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Non-Cytotoxic,Bifunctional Eu~(III)and Tb~(III)Luminescent Macrocyclic Complexes for Luminescence Resonant Energy-Transfer Experiments

机译:无细胞毒性,双功能的Eu〜(III)和Tb〜(III)发光大环配合物用于发光共振能量转移实验

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摘要

A new macrocyclic ligand,L3,has been synthesised,based on the cyclen framework grafted with three phenacyl light-harvesting groups and a C_5-alkyl chain bearing a carboxylic acid function as a potential linker for biological material.Acidity constants are determined by spectrophotometric titrations,as well as conditional stability constants for the resulting 1:1 complexes with trivalent lanthanide ions.The complexes have stabilities comparable to l,4,7,10-tetrakis(carbamoyl-methyl)-l,4,7,10-tetraazacyclododecane(dtma)complexes,with pLn≈ 12-13.Photophysical properties of the ligand and of the EuL~3 and TbL~3 complexes have been determined for both micro-crystalline samples and solutions in water and acetonitrile.They point to the metal ion being present in an environment with axial symmetry derived from the C_4 point group.The hydration number determined for TbL~3 decreases with increasing pH value and becomes fractional at pH 7.5,which points to an equilibrium between two differently solvated species and probably to the participation of the deprotonated carboxylic acid chain in the complexation.The quantum yields in water(1.9% for Eu~(III),3.4% for Tb~(III))are smaller than those for complexes with the symmetri- cally substituted parent macrocycle,but efficient luminescence resonant energy transfer(LRET)was observed when Cy5 dye was added to the solutions.Finally,the influence of the TbL~3 complex on cell viability is tested on both malignant(5D10 mouse hybridoma,Jurkat human T leukaemia,MCF-7 human breast carcinoma)and non-malignant(Hacat human keratinocyte)cell lines.Cell viability after 24 h incubation at 37 °C with 500 mu m TbL~3 was >90% for all cell lines,except Jurkat(>70%).All of these properties make LnL~3 complexes interesting potential probes for bioanalyses.
机译:基于接枝了三个苯甲酰基光捕获基团和带有羧酸功能的C_5-烷基链作为生物材料潜在连接体的cycln骨架,合成了一种新的大环配体L3。酸度常数通过分光光度滴定法测定以及与三价镧系元素离子形成的1:1配合物的条件稳定性常数。该配合物的稳定性可与1,4,7,10-四(氨基甲酰基-甲基)-1,4,7,10-四氮杂环十二烷( dtma)络合物,pLn≈12-13。已测定了微晶样品以及在水和乙腈中的溶液的配体以及EuL〜3和TbL〜3配合物的光物理性质。 TbL〜3的水合数随pH值的增加而降低,并在pH 7.5时变为分数,这表明两个不同s之间的平衡水溶液中的量子产率(Eu〜(III)为1.9%,Tb〜(III)为3.4%)比具有对称性的配合物要小。 -取代的亲本大环,但在溶液中加入Cy5染料时观察到有效的发光共振能量转移(LRET)。最后,测试了TbL〜3复合物对两种恶性(5D10小鼠杂交瘤,Jurkat)细胞活力的影响人T白血病,MCF-7人乳腺癌和非恶性(Hacat人角质形成细胞)细胞系。在37°C与500μmTbL〜3孵育24小时后,所有细胞系的细胞存活率均> 90% Jurkat(> 70%)。所有这些特性使LnL〜3复合物成为潜在的生物分析探针。

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