Poly(ethylene oxide) helical conformation and alkali metal cation selectivity studied using electrospray ionization mass spectrometry

Rationale The poly(ethylene oxide) (PEO)–alkali metal cation interaction is widely used in many areas. The conformation of the PEO–alkali metal cation complex has been studied extensively, but the conformational mechanism is still unclear. Simulations have been used to explain the mechanism, but there is a lack of experimental data from long PEO chains to verify the simulation results. Methods The relative peak abundance of PEO (iso‐C 10 H 21 (OC 2 H 4 ) n OH ( n average = 7, where n denotes the number of ethylene oxide (EO) units) oligomers complexed to five alkali metal cations (Li + , Na + , K + , Rb + and Cs + ) was studied using positive electrospray ionization mass spectrometry (ESI‐MS). The ion selectivity of PEO oligomers to alkali metal cations corresponded to the peak abundance in competitive ESI‐MS. Results PEO formed its first helix when the number of EO units reached six and the helix played an important role in the ion selectivity of PEO. For larger PEO oligomers with a helix, the ion selectivity of PEO depended on the degree of host–guest matching of the cations and the helix. The highest selectivity of PEO to K + was due to K + providing the best shape matching with the helical cavity. For smaller PEO oligomers without a helix, the selectivity was mainly determined by the surface charge density of the cations. Conclusions The formational mechanism of the PEO–alkali metal cation complex was predicted. The results gave straightforward evidence to explain the conformational mechanism of the PEO–alkali metal cation complex and provided experimental data for further simulation studies.