Phenolic chemistry of the seagrass Zostera marina Linnaeus: First assessment of geographic variability among populations on a broad spatial scale.

The variability of the phenolic content of thirteen populations of Zostera marina L. (six narrow-leaved and seven wide-leaved ecotypes) from different geographical zones, i.e., Baltic Sea, Mediterranean, East and West Atlantic, and East Pacific coasts was evaluated. Depending on the location, three to five phenolic acids and nine to fourteen flavonoids were identified of which an undescribed flavonoid sulfate. The phenolic concentrations of the thirteen populations differ among countries and among sites within countries. However, the same individuals were found almost everywhere. Substantial phenolic concentrations were found at all study sites with the exception of Puck Bay (Baltic Sea). Some geographical differences in the flavonoid content were observed. The highest phenolic diversity was found with specimens from the French Atlantic coast and the lowest with the Northeastern American sample (Cape Cod, MA). Regardless of their leaf width, the content of phenolic compounds was found to be similar and mainly characterized by rosmarinic acid and luteolin 7,3'-disulfate. The results demonstrate that geographic origin influences the phenolic composition of Z. marina primarily in terms of concentration, but not in terms of individual compound identity, despite the large geographic scale and the contrasting climatic and environmental conditions associated with it. This work is the first study to consider the spatial variability of phenolic compounds for a seagrass species on a spatial scale covering four bioregions. This is also the first to compare the phenolic chemistry of the two ecotypes of Z. marina.

Phenolic fingerprints of the Pacific seagrass Phyllospadixtorreyi - Structural characterization and quantification of undescribed flavonoid sulfates.

Four undescribed flavonoid sulfates were isolated from Phyllospadix torreyi S. Watson foliar tissue. In addition, nine known flavonoid sulfates and three phenolic acids were isolated from the same extract, of which seven had never been reported for the genus Phyllospadix. Structural elucidation of individual phenolics was assigned using complementary informations from their spectral evidence (HPLC-DAD, LC-MS, NMR, and UV) and chemical behavior. The inter-annual variation in phenolic concentrations was determined by quantitative HPLC-DAD over a three-year period. The results showed a relative constancy of phenolic content over time and the high prevalence of flavonoid disulfates (70-90% of the total flavonoids detected). All samples were found dominated by the unreported nepetin 7, 3'-disulfate and 5-methoxyluteolin 7, 3'-disulfate, followed by luteolin 7, 3'-disulfate. Considering the economic potential of flavonoid sulfates in the pharmaceutical and nutraceutical segments, a sample of detrital leaves was also analyzed. The same phenolic pattern was found and the concentration of the individuals, although lower than in fresh material, makes this abundant biomass of interest for dietary and pharmaceutical applications.

Flavonoid pattern inheritance in the allopolyploid Spartina anglica - Comparison with the parental species S. maritima and S. alterniflora.

The invasive species Spartina anglica arose in Europe by a cross between the Afro-European species S. maritima (native, paternal ancestor) and the introduced North American S. alterniflora (invasive, maternal ancestor). Aqueous methanolic extracts were prepared from plant tissue for chemotaxonomical comparison between the three species and determination of the phenolic pattern inheritance in S. anglica. A total of 20 phenolic compounds were detected in the aerial tissues of S. anglica and S. alterniflora, but only seven in S. maritima. They were isolated from their respective crude extracts, and their structures were determined according to spectroscopic data analysis and chemical evidence. They all belong to the flavonoid class, with 13 of them identified as C-glycoflavonoid and seven as O-glycoflavonoid. All these products were detected for the first time from S. anglica, fourteen of them for the first time from S. alterniflora, and three of them for the first time from S. maritima. The individual concentrations in the three species were determined by quantitative HPLC. The two parental species were found to differ markedly in their foliar phenolic fingerprint, whereas that of S. anglica showed a clear maternal dominance. Eight of the fourteen major compounds identified were of maternal origin among which, six were over-expressed, only three were from paternal origin but under-regulated, while two originated from the two parents. As far as we know, this work represents the first exhaustive report of the phenolic fingerprints of S. alterniflora and S. anglica and of the phenolic pattern inheritance in S. anglica. The similarity in the phenolic chemistry of the introduced and invasive S. alterniflora to its progeny could play a role in the physiological vigour and invasion success of S. anglica. This work provide a foundation for further studies, considering the reported biological activities of C-glycosidic flavonoids and tricin derivatives, and the lack of knowledge of the ecological chemistry of the genus Spartina.

Phenolic chemistry of the seagrass Zostera noltei Hornem. Part 1: First evidence of three infraspecific flavonoid chemotypes in three distinctive geographical regions.

The flavonoid content of Zostera noltei leaves was investigated over a broad spatial scale using chromatographic and spectroscopic techniques (HPLC-DAD, LC/MS and NMR). Samples were collected at fifteen localities covering Mediterranean Sea and NE Atlantic coast, and representative of three types of coastal ecosystems: mesotidal bays, coastal lagoons, and open-sea. Three geographically distinct flavonoid chemotypes were identified on the basis of their respective major compound. One is characterized by apigenin 7-sulfate (Eastern part of Gulf of Cadiz), one by diosmetin 7-sulfate (French Atlantic coast and Mediterranean Sea), and the third contained similar quantities of the above two compounds (Mauritania and South Portugal). Our results show that metabolomic profiling using a combination of analytical techniques is a tool of choice to characterize chemical phenotype accurately. This work emphasizes for the first time the spatial variability in the flavonoid chemistry of Z. noltei throughout Atlantic and Mediterranean range, and constitutes the first report of chemical races in the Zosteraceae family. This infraspecific chemical differentiation should be considered when dealing with the role of Z. noltei in coastal ecosystems or in the selection of the best population donor for Z. noltei beds restoration. Combined with molecular identification, phenolic fingerprinting might be helpful to elucidate the evolutionary history of Z. noltei.

First Phytochemical Evidence of Chemotypes for the Seagrass Zostera noltii.

The variability of the flavonoid content of two populations of Z. noltii from different geographical zones, i.e., the Bay of Arcachon and the Bay of Cadiz, was evaluated. Samples were collected in spring and autumn at the two sites, and extracts were prepared by maceration in water. The phenolic content was fully characterized using Nuclear Magnetic Resonance (NMR), UV and Liquid Chromatography-Mass Spectrometry (LC-MS), and the concentration of the individual phenolic was determined by quantitative High-Performance Liquid Chromatography with Diode-Array Detection (HPLC-DAD). The two populations show a strong geographical differentiation in their flavonoid content. The samples from Cadiz were dominated by apigenin 7-sulfate, which represents 71% (autumn collection) and 83% (spring collection) of the total flavonoids, whereas the samples from Arcachon were characterized by diosmetin 7-sulfate (85 and 93% of the total flavonoids). Structural elucidation of the individual phenolics was assigned using the complementary information from their spectral evidence. In addition, the results were confirmed by acid hydrolysis of the flavonoid sulfates, and comparison to synthetic standards obtained by sulfation of apigenin, diosmetin and luteolin. The results represent the first experimental evidence of the existence of chemotypes within the species Z. noltii.

Composition of sugarcane waxes in rum factory wastes.

Wastes produced during fermentation and distillation of crude sugarcane juice in rum factories were evaluated as a new source of waxes. The chemical composition of the crude wax extracted from adsorbat of the wastes on fuller's earth was studied by GC-mass spectrometry. Series of linear alkanes (C19-C33), and wax esters constitute the main components. In addition, phytosterols, triterpene methyl ethers, ethyl and methyl esters of fatty acids, and free fatty acids were found as minor components. Acid (predominance of C16 and C18) and alcohol portions (C26-C32) of the wax esters were analysed after saponification.

One-pot synthesis of pentacyclic diamines from quinolines by a new Zn/AcOH-promoted cascade reaction.

A simple and efficient method for the one-pot synthesis of pentacyclic diamines from quinolines is described. It involves a new Zn/AcOH-promoted cascade reaction, in which two C[bond]C bonds and four to five stereogenic centers are established under mild conditions. The regiochemistry of the dimerization and cyclization step is governed by substituent effects, allowing access to a head-to-head (2, 3) or head-to-tail skeleton (4, 5).