TY - JOUR
T1 - Analysis of Mycosporine-Like Amino Acids in Selected Algae and Cyanobacteria by Hydrophilic Interaction Liquid Chromatography and a Novel MAA from the Red Alga Catenella repens
AU - Hartmann, Anja
AU - Karsten, Ulf
AU - Becker, Kathrin
AU - Remias, Daniel
AU - Ganzera, Markus
N1 - Publisher Copyright:
© 2015 by the authors; licensee MDPI, Basel, Switzerland.
PY - 2015/10/1
Y1 - 2015/10/1
N2 - Mycosporine-like amino acids (MAAs), a group of small secondary metabolites found in algae, cyanobacteria, lichens and fungi, have become ecologically and pharmacologically relevant because of their pronounced UV-absorbing and photo-protective potential. Their analytical characterization is generally achieved by reversed phase HPLC and the compounds are often quantified based on molar extinction coefficients. As an alternative approach, in our study a fully validated hydrophilic interaction liquid chromatography (HILIC) method is presented. It enables the precise quantification of several analytes with adequate retention times in a single run, and can be coupled directly to MS. Excellent linear correlation coefficients (R
2 > 0.9991) were obtained, with limit of detection (LOD) values ranging from 0.16 to 0.43 μg/mL. Furthermore, the assay was found to be accurate (recovery rates from 89.8% to 104.1%) and precise (intra-day precision: 5.6%, inter-day precision ≤6.6%). Several algae were assayed for their content of known MAAs like porphyra-334, shinorine, and palythine. Liquid chromatography-mass spectrometry (LC-MS) data indicated a novel compound in some of them, which could be isolated from the marine species Catenella repens and structurally elucidated by nuclear magnetic resonance spectroscopy (NMR) as (E)-3-hydroxy-2-((5-hydroxy-5-(hydroxymethyl)-2-methoxy-3-((2-sulfoethyl)amino)cyclohex-2-en-1-ylidene)amino) propanoic acid, a novel MAA called catenelline.
AB - Mycosporine-like amino acids (MAAs), a group of small secondary metabolites found in algae, cyanobacteria, lichens and fungi, have become ecologically and pharmacologically relevant because of their pronounced UV-absorbing and photo-protective potential. Their analytical characterization is generally achieved by reversed phase HPLC and the compounds are often quantified based on molar extinction coefficients. As an alternative approach, in our study a fully validated hydrophilic interaction liquid chromatography (HILIC) method is presented. It enables the precise quantification of several analytes with adequate retention times in a single run, and can be coupled directly to MS. Excellent linear correlation coefficients (R
2 > 0.9991) were obtained, with limit of detection (LOD) values ranging from 0.16 to 0.43 μg/mL. Furthermore, the assay was found to be accurate (recovery rates from 89.8% to 104.1%) and precise (intra-day precision: 5.6%, inter-day precision ≤6.6%). Several algae were assayed for their content of known MAAs like porphyra-334, shinorine, and palythine. Liquid chromatography-mass spectrometry (LC-MS) data indicated a novel compound in some of them, which could be isolated from the marine species Catenella repens and structurally elucidated by nuclear magnetic resonance spectroscopy (NMR) as (E)-3-hydroxy-2-((5-hydroxy-5-(hydroxymethyl)-2-methoxy-3-((2-sulfoethyl)amino)cyclohex-2-en-1-ylidene)amino) propanoic acid, a novel MAA called catenelline.
KW - HILIC
KW - Isolation
KW - LC-MS
KW - Mycosporine-like amino acids
KW - Quantification
KW - UV-sunscreen
KW - Validation
KW - Chromatography, Liquid/methods
KW - Limit of Detection
KW - Magnetic Resonance Spectroscopy
KW - Amino Acids/chemistry
KW - Cyclohexanols/chemistry
KW - Rhodophyta/metabolism
KW - Cyclohexylamines/chemistry
KW - Secondary Metabolism
KW - Cyanobacteria/metabolism
KW - Mass Spectrometry/methods
KW - Hydrophobic and Hydrophilic Interactions
KW - Glycine/analogs & derivatives
KW - Cyclohexanones/chemistry
UR - http://www.scopus.com/inward/record.url?scp=84946101412&partnerID=8YFLogxK
U2 - 10.3390/md13106291
DO - 10.3390/md13106291
M3 - Article
C2 - 26473886
VL - 13
SP - 6291
EP - 6305
JO - Marine Drugs
JF - Marine Drugs
IS - 10
ER -