Haddache Fatima, Le Goff Alan, Reuillard Bertrand, Gorgy Karine, Gondran Chantal, Spinelli Nicolas, Defrancq Eric, Cosnier Serge
Université Grenoble Alpes - CNRS, DCM UMR 5250, 38000 Grenoble (France).
Chemistry. 2014 Nov 17;20(47):15555-60. doi: 10.1002/chem.201404335. Epub 2014 Sep 26.
The design of photoactive functionalized electrodes for the sensitive transduction of double-stranded DNA hybridization is reported. Multifunctional complex Ru(bpy-pyrrole)2 (dppn) (bpy-pyrrole=4-methyl-4'-butylpyrrole-2,2'-bipyridine, dppn=benzo[i]dipyrido[3,2-a:2',3'-c]phenazine) exhibiting photosensitive, DNA-intercalating, and electropolymerizable properties was synthesized and characterized. The pyrrole groups undergo oxidative electropolymerization on planar electrodes forming a metallopolymer layer on the electrode. Thanks to the photoelectrochemical and intercalating properties of the immobilized Ru(II) complex, the binding of a double-stranded HIV DNA target was photoelectrochemically detected on planar electrodes. Photocurrent generation through visible irradiation was correlated to the interaction between double-stranded DNA and the metallointercalator polymer. These interactions were well fitted by using a Langmuir isotherm, which allowed a dissociation constant of 2×10(6) L mol(-1) to be estimated. The low detection limit of 1 fmol L(-1) and sensitivity of 0.01 units per decade demonstrate excellent suitability of these modified electrodes for detection of duplex DNA.
报道了用于双链DNA杂交灵敏转导的光活性功能化电极的设计。合成并表征了具有光敏、DNA嵌入和可电聚合性质的多功能配合物[Ru(bpy - 吡咯)2(dppn)](2 +)（bpy - 吡咯 = 4 - 甲基 - 4'- 丁基吡咯 - 2,2'- 联吡啶，dppn = 苯并[i]二吡啶并[3,2 - a:2',3'- c]吩嗪）。吡咯基团在平面电极上进行氧化电聚合，在电极上形成金属聚合物层。由于固定化Ru(II)配合物的光电化学和嵌入性质，在平面电极上通过光电化学方法检测到双链HIV DNA靶标的结合。通过可见光照射产生的光电流与双链DNA和金属嵌入聚合物之间的相互作用相关。这些相互作用通过使用朗缪尔等温线得到很好的拟合，据此估计解离常数为2×10(6) L mol(-1)。1 fmol L(-1)的低检测限和每十倍浓度变化0.01单位的灵敏度表明这些修饰电极非常适合用于双链DNA的检测。
