Stoichiometry between Humate Unit Molecules and Metal Ions in Supramolecular Assembly Induced by Cu2+ and Tb3+ Measured by Gel Electrophoresis TechniquesClick to copy article linkArticle link copied!
- Sumika NakanoSumika NakanoGraduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, JapanMore by Sumika Nakano
- Kazuki MarumoKazuki MarumoGraduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, JapanMore by Kazuki Marumo
- Rintaro KazamiRintaro KazamiGraduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, JapanMore by Rintaro Kazami
- Takumi SaitoTakumi SaitoNuclear Professional School, Graduate School of Engineering, The University of Tokyo, 2-21 Shirakata-Shirane, Tokai-mura, Ibaraki 319-1188, JapanMore by Takumi Saito
- Tomoko HaragaTomoko HaragaDepartment of Decommissioning and Waste Management, Japan Atomic Energy Agency, 2-4 Shirakata, Tokai-mura, Naka-gun, Ibaraki 319-1195, JapanMore by Tomoko Haraga
- Yuiko Tasaki-HandaYuiko Tasaki-HandaGraduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, JapanMore by Yuiko Tasaki-Handa
- Shingo Saito*Shingo Saito*Email: [email protected]. Phone: +81 48 858 3559.Graduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, JapanMore by Shingo Saito
Abstract

Humic acid (HA), a fraction of humic substances, can strongly complex with metal ions to form a supramolecular assembly via coordination binding and other intermolecular forces. However, determining the supramolecular size distribution and stoichiometry between small HA unit molecules constituting HA supramolecules and metal ions has proven to be challenging. Here, we investigated the changes in the size distributions of HAs induced by Cu2+ and Tb3+ ions using unique PAGE for the separation and quantification of HA complexes and metal ions bound, followed by UV–vis spectroscopy and excitation–emission matrix–parallel factor analysis. By determining the concentrations of HA and metal ions, it was possible to estimate the stoichiometry of the HA unit molecule to metal ions in supramolecular complexes. It was found that the supramolecular behaviors of Cu2+ and Tb3+ complexes with HA collected from peat (PAHA) and deep groundwater (HHA) differed. For example, two HHA unit molecules form a supramolecule via cross-linking by a Cu2+ ion in the case of Cu2+–HHA. Our results suggest that this supramolecular stoichiometry is related to the abundance of sulfur atoms in the elemental composition of HHA. Our experimental results and analysis provide new insights into HA supramolecules formed via metal complexation.
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