147-6513(91)90083-2
Kaur, G., Jain, A. K. & Singh, S. CYP/PON genetic variations as determinant of organophosphate pesticides toxicity. J. Genet. 96, 187–201 (2017).
pubmed: 28360405 doi: 10.1007/s12041-017-0741-7
Maček Hrvat, N. & Kovarik, Z. Counteracting poisoning with chemical warfare nerve agents. Arh. Hig. Rada Toksikol. 71, 266–284 (2021).
Timperley, C. M. et al. Advice on assistance and protection from the Scientific Advisory Board of the Organisation for the Prohibition of Chemical Weapons: Part 2. On preventing and treating health effects from acute, prolonged, and repeated nerve agent exposure, and the identif. Toxicology 413, 13–23 (2019).
pubmed: 30500381 doi: 10.1016/j.tox.2018.11.009
Timperley, C. M. et al. Advice on assistance and protection provided by the Scientific Advisory Board of the Organisation for the Prohibition of Chemical Weapons: Part 1. On medical care and treatment of injuries from nerve agents. Toxicology 415, 56–69 (2019).
pubmed: 30639304 doi: 10.1016/j.tox.2019.01.004
Kovarik, Z. et al. Reversal of tabun toxicity enabled by a triazole-annulated oxime library—reactivators of acetylcholinesterase. Chem. A Eur. J. 25, 4100–4114 (2019).
doi: 10.1002/chem.201805051
Radić, Z. et al. Refinement of structural leads for centrally acting oxime reactivators of phosphylated cholinesterases. J. Biol. Chem. 287, 11798–11809 (2012).
pubmed: 22343626 pmcid: 3320928 doi: 10.1074/jbc.M111.333732
Rosenberg, Y. J. et al. Post-exposure treatment with the oxime RS194B rapidly reactivates and reverses advanced symptoms of lethal inhaled paraoxon in macaques. Toxicol. Lett. 293, 229–234 (2017).
pubmed: 29129799 pmcid: 5943181 doi: 10.1016/j.toxlet.2017.10.025
Sit, R. K. et al. Pharmacology, pharmacokinetics, and tissue disposition of zwitterionic hydroxyiminoacetamido alkylamines as reactivating antidotes for organophosphate exposure. J. Pharmacol. Exp. Ther. 367, 363–372 (2018).
pubmed: 30190337 pmcid: 6223194 doi: 10.1124/jpet.118.249383
Shyong, Y.-J. et al. Enhancing target tissue levels and diminishing plasma clearance of ionizing zwitterionic antidotes in organophosphate exposures. J. Pharmacol. Exp. Ther. 378, 315–321 (2021). 
pubmed: 34145064 doi: 10.1124/jpet.121.000715
de Jong, L. P. A., Verhagen, M. A. A., Langenberg, J. P., Hagedorn, I. & Löffler, M. The bispyridinium-dioxime HLö-7. A potent reactivator for acetylcholinesterase inhibited by the stereoisomers of tabun and soman. Biochem. Pharmacol. 38, 633–640 (1989).
pubmed: 2917018
Carletti, E. et al. Aging of cholinesterases phosphylated by tabun proceeds through O-dealkylation. J. Am. Chem. Soc. 130, 16011–16020 (2008).
pubmed: 18975951 doi: 10.1021/ja804941z
Maraković, N. et al. Enantioseparation, in vitro testing, and structural characterization of triple-binding reactivators of organophosphate-inhibited cholinesterases. Biochem. J. 477, 2771–2790 (2020).
pubmed: 32639532 doi: 10.1042/BCJ20200192
Ngamelue, M. N., Homma, K., Lockridge, O. & Asojo, O. A. Crystallization and X-ray structure of full-length recombinant human butyrylcholinesterase. Acta Crystallogr. Sect. F Struct. Biol. Cryst. Commun. 63, 723–727 (2007).
doi: 10.1107/S1744309107037335
Rosenberry, T. L. et al. Comparison of the binding of reversible inhibitors to human butyrylcholinesterase and acetylcholinesterase: A crystallographic, kinetic and calorimetric study. Molecules 22, 1–21 (2017).
doi: 10.3390/molecules22122098
Saxena, A., Redman, A. M. G., Jiang, X., Lockridge, O. & Doctor, B. P. Differences in active-site gorge dimensions of cholinesterases revealed by binding of inhibitors to human butyrylcholinesterase. Chem. Biol. Interact. 119–120, 61–69 (1999).
pubmed: 10421439 doi: 10.1016/S0009-2797(99)00014-9
Kovarik, Z., Bosak, A., Šinko, G. & Latas, T. Exploring the active sites of cholinesterases by inhibition with bambuterol and haloxon. Croat. Chem. Acta 76, 63–67 (2003).
Bosak, A., Gazić Smilović, I., Šinko, G., Vinković, V. & Kovarik, Z. Metaproterenol, isoproterenol, and their bisdimethylcarbamate derivatives as human cholinesterase inhibitors. J. Med. Chem. 55, 6716–6723 (2012).
pubmed: 22817559 doi: 10.1021/jm300289k
Kovarik, Z. et al. Amino acid residues involved in the interaction of acetylcholinesterase and butyrylcholinesterase with the carbamates Ro 02–0683 and bambuterol, and with terbutaline. Biochim. Biophys. Acta 1433, 261–271 (1999).
pubmed: 10446376 doi: 10.1016/S0167-4838(99)00124-7
Bosak, A. et al. Peripheral site and acyl pocket define selective inhibition of mouse butyrylcholinesterase by two biscarbamates. Arch. Biochem. Biophys. 529, 140–145 (2013).
pubmed: 23219600 doi: 10.1016/j.abb.2012.11.012
Ekström, F., Akfur, C., Tunemalm, A. K. & Lundberg, S. Structural changes of phenylalanine 338 and histidine 447 revealed by the crystal structures of tabun-inhibited murine acetylcholinesterase. Biochemistry 45, 74–81 (2006).
pubmed: 16388582 doi: 10.1021/bi051286t
Maček Hrvat, N. et al. Evaluation of high-affinity phenyltetrahydroisoquinoline aldoximes, linked through anti-triazoles, as reactivators of phosphylated cholinesterases. Toxicol. Lett. 321, 83–89 (2020).
pubmed: 31863869 doi: 10.1016/j.toxlet.2019.12.016
Kovarik, Z. et al. Evaluation of oxime K203 as antidote in tabun poisoning. Arh. Hig. Rada Toksikol. 60, 19–26 (2009).
pubmed: 19329372 doi: 10.2478/10004-1254-60-2009-1890
Kovarik, Z., Čalić, M., Bosak, A., Šinko, G. & Jelić, D. In vitro evaluation of aldoxime interactions with human acetylcholinesterase. Croat. Chem. Acta 81, 47–57 (2008).
Čalić, M. et al. In vitro and in vivo evaluation of pyridinium oximes: Mode of interaction with acetylcholinesterase, effect on tabun- and soman-poisoned mice and their cytotoxicity. Toxicology 219, 85–96 (2006).
pubmed: 16332406 doi: 10.1016/j.tox.2005.11.003
Kovarik, Z., Čalić, M., Šinko, G. & Bosak, A. Structure-activity approach in the reactivation of tabun-phosphorylated human acetylcholinesterase with bispyridinium para-aldoximes. Arh. Hig. Rada Toksikol. 58, 201–209 (2007).
pubmed: 17562604 doi: 10.2478/v10004-007-0013-7
Worek, F., von der Wellen, J., Musilek, K., Kuca, K. & Thiermann, H. Reactivation kinetics of a homologous series of bispyridinium bis-oximes with nerve agent-inhibited human acetylcholinesterase. Arch. Toxicol. 86, 1379–1386 (2012).
pubmed: 22437842 doi: 10.1007/s00204-012-0842-2
Šinko, G., Čalić, M. & Kovarik, Z. para- and ortho-Pyridinium aldoximes in reaction with acetylthiocholine. FEBS Lett. 580, 3167–3172 (2006).
pubmed: 16684539 doi: 10.1016/j.febslet.2006.04.070
Gorecki, L. et al. Rational design, synthesis, and evaluation of uncharged, “smart” bis-oxime antidotes of organophosphate-inhibited human acetylcholinesterase. J. Biol. Chem. 295, 4079–4092 (2020).
pubmed: 32019865 pmcid: 7105318 doi: 10.1074/jbc.RA119.012400
Taylor, P. et al. Ligand design for human acetylcholinesterase and nicotinic acetylcholine receptors, extending beyond the conventional and canonical. J. Neurochem. 158, 1217–1222 (2021).
pubmed: 33638151 doi: 10.1111/jnc.15335
Kovarik, Z. et al. Centrally acting oximes in reactivation of tabun-phosphoramidated AChE. Chem. Biol. Interact. 203, 77–80 (2013).
pubmed: 22960624 doi: 10.1016/j.cbi.2012.08.019
Kovarik, Z. et al. Mutant cholinesterases possessing enhanced capacity for reactivation of their phosphonylated conjugates. Biochemistry 43, 3222–3229 (2004).
pubmed: 15023072 doi: 10.1021/bi036191a
Cochran, R. et al. Oxime-assisted acetylcholinesterase catalytic scavengers of organophosphates that resist aging. J. Biol. Chem. 286, 29718–29724 (2011).
pubmed: 21730071 pmcid: 3191013 doi: 10.1074/jbc.M111.264739
Ellman, G. L., Courtney, K. D., Andres, V. & Featherstone, R. M. A new and rapid colorimetric determination of acetylcholinesterase activity. Biochem. Pharmacol. 7, 88–95 (1961).
pubmed: 13726518 doi: 10.1016/0006-2952(61)90145-9
Momany, F. & Rone, R. Validation of the general purpose QUANTA 3.2/CHARMm force field. J. Comp. Chem. 13, 888–900 (1992).
doi: 10.1002/jcc.540130714
Brooks, B. R. et al. CHARMM: A program for macromolecular energy, minimization, and dynamics calculations. J. Comp. Chem. 4, 187–217 (1983).
doi: 10.1002/jcc.540040211
Dym, O., Unger, T., Toker, L., Silman, I. & Sussman, J. Israel Structural Proteomics Center (ISPC) Crystal Structure of Human Acetylcholinesterase. (2015) doi: https://doi.org/10.2210/pdb4PQE/pdb .
Maraković, N., Knežević, A., Vinković, V., Kovarik, Z. & Šinko, G. Design and synthesis of N-substituted-2-hydroxyiminoacetamides and interactions with cholinesterases. Chem. Biol. Interact. 259, 122–132 (2016).
pubmed: 27238725 doi: 10.1016/j.cbi.2016.05.035
Hörnberg, A., Artursson, E., Wärme, R., Pang, Y. P. & Ekström, F. Crystal structures of oxime-bound fenamiphos-acetylcholinesterases: Reactivation involving flipping of the His447 ring to form a reactive Glu334-His447-oxime triad. Biochem. Pharmacol. 79, 507–515 (2010).
pubmed: 19732756 doi: 10.1016/j.bcp.2009.08.027

Auteurs

Tena Čadež (T)

Institute for Medical Research and Occupational Health, Ksaverska cesta 2, 10 000, Zagreb, Croatia.

Dora Kolić (D)

Institute for Medical Research and Occupational Health, Ksaverska cesta 2, 10 000, Zagreb, Croatia.

Goran Šinko (G)

Institute for Medical Research and Occupational Health, Ksaverska cesta 2, 10 000, Zagreb, Croatia.

Zrinka Kovarik (Z)

Institute for Medical Research and Occupational Health, Ksaverska cesta 2, 10 000, Zagreb, Croatia. zkovarik@imi.hr.

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