Effect of ion source polarity and dopants on the detection of auxin plant hormones by ion mobility-mass spectrometry

Ion mobility spectrometry (IMS) equipped with a corona discharge (CD) ion source was used for measurement of three auxin plant hormones including indole-3-acetic acid (IAA), indole-3-propionic acid (IPA), and indole-3-butyric acid (IBA). The measurements were performed in both positive and negative polarities of the CD ion source. Dopant gases NH3, CCl4, and CHBr3 were used to modify the ionization mechanism. A time-of-flight mass spectrometer (TOFMS) orthogonal to the IMS cell was used for identification of the product ions. Density functional theory was used to rationalize formation of the ions, theoretically. The mixtures of the auxins were analyzed by CD-IMS. The separation performance depended on the ion polarity and the dopants. In the positive polarity without dopants, auxins were ionized via protonation and three distinguished peaks were observed. Application of NH3 dopant resulted in two ionization channels, protonation, and NH4+ attachment leading to peak overlapping. In the negative polarity, two ionization reactions were operative, via deprotonation and O-2(-) attachment. The separation of the monomer peaks was not achieved while the peaks of anionic dimers [2 M-H](-) were separated well. The best LOD (4 ng) was obtained in negative polarity with CCl4 dopant. Methylation (esterification) of IAA improved LODs by about one order.