Can Nonpolar Polyisobutylenes be Measured by Electrospray Ionization Mass Spectrometry? Anion-Attachment Proved to be an Appropriate Method.

Polyisobutylenes (PIBs) with different end-groups including chlorine, exo-olefin, hydroxyl, and methyl prepared from aliphatic and aromatic initiators were studied by electrospray ionization mass spectrometry (ESI-MS). Independently of the end-groups, presence or absence of aromatic initiator moiety, these PIB derivatives were capable of forming adduct ions with NO3 (-) and Cl(-) ions, thus allowing the direct characterization of these compounds in the negative ion mode of ESI-MS. To obtain [PIB + NO3](-) and [PIB + Cl](-) adduct ions with appreciable intensities, addition of polar solvents such as acetone, 2-propanol, or ethanol to the dichloromethane solution of PIBs was necessary. Furthermore, increasing both the polarity (by increasing the acetone content) and the ion-source temperature give rise to enhanced intensities for both [PIB + NO3](-) and [PIB + Cl](-) ions. Energy-dependent collision induced dissociation studies (CID) revealed that increasing the collision voltages resulted in the shift of the apparent molecular masses to higher ones. CID studies also showed that dissociation of the [PIB + Cl](-) ions requires higher collision energy than that of [PIB + NO3](-). In addition, Density Functional Theory calculations were performed to gain insights into the nature of the interactions between the highly non-polar PIB chains and anions NO3 (-) and Cl(-) as well as to determine the zero-point corrected electronic energies for the formation of [PIB + NO3](-) and [PIB + Cl](-) adduct ions.