DNA G-quadruplex (G4) could adopt
multiple conformations, and the exact conformation is related to the
presence of cations. However, the fact that cations with various concentrations
could competitively bind with G4 is rarely investigated, which greatly
limits the potential applications of G4-based sensors. Here, with
PW17 (a G4-forming DNA sequence) as an example, Na+ and
K+ with different concentrations competitively binding
with PW17 are clarified by circular dichroism spectroscopy and electrospray
ionization mass spectroscopy. Although Na+ could induce
PW17 switching to unstable and antiparallel Na+-stabilized
PW17 (2Na+-PW17) (C
Na+
= 5–70 mM) and further to stable and hybrid 2Na+-PW17 (C
Na+
= 70–800
mM), K+ (C
K+
= 0.1–10
mM) could replace Na+ in 2Na+-PW17 with 2Na+-PW17 transforming into K+-stabilized PW17 (2K+-PW17). Moreover, the replacing ability strictly relied on C
K+
and C
Na+
. In the switching process, a stable intermediate including
a K+ and an Na+ in one G4 (K+–Na+-PW17) is firstly detected. Importantly, the stable K+–Na+-PW17 is detected at 0.5 mM K+ and 140 mM Na+. Based on the facts, the interferences
of Na+ with the performance of PW17-based K+ sensors are investigated. With the stable K+–Na+-PW17 as a sensing probe and protoporphyrin IX (PPIX) as a
G4 fluorescent read-out probe, a linear relationship between C
K+
(500 nM–10 mM) and PPIX
fluorescence is observed, which provides a fluorescence assay for
detecting K+ with the co-existing 140 mM Na+. This study exhibits clear evidence of Na+ and K+ competitively binding with G4 and finds a novel and stable
K+–Na+-PW17, which provides a clue to
further explore G4 functions in Na+-contained samples.