Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media,European Journal of Inorganic Chemistry

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Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2016-12-30 , DOI: 10.1002/ejic.201601442
Harrison A. Neal ₁ , Jennifer Szymanowski ₂ , Jeremy B. Fein ₂ , Peter C. Burns ₂ , May Nyman ₁

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Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface.

中文翻译：

有机介质中过氧化铀胶囊化学的基准测试

过氧化铀酰胶囊是多金属氧酸盐 (POM) 化学中的最新成员。十年的发展仅在水中进行，而过渡金属 POM 通常在水和有机介质中开发，由反离子或连接控制以使簇具有亲水性或疏水性。在这里，新的铀酰 POM 行为在有机介质中被识别，包括 (1) 包封的亲水性抗衡阳离子的稳定和固定，由锂核磁共振 (NMR) 光谱鉴定，(2) 相转移时新簇物种的形成，(3)从不同的起始材料（包括模拟的乏核燃料）中提取铀酰簇，（4）从混合物中选择性地转移一种簇类型，以及（5）从酸性和碱性介质中进行簇的相转移。铀酰 POM 的胶囊形态通过 X 射线散射进行准确表征，包括几何相似簇的区别。萃取后水相的组成分析提供了离子交换过程的定量测定，该过程能够将簇转移到有机相中。铀酰 POM 优先分配到有机介质中为金属离子行为和疏水介质中团簇胶囊的密闭空间中的化学反应以及团簇在有机/水界面的反应性提供了新的前沿。萃取后水相的组成分析提供了离子交换过程的定量测定，该过程能够将簇转移到有机相中。铀酰 POM 优先分配到有机介质中为金属离子行为和疏水介质中团簇胶囊的密闭空间中的化学反应以及团簇在有机/水界面的反应性提供了新的前沿。萃取后水相的组成分析提供了离子交换过程的定量测定，该过程能够将簇转移到有机相中。铀酰 POM 优先分配到有机介质中为金属离子行为和疏水介质中团簇胶囊的密闭空间中的化学反应以及团簇在有机/水界面的反应性提供了新的前沿。

更新日期：2016-12-30

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