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Luminescent Re(I)/Au(I) Species As Selective Anticancer Agents for HeLa Cells.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-05-18 , DOI: 10.1021/acs.inorgchem.0c00813 Andrés Luengo 1 , Marta Redrado 1 , Isabel Marzo 2 , Vanesa Fernández-Moreira 1 , M Concepción Gimeno 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-05-18 , DOI: 10.1021/acs.inorgchem.0c00813 Andrés Luengo 1 , Marta Redrado 1 , Isabel Marzo 2 , Vanesa Fernández-Moreira 1 , M Concepción Gimeno 1
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A series of neutral and cationic heterotrimetallic complexes of the type fac-[Re(CO)3(bipy(CC)2-(AuL)2)X]n, where bipy(CC)2 is 4,4′-alkynyl-2,2′-bipyridine; L is either triphenylphosphine (PPh3), [1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene] (IPr), or tert-butyl isocyanide (CNtBu); and X is a chloride (n = 0) or acetonitrile (n = 1), were synthesized and characterized together with their Re(I) precursors, i.e., fac-[Re(CO)3(bipy(CC)2)X]n. X-ray diffraction of complexes 1, 3, and 6 corroborated the expected octahedral and linear distribution of the ligands along the Re(I) and Au(I) centers, respectively. Luminescent studies showed that all the complexes displayed a broad emission band centered between 565 and 680 nm, corresponding to a 3MLCT from the Re(I) to the diimine derivative. The presence of the gold fragment coordinated to the diimine ligand shifted in all cases the emission maxima toward higher energies. Such an emission difference could be potentially used for assessing the precise moment of interaction of the probe with the biological target if the gold fragment is implicated. Antiproliferative studies in cancer cells, A549 (lung cancer) and HeLa (cervix cancer), showed a generalized selectivity toward HeLa cells for those heterotrimetallic species incubated at longer times (72 vs 24 h). ICP-MS spectrometry revealed the greater cell internalization of cationic vs neutral species. Preliminary fluorescence microscopy experiments showed a different behavior of the complexes in HeLa and A549 cell lines. Whereas the complexes in A549 were randomly distributed in the outside of the cell, those incubated with HeLa cells were located close to the cellular membrane, suggesting some type of interaction, and possibly explaining their cellular selectivity when it comes to the antiproliferative activity displayed in the different cell lines.
中文翻译：
发光Re（I）/ Au（I）物种作为HeLa细胞的选择性抗癌剂。
一系列类型为fac- [Re（CO）3（bipy（CC）2-（AuL）2）X] n的中性和阳离子异三金属配合物，其中bipy（CC）2为4,4'-炔基-2 ，2'-联吡啶；L为三苯基膦（PPh 3），[1,3-双（2,6-二异丙基苯基）-咪唑-2-亚烷基]（IPr）或叔丁基异氰化物（CN t Bu）；X是氯化物（n = 0）或乙腈（n = 1），与它们的Re（I）前体即fac- [Re（CO）3（bipy（CC）2）X]一起合成和表征ñ。复合物的X射线衍射1，3，和6分别证实沿的Re（I）和Au（I）中心的配位体的预期八面体和线性分布。发光研究表明，所有配合物均显示出在565至680 nm之间的宽发射带，对应于3从Re（I）到二亚胺衍生物的MLCT。在所有情况下，与二亚胺配体配位的金片段的存在将发射最大值移向更高的能量。如果涉及金片段，则这种发射差异可潜在地用于评估探针与生物靶标相互作用的精确时刻。在癌细胞，A549（肺癌）和HeLa（子宫颈癌）中进行的抗增殖研究显示，这些异质三金属物种在更长的时间（72 vs 24 h）下对HeLa细胞具有普遍的选择性。ICP-MS光谱显示，阳离子和中性物质的细胞内在化程度更高。初步的荧光显微镜实验表明，该复合物在HeLa和A549细胞系中的行为不同。
更新日期：2020-07-06
中文翻译：
发光Re（I）/ Au（I）物种作为HeLa细胞的选择性抗癌剂。
一系列类型为fac- [Re（CO）3（bipy（CC）2-（AuL）2）X] n的中性和阳离子异三金属配合物，其中bipy（CC）2为4,4'-炔基-2 ，2'-联吡啶；L为三苯基膦（PPh 3），[1,3-双（2,6-二异丙基苯基）-咪唑-2-亚烷基]（IPr）或叔丁基异氰化物（CN t Bu）；X是氯化物（n = 0）或乙腈（n = 1），与它们的Re（I）前体即fac- [Re（CO）3（bipy（CC）2）X]一起合成和表征ñ。复合物的X射线衍射1，3，和6分别证实沿的Re（I）和Au（I）中心的配位体的预期八面体和线性分布。发光研究表明，所有配合物均显示出在565至680 nm之间的宽发射带，对应于3从Re（I）到二亚胺衍生物的MLCT。在所有情况下，与二亚胺配体配位的金片段的存在将发射最大值移向更高的能量。如果涉及金片段，则这种发射差异可潜在地用于评估探针与生物靶标相互作用的精确时刻。在癌细胞，A549（肺癌）和HeLa（子宫颈癌）中进行的抗增殖研究显示，这些异质三金属物种在更长的时间（72 vs 24 h）下对HeLa细胞具有普遍的选择性。ICP-MS光谱显示，阳离子和中性物质的细胞内在化程度更高。初步的荧光显微镜实验表明，该复合物在HeLa和A549细胞系中的行为不同。
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