Fragmentation of diketopiperazines from Aspergillus fumigatus by electrospray ionization tandem mass spectrometry (ESI-MS/MS).
Diketopiperazines (DKPs) corresponding to cyclic dipeptides have been reported to exhibit antimicrobial, antitumor, antimutagenic and antiviral properties. These compounds are commonly isolated from microorganisms and sponges and from a variety of tissues and body fluids. In this work, we used electrospray ionization tandem mass spectrometry (ESI-MS/MS) to investigate the fragmentation of a series of DKPs previously isolated from Aspergillus fumigatus, which exhibit the same structural core. Loss of CO directly from the protonated molecule was found to be a fragmentation process common to all the compounds analyzed. However, our results revealed a series of ions that are diagnostic for the substituents at C(4) and C(9). In order to rationalize the differences in the fragmentation pathways of substituted and nonsubstituted DKPs, the relative Gibbs energies (DeltaG) of the product ions and intermediate ions were estimated using the B3LYP/6-31 + + G(d,p) model. The data reported here can be used for the structural elucidation of DKPs from low sample amounts, as an alternative to NMR.
Furtado
Niege A J C
NA
Núcleo de Pesquisas em Ciências Exatas e Tecnológicas, Universidade de Franca, Franca, SP, Brazil.
Vessecchi
Ricardo
R
Tomaz
José Carlos
JC
Galembeck
Sérgio E
SE
Bastos
Jairo K
JK
Lopes
Norberto P
NP
Crotti
Antonio E M
AE
D001232:Aspergillus fumigatus / Q000737:chemistry*; D054659:Diketopiperazines / Q000737:chemistry*; D015394:Molecular Structure; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*
D054659:Diketopiperazines