Insights into enantioselective separations of ionic metal complexes by sub/supercritical fluid chromatography.
Insights into enantioselective separations of ionic metal complexes by sub/supercritical fluid chromatography.
复制标题
通过亚/超临界流体色谱法对离子金属复合物的对映选择性分离的见解。
DOI：
10.1016/j.aca.2022.340156
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发表时间：
2022-10-02
影响因子：
6.2
通讯作者：
Armstrong, Daniel W.
中科院分区：
文献类型：
--
作者：
Handlovic, Troy T.;Wahab, M. Farooq;Cole, Houston D.;Alatrash, Nagham;Ramasamy, Elamparuthi;MacDonnell, Frederick M.;McFarland, Sherri A.;Armstrong, Daniel W.
关键词：
亚/超临界流体色谱 (SFC) 是一种绿色分离技术，已用于分离多种化合物，并被证明对于手性分离非常有用。然而，SFC 目前被认为不适用于离子化合物，因为它们在 CO2 中的溶解度较低，即使有添加剂和有机改性剂也是如此。最近，大量研究集中在 Ru(II) 和 Os(II) 与二齿多吡啶基配体的八面体配合物上，因为它们能够用于癌症治疗和其他生物活性。这些化合物以 δ (Δ) 和 lambda (Λ) 对映体形式存在。此前，类似的化合物已使用 HPLC 和毛细管电泳进行对映体分离，但从未使用过 SFC。 (R)-萘乙基 (RN) 基团衍生的环果聚糖-6 (CF6) 已被证明是 HPLC 中这些分离的有效手性固定相。该色谱柱化学性质扩展到 SFC，首次对多种（总共 23 种络合物）离子八面体聚吡啶络合物进行手性分离。将讨论混合甲醇和乙腈作为有机改性剂的意外行为以及添加剂的影响。 CF6-RN 化学的对映选择性取决于金属配合物的共轭水平和刚性。还显示了传质动力学行为，并显示了高效基线解析的快速分离，用于快速筛选或定量代表性配位复合物。
Sub/supercritical fluid chromatography (SFC) is a green separation technique that has been used to separate a wide variety of compounds and is proven to be immensely useful for chiral separations. However, SFC is currently not thought to be applicable for ionic compounds due to their low solubility in CO2, even with additives and organic modifiers. Recently, a large amount of research has been centered on octahedral complexes of Ru(II) and Os(II) with bidentate polypyridyl ligands due to their ability to serve in cancer treatment and other biological activities. These compounds exist as the delta (Δ) and lambda (Λ) enantiomers. Previously, similar compounds have been enantiomerically separated using HPLC and capillary electrophoresis, but never with SFC. Cyclofructan-6 (CF6) derivatized with (R)-naphthyl ethyl (RN) groups has been proven to be an effective chiral stationary phase for these separations in HPLC. This column chemistry was expanded to SFC to provide the first chiral separation of a wide variety (23 complexes in total) of ionic octahedral polypyridyl complexes. Unexpected behavior for mixing methanol and acetonitrile as the organic modifier will be discussed, along with the effects of additives. Enantioselectivity on CF6-RN chemistry is shown to be dependent on the conjugation level and rigidity of the metal complexes. Mass transfer kinetic behavior is also shown, and high-efficiency baseline resolved rapid separations are shown for fast screening or quantitation of representative coordination complexes.
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DOI：
10.1016/j.jpba.2021.114233
发表时间：
2021-09-10
影响因子：
3.4
作者：
Armstrong DW;Yu J;Cole HD;McFarland SA;Nafie J
通讯作者：
Nafie J
影响因子：
7.4
作者：
Liu, Jinchu;Makarov, Alexey A.;Regalado, Erik L.
通讯作者：
Regalado, Erik L.
影响因子：
4.1
作者：
Gritti, Fabrice;Cavazzini, Alberto;Guiochon, Georges
通讯作者：
Guiochon, Georges
影响因子：
4.1
作者：
Liu, Y;Berthod, A;Armstrong, DW
通讯作者：
Armstrong, DW
影响因子：
7.4
作者：
Barhate, Chandan L.;Wahab, M. Farooq;Armstrong, Daniel W.
通讯作者：
Armstrong, Daniel W.