Identification of novel nucleotides found in the red seaweed Porphyra umbilicalis

Abstract

Extracts of the red seaweed Porphyra umbilicalis are a valuable constituent of herbal medicines. The nucleotide complement of such an extract was purified and compounds identified by chromatographic behaviour, UV absorbance/pH profile, base-to-phosphate ratio, acid hydrolysis, and by fast-atom bombardment mass spectrometry with mass-analysed ion kinetic energy spectrum scanning. In addition to eighteen common nucleotides, and two cyclic nucleotides, fifteen novel nucleotides were identified, comprising eight deoxynucleotides and two cyclic deoxynucleotides, ten aminoacylnucleotides and two nucleoside trisphosphates together with 2'-phosphoadenosine-3',5'-cyclic pyrophosphate, 5'-phosphoadenosine-2',3'-cyclic monophosphate and N6,N6-dimethyladenosine-5'-monophosphate. The possible origin and potential actions of these novel compounds are discussed.

Simultaneous quantification of GMP, AMP, cyclic GMP and cyclic AMP by liquid chromatography coupled to tandem mass spectrometry

“…Ionization methods commonly used such as fast atom bombardment (FAB) [13,14] matrix-assisted laser desorption ionization (MALDI) [15] and electrospray ionization (ESI) [16]. In the field of nucleotide chemistry, static fast atom bombardment mass spectrometry (FAB-MS) was a monumental step forward, and its potency for the identification of cyclic nucleotides was demonstrated by Newton et al [13,17,18]. Witters et al [19] showed that cyclic nucleotides (among cAMP and cGMP), can be identified using specific collision-activated dissociation (CAD) fragments as diagnostic ions.…”

Kinetic analysis of cyclic CMP-specific and multifunctional phosphodiesterases by quantitative positive-ion fast-atom bombardment mass spectrometry

“…Consequently enzymes concerned with the metabolism and action of cyclic nucleotides are important pharmacological targets. Application of qualitative fastatom bombardment (FAB) mass spectrometry (MS) with mass-analysed ion kinetic energy (MIKE) spectrum scanning has proved invaluable in the identification of endogenous cyclic nucleotides 1-3 and of their analogues 4,5 and derivatives, 6-8 by virtue of the characteristic fragmentations 9,10 observed in the MIKE spectra obtained after collisionally-induced dissociation (CID) of the protonated molecule in the FAB mass spectrum. The advantage of softionization methods such as FAB is the production of cyclic nucleotide mass spectra without a requirement for derivatization and, combined with CID/MIKE analysis, this permits the differentiation of the 3',5'-cyclic nucleotides, 9,10 which are the biochemical second messengers, from the 2',3'-cyclic nucleotide isomers, which are merely intermediates of nucleic acid catabolism.…”

Polyphosphates and Pyrophosphates of Hexopyranoses as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Effect on Oxygen Release

“…[33d, 35,36] These characteristic features also apply for our derivatives, both protected phosphorylated (19,20,25,26) and sodium salts (31,32), as shown in Table 1.…”

“…[25] 3',5'-PP nucleotide derivatives phosphorylated at position 2' have been isolated from the red seaweed Porphyra umbilicalis, which is a constituent of herbal medicines. [26] Finally, several 3',5'-deoxyribose phosphate and PP nucleotides were proven to be human P2Y6 receptor ligands, P2Y1 receptor antagonists and partial agonists, and recombinant rat P2X receptor agonists and antagonists. [27,28] In the work presented herein, we targeted polyphosphates (with three or more phosphate groups) and seven-and/or eight-membered cyclic PPs of hexopyranoses, which are all novel compounds, except one.…”