Strong electrochemiluminescence (ECL) of titania dioxide nanotubes at physiological condition was observed, with relatively low cathodic potential due to its large surface area and high electron transfer efficiency. The coreactant of the ECL emission was proved to be H 2 O 2 , produced from the reduction of dissolved oxygen, leading to a mild ECL system for biosensing. Based on "coreactant inhibition" mechanism, the ECL quenchers could be measured by inhibiting the transformation of O 2 to H 2 O 2 . Using hemoglobin as a model, the quenched ECL emission followed SternÀVolmer equation in a wide linear range. Thus a novel methodology for detection of "coreactant inhibition"-related quencher could be developed with acceptable sensitivity. [4]. However, the overwhelming used QDs ECL emitters were focused on II-VI QDs, which were of great biotoxicity and suffered instability during storage even at 4 8C. Recently, many nanostructures with low biotoxicity such as Au 25 [5] and Ag [6] nanoclusters, C-dots [7], and ZnO [8] and TiO 2 nanoparticles (NPs) [9] have shown excellent ECL emission and been used as ECL emitters. However, most of these nano-ECL emitters show relatively high emission potential and need strong oxidant S 2 O 8 2À as coreactant to produce ECL signal, which greatly increase the occurrence of undesired reaction and are adverse for both bioanalysis and fabrication of energy devices. Here, a novel nano-ECL emitter, TiO 2 nanotube (TNT) with lower biotoxicity, was suggested to overcome these limits.
KeywordsTiO 2 nanoparticles have been extensively used as advanced photocatalytic materials. The photoluminescent behaviors of TiO 2 nanostructures have been widely reported [10]. Compared with general QDs, TNT possesses large surface areas and narrower surface band gap, which will produces high quantum transfer efficiency, higher ECL efficiency and lower emission potential [11,12]. However, its ECL characteristics and applications have rarely been investigated. This work observed a strong ECL emission from TNT in air-saturated neutral buffer with a relatively low potential, approximately 500 mV more positive than those reported cathodic ECL systems using TiO 2 NPs [9] or TNT [13,14] as ECL emitters. The ECL mechanism was proved to be a coreactant-induced process. The coreactant H 2 O 2 was produced from the reduction of dissolved oxygen, leading to a mild ECL system without assistance of any other strong oxidant. A "coreactant inhibition" mechanism was further proposed to develop a novel methodology for ECL detection of quenchers using hemoglobin (HB) as a model.The powder X-ray diffraction (XRD) spectrum showed an anatase crystal form of the as-prepared TNT (Figure 1A). Its high-resolution transmission electron microscope (HRTEM, JEM-2100, JEOL) showed a nanotube structure with a length of~90 nm and a diameter of 12 nm (Inset, Figure 1B). The formed TNT film exhibited a uniform morphology with the homogeneous aggregation size maintaining the original shape of the TNT (Figure 1B).Compared with the bar...