By Linda on Thursday, August 26, 2004 - 04:42 pm:

Hi, everybody,

Could somebody there explain if Ammonium Trifluoroacetate and Trifluoroacetic Acid have the same ion pairing and ion suppression impact on LC-MS analysis? Thanks a lot.

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By Uwe Neue on Thursday, August 26, 2004 - 09:23 pm:

The problem is supposed to be associated with the TFA. No TFA, no ion suppression from TFA. Maybe a MS expert can explain why TFA causes ion suppression, and formic acid or acetic acid don't...

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By Kevin on Friday, August 27, 2004 - 12:08 pm:

Ammonium trifluoroacetate and trifluoroacetic acid will both produce the trifluoroacetate ion in aqueous solutions. As noted, the trifluoroacetate ion is a strong ion pairing agent. This is advantageous for chromatographing positively charged species by reverse-phase LC, as the TFA anion creates a net zero charged species as the compound passes though the column.

While this is advantageous for RPLC, it is problematic for mass spectrometry. This is due to the fact that a mass spectrometer detects ions, and those ions must be unassociated from any counterions. A trifluoroacetate anion paired with a positively charged compound has a net zero charge and hence cannot be detected by mass spectrometry.

Formic acid and acetic acid are preferred acid modifiers for LC/MS because they are much weaker ion pairing agents than TFA, and readily dissociate from positively charged compounds in the ion source.

Kevin

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By Linda on Saturday, August 28, 2004 - 09:31 am:

Many thanks to Uwe and Kevin for your reply.

The lab I worked with before routinely usese ATFA in their LC-MS mobile phase for ESI+ mode and the response was much higher than using Formic acid/ammonium formate or acetic acid/ammonium acetate. I couldn't understand the phenomenon because I thought the TFA- ion in ATFA would suppress positive ions through ion pairing the same way as TFA, but I was told TFA and ATFA are working different way.