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TD-DFT Guided Advanced E-Eye Sensing Technique for On-site Quantification of Fe, Cr, F, and As in the Environmental, Biological, and Food Samples
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TD-DFT Guided Advanced E-Eye Sensing Technique for On-site Quantification of Fe, Cr, F, and As in the Environmental, Biological, and Food Samples

Published on: September 19, 2025

Iron(III) citrate speciation in aqueous solution.

Andre M N Silva1, XiaoLe Kong, Mark C Parkin

  • 1Pharmaceutical Sciences Research Division, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London, UK SE1 9NH.

Dalton Transactions (Cambridge, England : 2003)
|October 8, 2009
PubMed
Summary
This summary is machine-generated.

This study clarifies ferric citrate speciation at neutral pH, identifying key iron complexes. It reports the formation constant for the biologically relevant [Fe(Cit)2]5- species for the first time.

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Area of Science:

  • Biochemistry
  • Inorganic Chemistry
  • Plant Physiology

Background:

  • Citrate is a key iron chelator in plant xylem sap and in plasma non-transferrin bound iron (NTBI) in iron overload conditions.
  • Ferric citrate chemistry at neutral pH is complex, with previous studies lacking definitive aqueous speciation due to challenges in accounting for citrate deprotonation during complex formation.

Purpose of the Study:

  • To investigate the aqueous speciation of ferric citrate at neutral pH.
  • To determine the formation constant for the biologically relevant monoiron dicitrate species, [Fe(Cit)2]5-.

Main Methods:

  • Mass spectrometry and EPR spectroscopy were used to investigate ferric citrate speciation.
  • Spectrophotometric titration was employed to determine affinity constants.
  • X-ray crystallography data informed the understanding of Fe(III) coordination with citrate's alcohol function.

Main Results:

  • The study identified monoiron dicitrate, dinuclear, and trinuclear oligomeric complexes as the predominant ferric citrate species.
  • The relative concentrations of these species are dependent on pH and the iron:citric acid molar ratio.
  • The formation constant for the [Fe(Cit)2]5- complex was determined for the first time.

Conclusions:

  • The recent determination of citric acid's alcoholic pKa enabled a more accurate reassessment of ferric citrate speciation.
  • This work provides a definitive description of ferric citrate aqueous speciation, resolving previous discrepancies.
  • The reported formation constant for [Fe(Cit)2]5- is crucial for understanding iron transport and metabolism in biological systems.