Herein, we observed near-infrared electrochemiluminescence (NIR ECL) emission from tetraphenylethylene nanocrystals (TPE NCs), which exhibit high ECL efficiency and excellent biocompatibility compared with the current NIR ECL emitters (such as semiconductor quantum dots and metal nanoclusters). The strong ECL signal of TPE NCs originates from the aggregation-induced enhanced ECL emission via improvement of the efficiency of electron hole recombination and suppression of the nonradiative transition. Impressively, the TPE NCs exhibit an enormous red-shifted ECL emission (678 nm) relative to the blue-light photoluminescence (PL) emission (440 nm). Compared to fluorescence imaging which is limited by photobleaching and autofluorescence, the NIR ECL emission of TPE NCs is highly favorable to diminish background interference over visible light and realize deeper tissue penetration, which expands the ECL emission of organic nanomaterials to the NIR region for broader biological applications.
A new type of multifunctional metal–organic framework (MOF) has been synthesized by encapsulating hemin into the nano-sized Fe-MIL-88 MOFs (hemin@MOFs) and first applied in an electrochemical aptasensor to detect thrombin (TB) with the aid of an enzyme for signal amplification. The gold nanoparticle functionalized hemin@MOFs (Au/hemin@MOFs) have not only simultaneously served as redox mediators and solid electrocatalysts, but have also been utilized as an ideal loading platform to immobilize a large number of biomolecules. In this aptasensor, Au/hemin@MOFs conjugated with glucose oxidase (GOD) and thrombin binding aptamer (TBA II) were used as the secondary aptamer bioconjugates (Au/hemin@MOF–TBA II–GOD bioconjugates), and TB was sandwiched between Au/hemin@MOF–TBA II–GOD bioconjugates and the amino-terminated TBA I which was self-assembled on the gold nanoparticle (AuNP) modified electrode. The GOD could oxidize glucose into gluconic acid accompanied by the generation of H2O2. The generated H2O2 on the electrode surface was further electrocatalyzed by hemin@MOFs to amplify the electrochemical signal of hemin contained in hemin@MOFs. Therefore, the synthesized hemin@MOFs represented a new paradigm for multifunctional materials since it combined three different functions including serving as catalysts, redox mediators and loading platforms within a single material. With such an ingenious design, a wide linear range of 0.0001 nM to 30 nM was acquired with a relatively low detection limit of 0.068 pM for TB detection.