Secondary metal doped cuprous-cyanoimidazole frameworks for triple-mode detection of dopamine

Abstract

Backgrounds: Metal-organic framework-based nanozymes enable several opportunities for designing novel analysis methods for the detection of pesticides, heavy metal ions, and biomolecules; however, practical applications are still limited by a complicated synthesis route, lower catalytic activity, and single detection mode. Dopamine (DA) is a crucial catecholamine substance in the human body that acts as a neurotransmitter regulating a variety of physiological functions of the central nervous system. Therefore, it is highly significant to explore simple nanozymes synthesis methods for constructing a multiple analysis system to detection DA.

Results: Herein, we elaborately selected cobalt ions as the secondary metal doping in cuprous-cyanoimidazole frameworks (CuCo-CIFs) with a mass-production strategy. CuCo-CIFs possess intrinsic peroxidase-like activity that can convert hydrogen peroxide into various reactive oxygen species (i.e., ¹O₂, OH·, O₂·^-) and thereby oxidize colorless 3,3',5,5'-tetramethylbenzidine (TMB) and DA to blue oxTMB and orange polydopamine (PDA), respectively. The absorption of the detection system increases at 460 nm while decreases at 652 nm as the concentration of DA increases under near-neutral pH (6.1), resulting in a color transition from blue to orange. Consequently, an unprecedented triple-mode analysis system of DA monitored by naked eyes, ratiometric-absorption, and scanometric was constructed. The limit of detection for the ratiometric-absorption and scanometric mode can reach 20 nM and 28 nM, respectively. CuCo-CIFs were successfully used for the rapid and accurate detection of DA in practical samples.

Significance: As a simple, low-cost, multi-mode colorimetric platform, this kind of nanozyme detection with peroxidase-like activity exhibits significant potential for the detection of DA. Our work not only expands the applications of MOFs in analytical fields but also addresses the general challenges faced by nanozyme-based colorimetric detection systems of DA. This work provides valuable insights for the rational application of nanozyme and the design of new analysis systems.

Keywords: CuCo-CIFs; Dopamine detection; Secondary metal doping; Triple-mode analysis.