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Ligand selectivity to specific lanthanide (Ln) ions is key to the separation of rare earth elements from each other. Ligand selectivity can be quantified with relative stability constants (measured experimentally) or relative binding energies (calculated computationally). The relative stability constants of EDTA (ethylenediaminetetraacetic acid) with La 3+ , Eu 3+ , Gd 3+ , and Lu 3+ were predicted from relative binding energies, which were quantified using electronic structure calculations with relativistic effects and based on the molecular structures of Ln–EDTA complexes in solution from density functional theory molecular dynamics simulations. The protonation state of an EDTA amine group was varied to study pH ∼7 and ∼11 conditions. Further, simulations at 25 °C and 90 °C were performed to elucidate how structures of Ln–EDTA complexes varying with temperature are related to complex stabilities at different pH conditions. Relative stability trends are predicted from computation for varying Ln 3+ ions (La, Eu, Gd, Lu) with a single ligand (EDTA at pH ∼11), as well as for a single Ln 3+ ion (La) with varying ligands (EDTA at pH ∼7 and ∼11). Changing the protonation state of an EDTA amine site significantly changes the solution structure of the Ln–EDTA complex resulting in a reduction of the complex stability. Increased Ln–ligand complex stability is correlated to reduced structural variations in solution upon an increase in temperature.
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Using transglutaminase to cross‐link complexes of lactoferrin and α‐lactalbumin to increase thermal stability
Abstract The poor thermal stability of lactoferrin (LF) hinders its bioavailability and use in commercial food products. To preserve LF from thermal denaturation, complexation with other biopolymers has been studied. Here we present the complex formation conditions, structural stability, and functional protection of LF by α‐lactalbumin (α‐LA). The formation of the LF–α‐LA complexes was dependent on pH, mass ratio, and ionic strength. Changing the formation conditions and cross‐linking by transglutaminase impacted the turbidity, particle size, and zeta‐potential of the resulting complexes. Electrophoresis, Fourier‐transform infrared spectroscopy, and circular dichroism measurements suggest that the secondary structure of LF in the LF–α‐LA complex was maintained after complexation and subsequent thermal treatments. At pH 7, the LF–α‐LA complex protected LF from thermal aggregation and denaturation, and the LF retained its functional and structural properties, including antibacterial capacity of LF after thermal treatments. The improved thermal stability and functional properties of LF in the LF–α‐LA complex are of interest to the food industry.
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- Award ID(s):
- 1719875
- PAR ID:
- 10548784
- Publisher / Repository:
- Wiley Online Library
- Date Published:
- Journal Name:
- Journal of Food Science
- Volume:
- 89
- Issue:
- 9
- ISSN:
- 0022-1147
- Page Range / eLocation ID:
- 5488 to 5502
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1111/1750-3841.17182
