Although Ru(bpy)₃²⁺‐doped silica nanoparticles have been widely explored as the labelling tags for electrochemiluminescence (ECL) sensing different targets, the poor electrical conductive properties of the silica nano‐matrix greatly limit their ECL sensitivity. Therefore, a novel scheme to overcome this drawback on Ru(bpy)₃²⁺‐doped silica nanoparticles ECL is desirable. Here, a new scheme for this purpose was developed based on electrochemically depositing a nanoscale chitosan hydrogel layer on the carbon nanotube (CNT) surface to form chitosan hydrogel shell@CNT core nanocomposites. In this case, the nanoscale chitosan hydrogel layer only formed on the CNT surface due to the superior electrocatalytic effect of CNT on H⁺ reduction compared with the basic glass carbon electrode. Due to both the superhydrophilic properties and polyelectrolyte features of nanoscale chitosan hydrogel on the CNT surface, chemical affinity as well as the electric conductivity between Ru(bpy)₃²⁺‐doped silica nanoparticles and CNT were obviously enhanced, and then the ECL effectivity of Ru(bpy)₃²⁺ inside silica nanoparticles was improved. Furthermore, based on the discriminative interaction of these Ru(bpy)₃²⁺‐doped silica nanoparticles towards both the ssDNA probes and the ssDNA probe/miRNA complex, as well as the specific adsorption effect of these nanoparticles on the nanoscale chitosan shell@Nafion/CNT core‐modified glass carbon electrode, a highly sensitive ECL method for miRNA determination was developed and successfully used to detect miRNA in human serum samples.

中文翻译：

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壳聚糖/ Nafion shell @碳纳米管核修饰电极增强Ru（bpy）32+掺杂的二氧化硅纳米粒子的电化学发光

尽管Ru（bpy）₃ ²⁺掺杂的二氧化硅纳米粒子已被广泛地用作检测不同目标的电化学发光（ECL）的标记标签，但二氧化硅纳米矩阵的较差的导电性能极大地限制了其ECL敏感性。因此，需要一种新颖的方案来克服Ru（bpy）₃ ²⁺掺杂的二氧化硅纳米粒子ECL的这一缺点。在此，基于在碳纳米管（CNT）表面上电化学沉积纳米级壳聚糖水凝胶层以形成壳聚糖水凝胶壳@CNT核心纳米复合材料的基础上，开发了一种用于该目的的新方案。在这种情况下，由于CNT对H ⁺的优异电催化作用，纳米级壳聚糖水凝胶层仅在CNT表面形成与碱性玻璃碳电极相比，还原率更高。由于纳米级壳聚糖水凝胶在CNT表面具有超亲水性能和聚电解质特性，Ru（bpy）₃ ²⁺掺杂的二氧化硅纳米颗粒与CNT之间的化学亲和性和电导率均得到明显增强，从而使ECL的ECL效果显着提高。二氧化硅纳米粒子内部的Ru（bpy）₃ ²⁺得到改善。此外，基于这些Ru（bpy）₃ ²⁺的判别相互作用对ssDNA探针和ssDNA探针/ miRNA复合物都掺杂了二氧化硅纳米颗粒，以及这些纳米颗粒对壳聚糖壳聚糖@ Nafion / CNT核修饰的玻璃碳电极纳米级的特异性吸附作用，这是一种对miRNA高度敏感的ECL方法开发了测定方法，并成功用于检测人血清样品中的miRNA。