Functionalization of High‐Density Polyethylene Capillaries for Open Tubular Ion Chromatography

Ion chromatography is the anion analysis benchmark. A miniature form, Open Tubular Ion Chromatography (OTIC), has attractive attributes for efficient ion separations. Here, we fabricate and characterize high-density polyethylene (HDPE) open tubular anion exchange columns (OTCs). We attach positively charged latex particles onto negatively charged capillary surfaces. For efficient OTIC, column diameters need to be < ∼20 µm; functionalizing the bore is challenging. Methods to introduce acid groups to an HDPE capillary bore, e.g., sulfonation using chlorosulfonic or sulfuric acid solutions, with or without grafting of an aromatic ring through photo- or chemical grafting first, are explored. Following quaternary ammonium latex attachment, the ion exchange capacity and separating abilities of each OTC were measured as an index of OTC performance. Gradual loss of capacity was observed for many of these; high-resolution mass spectrometry confirmed the leaching of detached oxidized/sulfonated oligomeric fragments and consequent poisoning of the latex sites. Ways to ameliorate this and/or to rejuvenate the columns are also described.