Caracterización in situ de poblaciones de Aloysia gratissima var. gratissima recolectadas del noreste de la provincia de San Luis, Argentina / In situ characterization of populations of Aloysia gratissima var. gratissima collected from the northeast of the province of San Luis, Argentina

Abstract: The aerial part of Aloysia gratissima (Gil lies & Hook. ex Hook.) Tronc., "Usillo", is used as aromatic and medicinal. It is a shrub of up to 3 meters, distributed in North America, from the south of the USA to the north of Mexico, and in South America up to the 37th parallel. As in other native sp ecies, the demand is covered by harvesting in wild populations, which brings about the deterioration of the resource and lack of homogeneity of the harvested product. The variability was characterized in nine populations of A. gratissima var. gratissima fr om the northeast of San Luis, Argentina, based on morphological and phytochemical characters. It was found that the species in the region presents considerable heterogeneity. Diversity was detected in the chemical characteristics of the essential oils anal yzed and the prevalence of mono and sesquiterpenes was related to the olfactory identities identified. The main components were the sesquiterpene spatulenol and the monoterpene 1,8 cineole

Resumen: La parte aérea de Aloysia gratissima (Gillies & Hook. ex Hook.) Tronc., "usillo", es utilizada como aromática y medicinal. Es un arbusto de hasta 3 metros, distribuido en Norteamerica, desde e l sur de EEUU hasta el norte de México, y en Sudamerica hasta el paralelo 37°. Al igual que en otras especies nativas, la demanda es cubierta por recolección en poblaciones silvestres, lo cual trae aparejado el deterioro del recurso y falta de homogeneidad del producto cosechado. Se caracterizó la variabilidad en nueve poblaciones de A. gratissima var. gratissima del noreste de San Luis, Argentina, en base a caracteres morfológicos y fitoquímicos. Se encontró que la especie en la región presenta una conside rable heterogeneidad. Se detectó diversidad en las características químicas de los aceites esenciales analizados y se relacionó la prevalencia de mono y sesquiterpenos con las identidades olfativas identificadas. Los componentes mayoritarios fueron el sesq uiterpeno espatulenol y el monoterpeno 1,8 cineol.

Dynamics of Polyphenol Biosynthesis by Calli Cultures, Suspension Cultures and Wild Specimens of the Medicinal Plant Ligaria cuneifolia (Ruiz & Pav.) Tiegh. (Loranthaceae). Analysis of Their Biological Activity.

Ligaria cuneifolia (R. et P.) Tiegh. (Loranthaceae) is a South American hemiparasitic species with antioxidant, antitumoral, antimicrobial, and antilipidemic activities attributed to its polyphenolic content. We studied the polyphenolic pattern of L. cuneifolia during different phenological stages: flowering, fruiting, and post-fruiting. The highest total phenolic content was found in stems at post-fruiting (214 ± 12.1 mg gallic acid eq·g-1 DW) and fruiting (209 ± 13.7 mg gallic acid eq·g-1 DW), followed by post-fruiting leaves (207 ± 17.5 mg gallic acid eq·g-1 DW). Flavonoids accumulated at higher levels in leaves and hydroxycinnamic acids in leaves at flowering and post-fruiting. The polyphenolic pattern was similar between organs from wild plants and in vitro cultures, although at a significantly lower level in the latter ones. The performance of calli growing under a 16 h photoperiod in a modified White medium with 1-naphthalene acetic acid (2.50 µM) and Kinetin (9.20 µM) was better than in the dark. When calli grew in media only with auxins (IAA, NAA, and 2,4-D, all at 2.50 µM concentration), its growth and polyphenolic content improved. Cell suspensions with 2.50 µM NAA and 9.20 µM KIN grew slowly and produced very small amounts of polyphenols. As for the antioxidant activity, it was detected in all samples (approximately 1000 µmol trolox eq·g-1 DW) except fruits, where a lower value was found (328 µmol trolox eq·g-1 DW). In vitro cultures have the lowest antioxidant activity when compared to methanolic extracts from organs of wild specimens. Finally, antimutagenic or mutagenic activity in wild plants and in vitro culture extracts was not detected by the Ames test.

Oregano Essential Oil Interactions with Photogenerated Singlet Molecular Oxygen.

Essential oils are a mixture of volatile compounds, products of the secondary metabolism of plants. Once extracted, they can be deteriorated losing their organoleptic and therapeutic properties due to various environmental factors, being light exposure in aerobic conditions the main cause. In this work, the oregano essential oil extraction and characterization from Origanum vulgare plants grown in the experimental field of the FTU-UNSL and its photodegradation in MeOH:H2 O 60:40 v/v solvent were studied. Characterization by EIMS and NIST Mass Spectrometry indicates the main compounds of oregano essential oil, quantified in the extracted oil by GC-MS, are carvacrol (7.14%) and thymol (47.37%). Degradation of essential oil and its two major components can be caused by reactive oxygen species photogenerated from endogenous sensitizers as riboflavin. Our results suggest degradation occurs involving singlet molecular oxygen. Interaction of carvacrol and thymol with singlet oxygen is mainly a physical process, while essential oil has an important reactive component, which indicates there might be other constituents which could contribute to reactive photoprotection. The effect of simultaneous presence of oregano essential oil and tryptophan amino acid-used as a photooxidizable model under riboflavin-photosensitizing conditions-was studied in order to evaluate the possible photoprotection exerted by the essential oil.

A kinetic study of the photodynamic effect on tryptophan methyl ester and tryptophan octyl ester in DOPC vesicles.

The photodynamic effect on tryptophan methyl ester (trpME) and tryptophan octyl ester (trpOE), using the O(2)((1)Delta(g))-photosensitizers Rose Bengal (RB) and Perinaphthenone (PN) has been studied in large unilamellar vesicles (LUVs) of the phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) by stationary photolysis and time-resolved methods. This work reports on the influence of both the site (O(2)((1)Delta(g))) generation and the location of the tryptophan derivatives (trpD), on the photo-oxidation process in a compartmentalized system. The apparent rate constant values for chemical quenching of O(2)((1)Delta(g)) by trpOE (k(r,app)), was higher in vesicles than in water. Also, the ratio between apparent reactive and overall rate constant values for the deactivation of O(2)((1)Delta(g)) (k(r,app)/k(t,app)), increases in vesicles as compared with water, when the oxidative species is generated in the lipidic region or at the interface. Nevertheless, this quotient is lower than the corresponding value in water when O(2)((1)Delta(g)) is generated in the aqueous pseudophase. For trpME, the k(r,app)/k(t,app)values in vesicles and in water are quite similar, confirming the fact that trpME is located in the water pseudophase. Results are discussed in terms of relative protection against O(2)((1)Delta(g)) attack in a microheterogeneous medium as compared with water.

Rose Bengal-sensitized photooxidation of the dipeptides L-tryptophyl-L-phenylalanine, L-tryptophyl-L-tyrosine and L-tryptophyl-L-tryptophan: kinetics, mechanism and photoproducts.

The Rose Bengal-sensitized photooxidations of the dipeptides l-tryptophyl-l-phenylalanine (Trp-Phe), l-tryptophyl-l-tyrosine (Trp-Tyr) and l-tryptophyl-l-tryptophan (Trp-Trp) have been studied in pH 7 water solution using static photolysis and time-resolved methods. Kinetic results indicate that the tryptophan (Trp) moiety interacts with singlet molecular oxygen (O(2)((1)Delta(g))) both through chemical reaction and through physical quenching, and that the photooxidations can be compared with those of equimolecular mixtures of the corresponding free amino acids, with minimum, if any, influence of the peptide bond on the chemical reaction. This is not a common behavior in other di- and polypeptides of photooxidizable amino acids. The ratio between chemical (k(r)) and overall (k(t)) rate constants for the interaction O(2)((1)Delta(g))-dipeptide indicates that Trp-Phe and Trp-Trp are good candidates to suffer photodynamic action, with k(r)/k(t) values of 0.72 and 0.60, respectively (0.65 for free Trp). In the case of Trp-Tyr, a lower k(r)/k(t) value (0.18) has been found, likely as a result of the high component of physical deactivation of O(2)((1)Delta(g)) by the tyrosine moiety. The analysis of the photooxidation products shows that the main target for O(2)((1)Delta(g)) attack is the Trp group and suggests a much lower accumulation of kynurenine-type products, as compared with free Trp. This is possibly because of the occurrence of another accepted alternative pathway of oxidation that gives rise to 3a-oxidized hydrogenated pyrrolo[2,3-b]indoles.