Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.

Malaria poses an enormous threat to human health. With ever-increasing resistance to currently deployed antimalarials, new targets and starting point compounds with novel mechanisms of action need to be identified. Here, we explore the antimalarial activity of the Streptomyces sp natural product, 5&...

Full description

Saved in:
Bibliographic Details
Main Authors: Nutpakal Ketprasit, Chia-Wei Tai, Vivek Kumar Sharma, Yogavel Manickam, Yogesh Khandokar, Xi Ye, Con Dogovski, David H Hilko, Craig J Morton, Anne-Sophie C Braun, Michael G Leeming, Bagale Siddharam, Gerald J Shami, Pushpangadan Indira Pradeepkumar, Santosh Panjikar, Sally-Ann Poulsen, Michael D W Griffin, Amit Sharma, Leann Tilley, Stanley C Xie
Format: Article
Language:English
Published: Public Library of Science (PLoS) 2025-07-01
Series:PLoS Pathogens
Online Access:https://doi.org/10.1371/journal.ppat.1013057
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849716961556037632
author Nutpakal Ketprasit
Chia-Wei Tai
Vivek Kumar Sharma
Yogavel Manickam
Yogesh Khandokar
Xi Ye
Con Dogovski
David H Hilko
Craig J Morton
Anne-Sophie C Braun
Michael G Leeming
Bagale Siddharam
Gerald J Shami
Pushpangadan Indira Pradeepkumar
Santosh Panjikar
Sally-Ann Poulsen
Michael D W Griffin
Amit Sharma
Leann Tilley
Stanley C Xie
author_facet Nutpakal Ketprasit
Chia-Wei Tai
Vivek Kumar Sharma
Yogavel Manickam
Yogesh Khandokar
Xi Ye
Con Dogovski
David H Hilko
Craig J Morton
Anne-Sophie C Braun
Michael G Leeming
Bagale Siddharam
Gerald J Shami
Pushpangadan Indira Pradeepkumar
Santosh Panjikar
Sally-Ann Poulsen
Michael D W Griffin
Amit Sharma
Leann Tilley
Stanley C Xie
author_sort Nutpakal Ketprasit
collection DOAJ
description Malaria poses an enormous threat to human health. With ever-increasing resistance to currently deployed antimalarials, new targets and starting point compounds with novel mechanisms of action need to be identified. Here, we explore the antimalarial activity of the Streptomyces sp natural product, 5'-O-sulfamoyl-2-chloroadenosine (dealanylascamycin, DACM) and compare it with the synthetic adenosine monophosphate (AMP) mimic, 5-O-sulfamoyladenosine (AMS). These nucleoside sulfamates exhibit potent inhibition of P. falciparum growth with an efficacy comparable to that of the current front-line antimalarial, dihydroartemisinin. Exposure of P. falciparum to DACM leads to inhibition of protein translation, driven by eIF2α phosphorylation. We show that DACM targets multiple aminoacyl-tRNA synthetases (aaRSs), including the cytoplasmic aspartyl tRNA synthetase (AspRS). The mechanism involves hijacking of the reaction product, leading to the formation of a tightly bound inhibitory amino acid-sulfamate conjugate. We show that recombinant P. falciparum and P. vivax AspRS are susceptible to hijacking by DACM and AMS, generating Asp-DACM and Asp-AMS adducts that stabilize these proteins. By contrast, human AspRS appears less susceptible to hijacking. X-ray crystallography reveals that apo P. vivax AspRS exhibits a stabilized flipping loop over the active site that is poised to bind substrates. By contrast, human AspRS exhibits disorder in an extended region around the flexible flipping loop as well as in a loop in motif II. These structural differences may underpin the decreased susceptibility of human AspRS to reaction-hijacking by DACM and AMS. Our work reveals Plasmodium AspRS as a promising antimalarial target and highlights structural features that underpin differences in the susceptibility of aaRSs to reaction hijacking inhibition.
format Article
id doaj-art-5aba95b5d7454ff6a01adb2cf206811b
institution DOAJ
issn 1553-7366
1553-7374
language English
publishDate 2025-07-01
publisher Public Library of Science (PLoS)
record_format Article
series PLoS Pathogens
spelling doaj-art-5aba95b5d7454ff6a01adb2cf206811b2025-08-20T03:12:49ZengPublic Library of Science (PLoS)PLoS Pathogens1553-73661553-73742025-07-01217e101305710.1371/journal.ppat.1013057Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.Nutpakal KetprasitChia-Wei TaiVivek Kumar SharmaYogavel ManickamYogesh KhandokarXi YeCon DogovskiDavid H HilkoCraig J MortonAnne-Sophie C BraunMichael G LeemingBagale SiddharamGerald J ShamiPushpangadan Indira PradeepkumarSantosh PanjikarSally-Ann PoulsenMichael D W GriffinAmit SharmaLeann TilleyStanley C XieMalaria poses an enormous threat to human health. With ever-increasing resistance to currently deployed antimalarials, new targets and starting point compounds with novel mechanisms of action need to be identified. Here, we explore the antimalarial activity of the Streptomyces sp natural product, 5'-O-sulfamoyl-2-chloroadenosine (dealanylascamycin, DACM) and compare it with the synthetic adenosine monophosphate (AMP) mimic, 5-O-sulfamoyladenosine (AMS). These nucleoside sulfamates exhibit potent inhibition of P. falciparum growth with an efficacy comparable to that of the current front-line antimalarial, dihydroartemisinin. Exposure of P. falciparum to DACM leads to inhibition of protein translation, driven by eIF2α phosphorylation. We show that DACM targets multiple aminoacyl-tRNA synthetases (aaRSs), including the cytoplasmic aspartyl tRNA synthetase (AspRS). The mechanism involves hijacking of the reaction product, leading to the formation of a tightly bound inhibitory amino acid-sulfamate conjugate. We show that recombinant P. falciparum and P. vivax AspRS are susceptible to hijacking by DACM and AMS, generating Asp-DACM and Asp-AMS adducts that stabilize these proteins. By contrast, human AspRS appears less susceptible to hijacking. X-ray crystallography reveals that apo P. vivax AspRS exhibits a stabilized flipping loop over the active site that is poised to bind substrates. By contrast, human AspRS exhibits disorder in an extended region around the flexible flipping loop as well as in a loop in motif II. These structural differences may underpin the decreased susceptibility of human AspRS to reaction-hijacking by DACM and AMS. Our work reveals Plasmodium AspRS as a promising antimalarial target and highlights structural features that underpin differences in the susceptibility of aaRSs to reaction hijacking inhibition.https://doi.org/10.1371/journal.ppat.1013057
spellingShingle Nutpakal Ketprasit
Chia-Wei Tai
Vivek Kumar Sharma
Yogavel Manickam
Yogesh Khandokar
Xi Ye
Con Dogovski
David H Hilko
Craig J Morton
Anne-Sophie C Braun
Michael G Leeming
Bagale Siddharam
Gerald J Shami
Pushpangadan Indira Pradeepkumar
Santosh Panjikar
Sally-Ann Poulsen
Michael D W Griffin
Amit Sharma
Leann Tilley
Stanley C Xie
Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.
PLoS Pathogens
title Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.
title_full Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.
title_fullStr Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.
title_full_unstemmed Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.
title_short Natural product-mediated reaction hijacking mechanism validates Plasmodium aspartyl-tRNA synthetase as an antimalarial drug target.
title_sort natural product mediated reaction hijacking mechanism validates plasmodium aspartyl trna synthetase as an antimalarial drug target
url https://doi.org/10.1371/journal.ppat.1013057
work_keys_str_mv AT nutpakalketprasit naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT chiaweitai naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT vivekkumarsharma naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT yogavelmanickam naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT yogeshkhandokar naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT xiye naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT condogovski naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT davidhhilko naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT craigjmorton naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT annesophiecbraun naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT michaelgleeming naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT bagalesiddharam naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT geraldjshami naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT pushpangadanindirapradeepkumar naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT santoshpanjikar naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT sallyannpoulsen naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT michaeldwgriffin naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT amitsharma naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT leanntilley naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget
AT stanleycxie naturalproductmediatedreactionhijackingmechanismvalidatesplasmodiumaspartyltrnasynthetaseasanantimalarialdrugtarget