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<p>Spin exchange interaction between nitroxide radicals (<b>R</b>) and transition metal ions such as Cu(II) and Zn(II) has been studied. In this work, basing on the results obtained on the analysis of [Polymer–Cu(II)–R] systems, we demonstrate peculiarities of small molecules diffusion inside such systems in aqueous solutions of complex-forming polymers: partially alkylated poly(4-vinylpyridine) (P4VP-β), poly(2-methyl-5-vinylpyridine) (P2M5VP-β), branched (BPEI) and linear (LPEI) poly(ethylenimine). The metal ion nature, concentration, spin–lattice relaxation time, the spin probe electric charge and size manifested significant effect on the collisions between Cu–polymer complexes and <b>R</b>. Correct selection of the radical (probe) makes possible obtaining reliable information on the structure of polymer–metal complexes in solutions and about the fraction of the functional groups of a macromolecule involved in the formation of complexes of various types. We believe that the spin-exchange titration (SET) approach will be useful for elucidation peculiarities of small molecules intercalation into ion-exchange resins, supported catalysts based on various nano- and micro-porous organic and inorganic carriers.</p>

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Spin Exchange Titration in Studying Spatial Organization of Polymer–Metal Coils in Liquid Solutions

  • 期刊论文

  • 发表日期：

    2025年8月24日

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  • Alexander I. Kokorin

摘要

Spin exchange interaction between nitroxide radicals (R) and transition metal ions such as Cu(II) and Zn(II) has been studied. In this work, basing on the results obtained on the analysis of [Polymer–Cu(II)–R] systems, we demonstrate peculiarities of small molecules diffusion inside such systems in aqueous solutions of complex-forming polymers: partially alkylated poly(4-vinylpyridine) (P4VP-β), poly(2-methyl-5-vinylpyridine) (P2M5VP-β), branched (BPEI) and linear (LPEI) poly(ethylenimine). The metal ion nature, concentration, spin–lattice relaxation time, the spin probe electric charge and size manifested significant effect on the collisions between Cu–polymer complexes and R. Correct selection of the radical (probe) makes possible obtaining reliable information on the structure of polymer–metal complexes in solutions and about the fraction of the functional groups of a macromolecule involved in the formation of complexes of various types. We believe that the spin-exchange titration (SET) approach will be useful for elucidation peculiarities of small molecules intercalation into ion-exchange resins, supported catalysts based on various nano- and micro-porous organic and inorganic carriers.