Cryo-tomography and 3D Electron Diffraction Reveal the Polar Habit and Chiral Structure of the Malaria Pigment Crystal Hemozoin

Author(s)
Paul Benjamin Klar, David Geoffrey Waterman, Tim Gruene, Debakshi Mullick, Yun Song, James Boris Gilchrist, C. David Owen, Wen Wen, Idan Biran, Lothar Houben, Neta Regev-Rudzki, Ron Dzikowski, Noa Marom, Lukas Palatinus, Peijun Zhang, Leslie Leiserowitz, Michael Elbaum
Abstract

Detoxification of heme in Plasmodium depends on its crystallization into hemozoin. This pathway is a major target of antimalarial drugs. The crystalline structure of hemozoin was established by X-ray powder diffraction using a synthetic analog, β-hematin. Here, we apply emerging methods of in situ cryo-electron tomography and 3D electron diffraction to obtain a definitive structure of hemozoin directly from ruptured parasite cells. Biogenic hemozoin crystals take a striking polar morphology. Like β-hematin, the unit cell contains a heme dimer, which may form four distinct stereoisomers: two centrosymmetric and two chiral enantiomers. Diffraction analysis, supported by density functional theory analysis, reveals a selective mixture in the hemozoin lattice of one centrosymmetric and one chiral dimer. Absolute configuration has been determined by morphological analysis and confirmed by a novel method of exit-wave reconstruction from a focal series. Atomic disorder appears on specific facets asymmetrically, and the polar morphology can be understood in light of water binding. Structural modeling of the heme detoxification protein suggests a function as a chiral agent to bias the dimer formation in favor of rapid growth of a single crystalline phase. The refined structure of hemozoin should serve as a guide to new drug development.

Organisation(s)
Department of Inorganic Chemistry, Core Facility Crystal Structure Analysis
External organisation(s)
Jacobs Universität Bremen, Czech Academy of Sciences, Rutherford Appleton Laboratory, Weizmann Institute of Science, Diamond Light Source Ltd, Carnegie Mellon University, Hebrew University Jerusalem, University of Oxford
Journal
ACS Central Science
Volume
10
Pages
1504-1514
No. of pages
11
ISSN
2374-7943
DOI
https://doi.org/10.1021/acscentsci.4c00162
Publication date
07-2024
Peer reviewed
Yes
Austrian Fields of Science 2012
106002 Biochemistry, 103006 Chemical physics, 105113 Crystallography
ASJC Scopus subject areas
General Chemistry, General Chemical Engineering
Sustainable Development Goals
SDG 3 - Good Health and Well-being
Portal url
https://ucrisportal.univie.ac.at/en/publications/c2825ff0-fa1f-45aa-9885-ccb9c728a085