Functionalization of luminescent lanthanide-gallium metallacrowns using copper-catalyzed alkyne-azide cycloaddition and thiol-maleimide Michael addition
Functionalization of luminescent lanthanide-gallium metallacrowns using copper-catalyzed alkyne-azide cycloaddition and thiol-maleimide Michael addition
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DOI：
10.1016/j.jinorgbio.2018.12.011
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发表时间：
2019-03-01
影响因子：
3.9
通讯作者：
Pecoraro, Vincent L.
中科院分区：
文献类型：
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作者：
Lutter, Jacob C.;Bermudez, Beatriz A. Lopez;Pecoraro, Vincent L.
报道了{Ln[12-MCGaN(EHI)III-4]}-(2)(IPH)4和{Ln[12-MCGaN(SHI)III-4]}-(2)(MIPH)(4)金属杂多酸盐(MC)的合成和表征，其中SHI(3-)为水杨基缩水杨酸，EHI(3-)为4-乙炔基水杨基缩水杨酸，IPH(2-)为间苯二甲酸酯，MIPH(2-)为5-马来酰亚胺基间苯二甲酸酯。乙炔基官能团允许使用铜(I)催化的炔-叠氮环加成(CuAAC)将MC偶联到叠氮化物，而马来亚胺官能团允许MC偶联到含硫醇的化合物。我们证明了这些偶联反应，前者使用苄基叠氮化物，后者使用半胱胺，并通过ESI-MS显示完全转化。对于Sm类似物，MC表现出Sm(III)的特征发光，在MC支架上引入乙炔基和马来酰亚胺基团后，这种发光被保留下来。此外，这些化合物在溶液中的高度稳定性表明，一旦功能化，MC将有望用于荧光成像应用。
The synthesis and characterization of {Ln[12-MCGaN(eshi)III-4]}-(2)(iph)4 and {Ln[12-MCGaN(shi)III-4]}-(2)(miph)(4) metallacrowns (MCs), where shi(3-) is salicylhydroximate, eshi(3-) is 4-ethynylsalicylhydroximate, iph(2-) is isopthalate, and miph(2-) is 5-maleimidoisophthalate, is reported. The ethynyl functionality allows for coupling of MCs to azides using copper(I) catalyzed alkyne-azide cycloaddition (CuAAC), while the maleimido functionality allows for coupling of the MCs to thiol-bearing compounds. We demonstrate these coupling reactions using benzyl azide for the former and cysteamine for the latter, with complete conversion shown by ESI-MS. With the Sm analogues, the MCs exhibit characteristic luminescent emission of Sm(III), which is preserved after introducing the ethynyl and maleimido groups onto the MC scaffold. Furthermore, the high stability of these compounds in solution illustrates that once functionalized, the MCs are promising for fluorescent imaging applications.