Study on the Isotope fractionation of Zinc in Complexation with Macrocyclic Polyethers

Fujii, Toshiyuki, Kato, Chizu, Mahan, Brandon, and Moynier, Frédéric (2021) Study on the Isotope fractionation of Zinc in Complexation with Macrocyclic Polyethers. Zeitschrift fuer Anorganische und Allgemeine Chemie, 647 (6). pp. 599-605.

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DOI: 10.1002/zaac.202000413

View at Publisher Website: https://doi.org/10.1002/zaac.202000413

Abstract

Isotope fractionation of Zn was studied via liquid-liquid extraction with aqueous phase of ZnCl2/HCl and organic phase of crown ethers(CEs), including benzo15-crown-5(B15C5), benzo-18-crown-6(B18C6) and Dicyclohexano-24-crown-8(DC24C8)/1,2- dichloroethane. The isotope enrichment factor (ϵ66), expressed in permil notation, of the isotope pair 66Zn−64Zn was found to be between −0.24 and −0.52 ‰ in the order of enrichment: B15C5≥B18C6>DC24C8. The magnitude of ϵ66was well explained by theoretical isotope fractionation factors obtained by density functional theory method for zinc chloride and ZnCl2/CE model molecules, and a thermochemical description that correlates ϵ66 with the differences in Gibbs free energy(ΔG) of the exchange reaction, here termed δΔG, based on the mass differences of Zn isotopes involved. Finally, results suggest that ϵ66 may be used as a diagnostic and metric of Zn metabolic derangement, such as in porphyrias.


Item ID:	66986
Item Type:	Article (Research - C1)
ISSN:	1521-3749
Keywords:	crown ethers, density functional theory, intramolecular vibrations, isotope fractionation, metallomics, solvent extraction, Zinc
Copyright Information:	© 2021 Wiley-VCH GmbH.
Funders:	Grantsin-Aidfor Scientific Research (GASR), Ministry of Education, Culture, Sports, Science and Technology of Japan (MECSST)
Projects and Grants:	GASR Grant Number: 17H03521
Date Deposited:	21 Jul 2021 05:14
FoR Codes:	32 BIOMEDICAL AND CLINICAL SCIENCES > 3205 Medical biochemistry and metabolomics > 320503 Medical biochemistry - inorganic elements and compounds @ 33% 34 CHEMICAL SCIENCES > 3405 Organic chemistry > 340599 Organic chemistry not elsewhere classified @ 33% 37 EARTH SCIENCES > 3703 Geochemistry > 370303 Isotope geochemistry @ 34%
SEO Codes:	20 HEALTH > 2099 Other health > 209999 Other health not elsewhere classified @ 33% 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280105 Expanding knowledge in the chemical sciences @ 33% 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280103 Expanding knowledge in the biomedical and clinical sciences @ 34%
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