Charge inversion via concurrent cation and anion transfer: application to corticosteroids.
A novel charge inversion process that involves the removal of an excess cation from an analyte ion and the transfer of an anion to the neutral analyte in a single ion/ion encounter is described. Polyamidoamine (PAMAM) half-generation dendrimer anions that contain small anions, such as the chloride ion, were used as charge inversion reagents. Several competing processes can occur that include removal of the cation to neutralize the analyte, the removal of the excess cation and an additional proton to yield the deprotonated molecule, or removal of the excess cation and transfer of a small anion to the analyte. For the latter process to dominate, several requirements for both the reagent anion and the analyte cation must be met. The reagent anion must form multiply charged anions and must be able to incorporate one or more small anions for transfer. The analyte must have no strongly acidic sites as well as a relatively high affinity for small anion attachment. The PAMAM dendrimer anions must meet the conditions for the reagent anions and the cations of the corticosteroids meet the conditions for the analyte. The estrogenic steroid estrone, on the other hand, does not meet the requirements and, as a result, is largely neutralized when reacted with the reagent anions. This reaction, therefore, is highly selective and might serve as a useful reaction for the screening of appropriate analytes.
Department of Chemistry, Purdue University, West Lafayette, IN 47907-1393, USA.
Kerry M
KM
Hassell
Yves
Y
LeBlanc
Scott A
SA
McLuckey
D000838:Anions / Q000737:chemistry; D001507:Beclomethasone / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D050091:Dendrimers / Q000737:chemistry; D003907:Dexamethasone / Q000737:chemistry; D004970:Estrone / Q000737:chemistry*; D009566:Nitrates / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry / Q000379:methods*
D000838:Anions; D002412:Cations; D050091:Dendrimers; D009566:Nitrates; C104700:PAMAM Starburst; D004970:Estrone; D003300:Copper; D003907:Dexamethasone; C516433:copper(II) nitrate; D001507:Beclomethasone