Vanessa Martínez-Francés

Molecular diversity is a key component of overall biodiversity, playing a vital role in evolution. It results from the adaptation of organisms to various habitats, which impacts their survival. The Amaryllidoideae subfamily is a significant group of monocotyledonous plants known for producing an exclusive and still-expanding group of molecules with diverse biological activities. Galanthamine (Gal), the most renowned metabolite from Amaryllidoideae subfamily, has been marketed for the palliative treatment of Alzheimer’s disease since 2001 due to its ability to inhibit the acetylcholinesterase enzyme. Due to the high cost and low yield of its synthesis, pharmaceutical companies extract this drug from Amaryllidoideae plants, such as Narcissus pseudonarcissus cv. Carlton in Europe and Lycoris radiata in China. The aim of this study was to describe the alkaloid profile of fifteen different species of Narcissus L. (commonly known as daffodils) collected in Spain using gas chromatography coupled with mass spectrometry. Fifty-one alkaloids were identified and quantified within these species through our private library of Amaryllidaceae alkaloids (AA) built over the last four decades, while thirty structures remained not identified in thirteen of these species. The highest concentration of these nitrogenate metabolites was quantified in N. confusus, 541 μg Gal·100 mg⁻¹ DW, which also exhibited a notably high concentration of Gal, 301 μg Gal·100 mg⁻¹ DW, which represents about 55% of the alkaloids identified in this species. The species N. bujei was also found to contain a significant quantity of this compound, amounting to 103.2 μg Gal·100 mg⁻¹ DW. The plant N. assoanus harbored a total of seven unidentified compounds, indicating that this species could be a potentially important source of novel alkaloids. In conclusion, this study facilitates a direct comparison of alkaloid profiles for fifteen Narcissus plant species. This serves as a valuable tool for identifying possible new sources of galanthamine, as well as other novel medicinal alkaloids. Finally, this work presents the first alkaloid profile of the species N. minor and N. nevadensis.

Homemade herbal preparations from the East of Spain are the witness of traditional medicine inherited from the ancient complex formulas of herbal teas and medicinal wines. In this study, we document the use of traditional alcoholic beverages, identify their ingredients, almost exclusively botanical, record the local medicinal uses of these mixtures, and discuss patterns of distribution of this knowledge in regions of eastern Spain, the Balearic Islands and Andorra. We determine marker species and relevant patterns of herbal formulas in the different regions of the territory. Homemade liquors and liqueurs are consumed for their digestive and tonic-restorative properties but they also play in some cases an important social role. The elderly remember other medicinal uses such as aperitif, emmenagogue, or antidiarrheal, for some of the most popular preparations. The herbal liqueur formulas include predominantly Lamiaceae, Asteraceae, Rosaceae, Rutaceae, and Apiaceae species. Herbs (58%), fruits (28%), and mixtures of both (12%) are ingredients of liquors and wines, being the aerial parts the most frequent in terms of species (30%) and records (49%).Dictamnus hispanicus, Santolina villosa, Salvia blancoanasubsp.mariolensis,Rosmarinus officinalis, Thymus vulgaris,andClinopodium serpyllifoliumsubsp.fruticosumare the species most frequently used. Others species used to a lesser extent asPolygonatum odoratum, Thymus moroderi,andSaxifraga longifoliaare restricted to locally homemade preparations because their collection and uses require special knowledge of the rare or endemic flora. Sustainability of these practices is strongly limited by the overall loss of local traditional knowledge and by the limited availability of most of the wild species; some of them are endangered or threatened mainly by the loss of their natural habitats. Cultivation and domestication are a promising alternative to collecting from wild populations. The cultivation ofThymus moroderiin the province of Alicante andPolygonatum odoratumin the province of Teruel are good examples. There is a notable decrease in the complexity of the formulas registered throughout the nearly 15 years of the study. This is interpreted as a consequence of a loss of knowledge, less accessibility to wild resources, and changes in traditions and preferences.

The aim of this work was to investigate the alkaloid patterns of Lapiedra martinezii and their relation to biogeography and phenology focused in a phylogenetic comparison. Plants from 14 populations of L. martinezii, covering almost its entire distribution area, were subjected to morphological, ecological, and phytochemical analysis. Experiments for different alkaloid‐type content are proposed as a new tool for analysis of plant distribution. Several plants were transplanted for weekly observation of their phenological changes, and alkaloids from different plant organs were extracted, listed, and compared. The alkaloid pattern of L. martinezii comprises 49 compounds of homolycorine, lycorine, tazettine, haemantamine, and narciclasine types. The populations located in the north and south margins of the distribution area displayed alkaloid patterns different from those of the central area. Changes in these patterns during their phenological cycle may be related to a better defence for plant reproduction. L. martinezii is an old relict plant, and it has maintained some of the more primitive morphological features and alkaloid profiles of the Mediterranean Amaryllidaceae. The variations in alkaloid content observed could be interpreted in a phylogenetic sense, and those found in their phenological changes, in an adaptive one.

Narcissus serotinus belongs to the Amaryllidaceae family, a group well known for an exclusive variety of alkaloids with interesting biological activities. This study was aimed at identifying the alkaloid constituents of N. serotinus collected in the Spanish region of Valencia, using a combination of chromatographic, spectroscopic, and spectrometric methods, including GC-MS and 2D NMR techniques. GC-MS analysis allowed for the direct identification of five known compounds. In addition, the isolation and structure elucidation of six new Amaryllidaceae alkaloids are described.