Dereplication of Bromotyrosine-derived Metabolites by LC-PDA-MS and Analysis of the Chemical Profile of 14 Aplysina Sponge Specimens from the Brazilian Coastline

2010 ◽  
Vol 63 (6) ◽  
pp. 886 ◽  
Author(s):  
Michelli M. Silva ◽  
Juliana Bergamasco ◽  
Simone P. Lira ◽  
Norberto P. Lopes ◽  
Eduardo Hajdu ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Electrospray Ionization ◽  
Electrospray Ionization Mass Spectrometry ◽  
Marine Sponges ◽  
Mass Spectrometry Analysis ◽  
Ionization Mass ◽  
Chemical Profile ◽  
Spectrometry Analysis ◽  
Ion Clusters ◽  
Single Compound

In order to investigate the chemical profile of 14 specimens of Aplysina spp. marine sponges, we have developed a method based on LC-PDA-MS for the detection of bromotyrosine-derived metabolites. The method enabled the dereplication of three distinct chemotypes of bromotyrosine-derived compounds based on UV absorptions, which were further refined by electrospray ionization-mass spectrometry analysis of the brominated quasi-molecular ion clusters. This procedure led to either a single compound assignment, or a maximum of two possible isobaric compounds. The dereplication study indicated that the chemical profile of the 14 specimens of Aplysina spp. analyzed presented practically the same dibromotyrosine-derived compounds. The results obtained suggested a possible biogenetic pathway for the formation of dibromotyrosine-derived compounds of wide occurrence in Verongida sponges.

scholarly journals A Non-Covalent Dimer Formation of Quaternary Ammonium Cation with Unusual Charge Neutralization in Electrospray-Ionization Mass Spectrometry

Molecules ◽  
2021 ◽  
Vol 26 (19) ◽  
pp. 5868
Author(s):  
Paulina Grocholska ◽  
Marta Kowalska ◽  
Robert Wieczorek ◽  
Remigiusz Bąchor
Keyword(s):  
Mass Spectrometry ◽  
Electrospray Ionization ◽  
Electrospray Ionization Mass Spectrometry ◽  
Quaternary Ammonium ◽  
Mass Spectrometry Analysis ◽  
Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Charge Neutralization ◽  
Spectrometry Analysis ◽  
Covalent Dimer

Specific and nonspecific non-covalent molecular association of biomolecules is characteristic for electrospray-ionization mass spectrometry analysis of biomolecules. Understanding the interaction between two associated molecules is of significance not only from the biological point of view but also gas phase analysis by mass spectrometry. Here we reported a formation of non-covalent dimer of quaternary ammonium denatonium cation with +1 charge detected in the positive ion mode electrospray ionization mass spectrometry analysis of denatonium benzoate. Hydrogen deuterium exchange of amide and carbon-bonded hydrogens revealed that charge neutralization of one denatonium cation is the consequence of amide hydrogen dissociation. DFT (Density Functional Theory) calculations proved high thermodynamic stable of formed dimer stabilized by the short and strong N..H-N hydrogen bond. The signal intensity of the peak characterizing non-covalent dimer is low intensity and does not depend on the sample concentration. Additionally, dimer observation was found to be instrument-dependent. The current investigation is the first experimental and theoretical study on the quaternary ammonium ions dimer. Thus the present study has great significance for understanding the structures of the biomolecules as well as materials.

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