For starters, I have no idea if you can use either solvent in RP-HPLC. My guess is probably "it depends". More info on either solvent...
Google tells me NMP is N-Methylpyrrolidone, and DMA is Dimethylacetamide.
NMP "is the lactam of 4-methylaminobutyric acid and a very weak base. NMP is a chemically stable and powerful polar solvent. These characteristics are highly useful in a variety of chemical reactions where an inert medium is of concern. Despite the stability of NMP, it can also play an active role in certain reactions: hydrolysis, oxidation, condensation, conversion with chlorinating agents, polymerization and o-alkylation, and related reactions."
http://www2.basf.us/diols/bcdiolsnmp.html
DMA is "used as a solvent for polyacrylonitrile, vinyl resins, cellulose derivatives, styrenes and linear polyesters. Also used as a catalyst and solvent in elimination, halogenation, cyclization, alkylation, interesterification, and phthaloylation reactions."
http://www2.dupont.com/Products/en_RU/D ... de_en.html
I assume more info from moonchips may be necessary (for the smart guys on the forum):
Column type? Perhaps manufacturer, packing material, length, I.D., etc?
Other mobile phase constituents?
pH?
Temperature?
Detector?
Analyte type/names?
I found one aplication note for a "N-Methylpyrrolidone (NMP) + 0.1M LiBr mobile phase" in the analysis of 'Poly (Vinylidene Fluoride)' on 'Jordi DVB GBR Mixed Bed Linear' column, 500 x 10mm ID
http://www.gentechscientific.com/an59.htm
I found an abstract more a method using DMA as a constituent of a mobile phase on a C8 column "for the sample preparation and handling for the determination of amino acids, monoamines and metabolites from microdissected brain regions of the rat".
http://www.medscape.com/medline/abstract/9698226
Mostly, though, it seems these solvents are used in SEC/GPC.