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A biomimetic magnetosome: formation of iron oxide within carboxylic acid terminated polymersomes

Bain, Jennifer, Legge, Christopher J., Beattie, Deborah L., Sahota, Annie, Dirks, Catherine, Lovett, Joseph R., Staniland, Sarah S.·2019·Nanoscale
DOI 10.1039/c9nr00498j
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Abstract

Bioinspired macromolecules can aid nucleation and crystallisation of minerals by mirroring processes observed in nature.

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Fig. 1 Schematic of natural and synthetic vesicle membranes (blue = hydrophilic membrane lea fl et, red = hydrophobic membrane lea fl et) representing, (a) the bacterial magnetosome in which iron is recruited into the core of the magnetosome using iron transporters, which also acts an antiporter pumping out internal protons. The e ffl ux of protons causes a pH increase resulting in the precipitation the magnetite crystal. The magnetite nucleation protein Mms6 (inset bottom left) which accumulates iron ions on the acidic amino acids on the inner lumen of the magnetosome. (b) Chemical composition of PEG-PHPMA and PMPC-PHPMA polymer which represent the hydrophilic (blue) and hydrophobic (red) lea fl ets of the vesicles, which features a carboxylic acid group on the PMPC monomer to mimic the iron ion binding/mineral nucleating sites of the Mms6 protein. The lighting represents electroporation to mimic the protein iron transporter, while the insert shows how the acidic end groups on PMPC mimic Mms6.
Fig. 1 Schematic of natural and synthetic vesicle membranes (blue = hydrophilic membrane lea fl et, red = hydrophobic membrane lea fl et) representing, (a) the bacterial magnetosome in which iron is recruited into the core of the magnetosome using iron transporters, which also acts an antiporter pumping out internal protons. The e ffl ux of protons causes a pH increase resulting in the precipitation the magnetite crystal. The magnetite nucleation protein Mms6 (inset bottom left) which accumulates iron ions on the acidic amino acids on the inner lumen of the magnetosome. (b) Chemical composition of PEG-PHPMA and PMPC-PHPMA polymer which represent the hydrophilic (blue) and hydrophobic (red) lea fl ets of the vesicles, which features a carboxylic acid group on the PMPC monomer to mimic the iron ion binding/mineral nucleating sites of the Mms6 protein. The lighting represents electroporation to mimic the protein iron transporter, while the insert shows how the acidic end groups on PMPC mimic Mms6.CC-BY · From the PDF
Fig. 2 Poly(ethylene glycol)-poly(2-hydroxypropyl methacrylate)/poly (2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-hydroxypropyl methacrylate) (PEG + PMPC)-PHPMA polymersomes are prepared by chain extension of a binary mixture of PEG113 and PMPC28 macro-CTAs via reversible addition -fragmentation chain transfer (RAFT) aqueous dispersion polymerisation of 2-hydroxypropyl methacrylate (HPMA). 45
Fig. 2 Poly(ethylene glycol)-poly(2-hydroxypropyl methacrylate)/poly (2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-hydroxypropyl methacrylate) (PEG + PMPC)-PHPMA polymersomes are prepared by chain extension of a binary mixture of PEG113 and PMPC28 macro-CTAs via reversible addition -fragmentation chain transfer (RAFT) aqueous dispersion polymerisation of 2-hydroxypropyl methacrylate (HPMA). 45CC-BY · From the PDF
Fig. 3 (a) Negatively stained TEM images of PMM28 polymersomes, (b) cryo-TEM image of PMM28 to show hydrated size is consistent with (a). (c) TEM grainsizing of the polymersome sample.
Fig. 3 (a) Negatively stained TEM images of PMM28 polymersomes, (b) cryo-TEM image of PMM28 to show hydrated size is consistent with (a). (c) TEM grainsizing of the polymersome sample.CC-BY · From the PDF
Fig. 4 Unstained TEM images of (a) PMM28Fe. The PMM28 sample was soaked in NaOH (10 mM) before electroporation at 750 V (5 pulses) in the presence of excess FeCl2·4H2O. The polymersomes show dark electron dense cores, attributed to the precipitation of magnetic iron oxide.
Fig. 4 Unstained TEM images of (a) PMM28Fe. The PMM28 sample was soaked in NaOH (10 mM) before electroporation at 750 V (5 pulses) in the presence of excess FeCl2·4H2O. The polymersomes show dark electron dense cores, attributed to the precipitation of magnetic iron oxide.CC-BY · From the PDF
Fig. 5 (a) Unstained TEM image of electroporated PMM28Fe polymersomes showing precipitation on the outer lea fl et of the polymersome as well as in the vesicle core. (b) A selected area electron di ff raction image of the same electroporated polymersome con fi rming the presence of a crystalline substance within the polymersome. (c) Cryo-EM micrograph of PEO-PBD polymersomes from the fi rst reported use of the electroporation method 29 and (d) show comparison of use of the electroporation method on PMOXA-DMS-MOXA tri-block polymersomes. 30
Fig. 5 (a) Unstained TEM image of electroporated PMM28Fe polymersomes showing precipitation on the outer lea fl et of the polymersome as well as in the vesicle core. (b) A selected area electron di ff raction image of the same electroporated polymersome con fi rming the presence of a crystalline substance within the polymersome. (c) Cryo-EM micrograph of PEO-PBD polymersomes from the fi rst reported use of the electroporation method 29 and (d) show comparison of use of the electroporation method on PMOXA-DMS-MOXA tri-block polymersomes. 30CC-BY · From the PDF
Fig. 6 Temperature increase vs. time curve obtained during magnetic hyperthermic heating of a 0.2% w/v aqueous dispersion of PMM28Fe polymersomes (0.11 mg ml -1 of iron). A temperature increase of 6 °C is observed over a period of 10 minutes (600 s).
Fig. 6 Temperature increase vs. time curve obtained during magnetic hyperthermic heating of a 0.2% w/v aqueous dispersion of PMM28Fe polymersomes (0.11 mg ml -1 of iron). A temperature increase of 6 °C is observed over a period of 10 minutes (600 s).CC-BY · From the PDF

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Metadata

Authors
Bain, J., Legge, C. J., Beattie, D. L., Sahota, A., Dirks, C., Lovett, J. R., & Staniland, S. S.
Affiliations
Department of Chemistry
ORCID
Staniland, Sarah S.
Venue
Nanoscale
Publisher
Royal Society of Chemistry (RSC)
Published
2019
Volume
11
Issue
24
Pages
11617-11625
ISSN
  • 2040-3364
  • 2040-3372
DOI
10.1039/c9nr00498j
Cited by
21
References
1
Language
en
Licence
creativecommons.org/licenses/by/3.0/ (vor, 157 d)
Funders
Engineering and Physical Sciences Research Council (EP/I032355/2)

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