Selective antioxidant recognition plays a critical role in various scientific and clinical fields, however, development of straightforward detection mechanisms and reduction of technique operation are still barriers nowadays. For example, convenient detection of epigallocatechin gallate (EGCG), the most effective antioxidant among all tea catechins, is highly sought but is severely limited due to the lack of appropriate indicators. To overcome the aforementioned obstacles and to provide more adequate processes that can be employed in antioxidant detection, specific analyte targeting and efficient signal reporting are necessary for the platform design. In this work, a fluorescence "turn on" strategy based on gold nanocluster (AuNC) interface-mediated radical scavenging for selective antioxidant detection is reported. This approach utilizes Lcysteine capped AuNCs with great fluorescence stability as the reporter, where the presence of reactive oxygen species (ROS) generated from the Fenton reaction results in obvious fluorescence quenching. The introduction of antioxidants, that is, EGCG molecules, interestingly, neutralizes the ROS by initiating direct electron and hydrogen atom transfer to eliminate the unpaired free radicals. Besides, the phenolic OH groups and the gallate ring of EGCG also provide a selective and efficient complexation orientation toward Fenton reaction metal ions, where ROS generation is consequently prohibited. This dual-effect phenomenon recovers the originally ROS quenched AuNC fluorescence, which is dependent upon the introduced EGCG quantity. Relying on this fluorescence turn on strategy, the current platform delivers a low detection limit of 1.20 μM with excellent selectivity toward EGCG under the presence of other interfering species. Meanwhile, this approach also provides great accuracy on detecting total antioxidant capacity in commercial green tea samples. This antioxidant fluorometric turn on design therefore gives a more straightforward route on EGCG detection, and its specific recognition capability is very suitable for practical real sample analysis.
Guiding metal organic framework (MOF) morphology, especially without the need for chemical additives, still remains a challenge. For the first time, we report a unique surface guiding approach in controlling the crystal morphology formation of zeolitic imidazole framework-8 (ZIF-8) and HKUST-1 MOFs on disrupted alkanethiol self-assembled monolayer (SAM)-covered Au substrates. Selective molecule removal is applied to generate diverse SAM matrices rich in artificial molecular defects in a monolayer to direct the dynamic crystal growth process. When a 11-mercaptoundecanol alkanethiol monolayer is ruptured, the hydroxyl tail groups of surface residue molecules act as nucleating sites by coordination with precursor metal ions. Meanwhile, the exposed alkane chain backbones stabilize a particular facet of MOF nuclei in the dynamic growth by slowing down their crystal growth rates along a specific direction. The competitive formation between the [110] and [100] planes of ZIF-8 ultimately regulates the crystal shapes from rhombic dodecahedron, truncated rhombic dodecahedron, and truncated cube to cube. Similarly, changeable morphologies of HKUST-1 crystals are also achieved from cube and tetrakaidekahedron to octahedron, originating from the competitive selection between the [100] and [111] planes. In addition to the artificial matrix preferred orientation of initial nucleation, parameters such as temperature also play a crucial role in the resulting crystal morphology. Standing on the additive-free MOF crystal morphology growth control, porous architectures prepared in this approach can act as templates for ligand-free metal (Au, Ag, and Cu) nanocluster synthesis. The nanocluster-embedded MOF structures represent distinct crystal morphology-dependent optical properties, and interestingly, their fluorescence emission can be highly enhanced by facet-induced nanocluster packing alignments. These findings not only provide a unique thought on MOF crystal morphology guidance but also pave a new route for the accompanied property investigation and further application.
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