Trinuclear ruthenium clusters as bivalent electrochemical probes for ligand-receptor binding interactions.
Trinuclear ruthenium clusters as bivalent electrochemical probes for ligand-receptor binding interactions.
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DOI：
10.1021/la202882k
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发表时间：
2012-01-10
期刊：
影响因子：
--
通讯作者：
Meade TJ
中科院分区：
文献类型：
--
作者：
Feld DJ;Hsu HT;Eckermann AL;Meade TJ
尽管电化学生物传感器很受欢迎，但它们往往存在灵敏度低的问题。克服蛋白质生物传感器低灵敏度的一个可能的方法是利用多价配体-受体相互作用。控制配体在表面的空间排列是电化学生物传感器设计的另一个重要方面。我们合成并表征了五个生物素化的三核Ru簇合物：[Ru3O(OAc)6CO(4-BMP)(Py)]0(3)，[Ru3O(OAc)6CO(4-BMP)2]0(4)，[Ru3O(OAc)6L(4-BMP)(Py)]+(8)，[Ru3O(OAc)6L(4-BMP)2]+(9)，[Ru3O(OAc)6L(Py)2]+(10)(OAc=乙酸酯，4-BMP=生物素胺甲基吡啶，py=生物素L=pyC16SH)。用HABA/Avidin比色法和等温滴定量热法测定了3和4的亲和素结合性能，结合常数为6.5~8.0×106M−1。QM、MM和MD计算表明，二价簇4能够与亲和素分子内结合。在3a和4a溶液中的电化学测量表明，在亲和素存在下，−58的E_1/2分别移动到−53 mV。研究了8-10分子自组装单分子膜作为生物传感器的模型体系。稀释剂/簇的比例和组成对亲和素与簇充分结合的能力有显著影响。络合物8和10在加入亲和素后，−43 mV的E1/2无明显变化，而络合物9则发生移位。这些结果表明，多价相互作用可以对电化学蛋白质生物传感器的灵敏度产生积极的影响。
Despite their popularity, electrochemical biosensors often suffer from low sensitivity. One possible approach to overcome low sensitivity in protein biosensors is to utilize multivalent ligand-receptor interactions. Controlling the spatial arrangement of ligands on surfaces is another crucial aspect of electrochemical biosensor design. We have synthesized and characterized five biotinylated trinuclear ruthenium clusters as potential new biosensor platforms : [Ru3O(OAc)6CO(4-BMP)(py)]0 (3), [Ru3O(OAc)6CO(4-BMP)2]0 (4), [Ru3O(OAc)6L(4-BMP)(py)]+ (8), [Ru3O(OAc)6L(4-BMP)2]+ (9), and [Ru3O(OAc)6L(py)2]+ (10) (OAc = acetate, 4-BMP = biotin aminomethylpyridine, py = pyridine, L = pyC16SH). HABA/avidin assays and isothermal titration calorimetry were used to evaluate the avidin binding properties of 3 and 4. The binding constants were found to range from 6.5 – 8.0 × 106 M−1. Intermolecular protein binding of 4 in solution was determined by native gel electrophoresis. QM, MM, and MD calculations show the capability for the bivalent cluster, 4, to intramolecularly bind to avidin. Electrochemical measurements in solution of 3a and 4a show shifts in E1/2 of −58 to −53 mV in the presence of avidin, respectively. Self-assembled monolayers formed with 8–10 were investigated as a model biosensor system. Diluent/cluster ratio and composition were found to have a significant effect on the ability of avidin to adequately bind to the cluster. Complexes 8 and 10 showed negligible changes in E1/2, while complex 9 showed a shift in E1/2 of −43 mV upon avidin addition. These results suggest that multivalent interactions can have a positive impact on the sensitivity of electrochemical protein biosensors.
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