Fe(III)-polyuronic acid photochemistry: radical chemistry in natural polysaccharide

Fe(III)-polyuronic acid photochemistry: radical chemistry in natural polysaccharide
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Fe(III)-聚糖醛酸光化学:天然多糖中的自由基化学

DOI:
10.1007/s43630-021-00014-0
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发表时间:
2021
影响因子:
3.1
通讯作者:
Ostrowski, Alexis D.
Ostrowski, Alexis D.
中科院分区:
化学3区
文献类型:
--
作者:
Karunarathna, M. H.;Ayodele, Mayokun J.;Giammanco, Giuseppe E.;Brugh, Alexander M.;Muizzi, Dayana A.;Bauman, Mariia A.;Torelli, Andrew T.;Alabanza, Anginelle M.;Forbes, Malcolm D.;Ostrowski, Alexis D.

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在水溶液中,Fe(III)配位到天然含糖醛酸多糖的光化学已被定量研究。它表明,光还原的协调Fe(III)的Fe(II)和氧化脱羧发生在各种含糖醛酸的多糖。的Fe(III)-多糖醛酸系统的光化学反应过程中产生的自由基物种,使用自旋捕获技术进行了研究。来自该反应的自由基物质的身份被确认为CO2·−,表明在配体与金属的电荷转移自由基反应后,羧酸酯的键断裂和氧化脱羧可能在辐照时发生。的聚糖醛酸链的降解进行了研究与动态光散射,显示减少的流体动力学半径的聚合物组件在溶液中的光照射后,与Fe(II)代。还观察到光照射后Fe(IIII)-藻酸盐的粘度降低。此外,在植物根组织(欧洲防风)的光化学反应进行了研究,证明在这些天然材料中的Fe(III)协调导致光反应性,降解果胶组分。这些结果强调了这种Fe(III)-多糖醛酸可以存在于许多自然系统中,并且可能在具有显著多糖醛酸含量的植物中的铁和亚铁生成的地球化学循环中发挥作用。
The photochemistry of Fe(III) coordinated to natural uronate-containing polysaccharides has been investigated quantitatively in aqueous solution. It is demonstrated that the photoreduction of the coordinated Fe(III) to Fe(II) and oxidative decarboxylation occurs in a variety of uronate-containing polysaccharides. The photochemistry of the Fe(III)-polyuronic acid system generated a radical species during the reaction which was studied using the spin trapping technique. The identity of the radical species from this reaction was confirmed as CO2•−indicating that both bond cleavage of the carboxylate and oxidative decarboxylation after ligand to metal charge transfer radical reactions may be taking place upon irradiation. Degradation of the polyuronic acid chain was investigated with dynamic light scattering, showing a decrease in the hydrodynamic radius of the polymer assemblies in solution after light irradiation that correlates with the Fe(II) generation. A decrease in viscosity of Fe(IIII)-alginate after light irradiation was also observed. Additionally, the photochemical reaction was investigated in plant root tissue (parsnip) demonstrating that Fe(III) coordination in these natural materials leads to photoreactivity that degrades the pectin component. These results highlight that this Fe(III)-polyuronic acid can occur in many natural systems and may play a role in biogeochemical cycling of iron and ferrous iron generation in plants with significant polyuronic acid content.Graphic abstract
电子显微镜中看到的染色果胶
DOI: --
发表时间: 1960
期刊: The Journal of Biophysical and Biochemical Cytology
影响因子: --
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