Fluorescent “AND” logic gates for simultaneous detection of thiols and protons: photophysical properties, mechanism and bioimaging of living cells

Abstract

Five fluorescent probes TP1–5 were demonstrated as two-input “AND” molecular logic gates for the detection of thiols and protons. The molecules were designed based on “thiol receptor-spacer₁-fluorophore-spacer₂-proton receptor” mode. The logic gates were constructed by employing maleimide, naphthalimide and morpholine (TP1–3)/N-methyl piperazine (TP4–5) as the thiol receptor, fluorophore and proton receptor, respectively. All probes show significant fluorescence enhancements upon addition of both protons and thiols. However, much weaker spectral responses were observed with the addition of only one single analyte. The fluorescence outputs, based on photoinduced electron transfer (PET) and (twisted) intramolecular charge transfer (TICT/ICT), were modulated by the proton receptor and linker. The length of spacer₁ affects the responses toward thiols, whereas spacer₂ influences the sensing performance toward protons. The difference between the pK_a values of morpholine (∼5.80) and N-methyl piperazine (∼7.10) enables us to detect thiols in divergent pH circumstances. TP1–3 exhibit an excellent “AND” logic function for simultaneous detection of protons and thiols as well as bioimaging thiols in weakly acidic living cells. However, TP4 and TP5 are not good candidates for executing “AND” logic operation possibly due to the stronger electron donating properties and steric effect of N-methyl piperazine.