Metal-Organic Frameworks Encapsulating Carbon Dots Enable Fast Speciation of Mono- and Divalent Copper

Copper is an essential element to play significant roles in human health associated to the strong redox properties of Cu(I) and Cu(II). The concurrent monitoring of copper species in biological matrixes is highly desired. Herein, a dual-channel fluorescence nanoprobe was designed for the speciation of mono- and divalent copper by conjugating carbon dots (CDs) with Eu-based metal-organic frameworks (Eu-MOFs). The obtained Eu-MOFs@CD nanoprobe exhibits fluorescence at λ_ex/λ_em = 380/454 nm from CDs and λ_ex/λ_em = 275/615 nm from Eu-MOFs. Bathocuproine disulfonate (BCS) specifically chelates Cu⁺ to produce a BCS-Cu⁺ adduct with absorption at 480 nm, which quenches the fluorescence of CDs at 454 nm due to the inner filter effect. On the other hand, Cu²⁺ quenches the fluorescence of Eu-MOFs due to the replacement of Eu³⁺ by Cu²⁺. Thus, Eu-MOFs@CDs enable extremely fast detection of Cu⁺ and Cu²⁺ within 1 min. Furthermore, the nanoprobe is demonstrated by monitoring the variation of Cu⁺ and Cu²⁺ in the degradation process of copper nanoparticles and Cu-based MOFs.