A novel ratiometric and reversible fluorescence probe with a large Stokes shift for Cu²⁺ based on a new clamp-on unit

A novel ratiometric and reversible chemosensor 4-((2-(Benzo[d]thiazol-2-yl)phenyl)ethynyl)-N,N-diethylaniline (BT-1) based on ortho-arylethynyl benzothiazole with large Stokes shift (Δλ≈190 nm) was designed and synthesized to recognize Cu²⁺. Copper ion induces a remarkable fluorescence enhancement and causes formation of a BT-1-Cu complex. The clamp-on coordination mode of BT-1 to Cu²⁺ was demonstrated using Job's plot, mass spectrum (MS) and DFT calculations. The calculations also indicate that Cu²⁺ was chelated to BT-1 through N and alkyne instead of S and alkyne. The probe could quantify Cu²⁺ with the detection limit of 3.2 × 10^-9 M. The in vitro imaging results indicated that the probe BT-1 was membrane-permeable and could be applied into the recognition of Cu²⁺ ions in living cells.