Chemical characterization, antioxidant activity, -amylase and acetylcholinesterase inhibitory potential of Angelica pancicii Vandas ex Velen / Caracterización química, actividad antioxidante, potencial inhibidor de -amilasa y acetilcolinesterasa de Angelica pancicii Vandas ex Velen

Abstract: Comparative study GC - FID /M S of essential oils of fruits, leaves and roots of the endemic plant Angelica pancicii Vandas ex Velen. revealed a significant difference in their chemical composition. The enantiomeric purity of the main component in the fruit oil (+) - ß - phellandrene was a lso confirmed. In addition, imperatorin, isoimperatorin, oxypeucedanin, oxypeucedanin hydrate, angeloylpangelin and umbelliprenin were isolated from the fruit hexane extract. The content of these coumarins in the hexane extracts from different plant parts was further determined by HPLC. The essential oils and hexane extracts were assessed for their antioxidant potential and inhibitory effect towards  - amylase and acetylcholinesterase enzymes. The fruit and leaf essential oils (> 80%) as well as the fruit he xane extract (> 62%) significantly inhibited acetylcholinesterase enzyme. Distinguish free radical scavenging properties were detected for the leaf (Inh. 95.0 ± 2.2 %) and the root (Inh. 66.0 ± 2.4 %) extracts.

Resumen: Estudio comparativo GC - FID / MS de aceites esenciales de frutas, hojas y raíces de la planta endémica Angelica pancicii Vandas ex Velen revelaron una dife rencia significativa en su composición química. También se confirmó la pureza enantiomérica del componente principal del aceite de fruta (+) - ß - felandreno. Además, se aislaron imperatorina, isoimperatorina, oxipeucedanina, hidrato de oxipeucedanina, angeloi lpangelina y umbeliprenina del extracto de hexano del fruto. El contenido de estas cumarinas en los extractos de hexano de diferentes partes de la planta se determinó adicionalmente mediante HPLC. Los aceites esenciales y extractos de hexano se evaluaron p or su potencial antioxidante efecto inhibidor de las enzimas -  - amilasa y acetilcolinesterasa. Los aceites esenciales de frutas y hojas (> 80%), así como el extracto de hexano de frutas (> 62%) inhibieron significativamente la enzima acetilcolinesterasa. Se detectaron propiedades de captación de radicales libres diferenciadas para los extractos de hoja (Inh. 95,0 ± 2,2%) y de raíz (Inh. 66,0 ± 2,4%).

Essential Oil Composition of Five Thymus Species from Bulgaria.

In this study, the essential oil composition of five Thymus species, belonging to Sect. Hyphodromi (A. Kerner) Halácsy - Thymus atticus Celak., T. leucotrichus Halácsy, T. striatus Vahl, T. zygioides Griseb. and T. perinicus (Velen.) Jalas. was studied by GC/MS/FID. T. atticus, T. leucotrichus, and T. striatus were characterized by high amounts of sesquiterpenoids (57.7, 78.9 and 79.7 %, respectively) with ß-caryophyllene and caryophyllene oxide as the main constituents. Aromatic compounds (61.2 %) were the most abundant group in T. zygioides essential oil, with thymol (51.2 %) as the principal component. The essential oil from the endemic species T. perinicus contained almost equal amounts of monoterpenoids (37.8 %) and aromatic compounds (36.0 %) with borneol (17.9 %) and thymol (20.9 %) as the major components. The obtained results revealed the existence of new chemotypes of T. atticus (caryophyllene oxide/ß-caryophyllene), T. leucotrichus (ß-caryophyllene/elemol/germacrene D) and T. striatus (ß-caryophyllene/germacrene D/caryophyllene oxide). The essential oil content of endemic T. perinicus is reported for the first time. Principal component analysis (PCA) and cluster analysis (CA) were used to investigate the variations in the essential oils of different Thymus species from Sect. Hyphodromi (A. Kerner) Halácsy.

Caffeoylquinic Acids, Cytotoxic, Antioxidant, Acetylcholinesterase and Tyrosinase Enzyme Inhibitory Activities of Six Inula Species from Bulgaria.

Chlorogenic (5-CQA), 1,5-, 3,5-, 4,5- and 3,4-dicaffeoylquinic (DCQA) acids were identified and quantified in the methanol extracts of Inula oculus-christi L., I. bifrons L., I. aschersoniana Janka var. aschersoniana, I. ensifolia L., I. conyza (Griess.) DC. and I. germanica L. by HPLC analysis. The amount of 5-CQA varied from 5.48 to 28.44 mg/g DE and the highest content was detected in I. ensifolia. 1,5-DCQA (4.05-55.25 mg/g DE) was the most abundant dicaffeoyl ester of quinic acid followed by 3,5-DCQA, 4,5-DCQA and 3,4-DCQA. The extract of I. ensifolia showed the highest total phenolic content (119.92±0.95 mg GAE/g DE) and exhibited the strongest DPPH radical scavenging activity (69.41±0.55 %). I. bifrons extract was found to be the most active sample against ABTS.+ (TEAC 0.257±0.012 mg/mL) and the best tyrosinase inhibitor. The studied extracts demonstrated a low inhibitory effect towards acetylcholinesterase and possessed low cytotoxicity in concentration range from 10 to 300 µg/mL toward non-cancer (MDCK II) and cancer (A 549) cells.

Phenolic profile and antioxidant, acetylcholinesterase, and tyrosinase inhibitor activities of Jurinea tzar-ferdinandii Davidov, an endemic plant of the Balkans / Perfil fenólico y actividad antioxidante, acetilcolinesterasa e inhibidora de tirosinasa de Jurinea tzar-ferdinandii Davidov, planta endémica de los Balcanes

The methanol extract of the Balkan endemic species Jurinea tzar-ferdinandii Davidov demonstrated weak antioxidant activity against DPPH• and ABTS+• and low inhibitory potential against acetylcholinesterase (8.3% Inh.) and tyrosinase (IC50 = 208 ± 8 µg/mL) enzymes. Phytochemical investigation of the extract led to isolation and identification of apigenin, luteolin, apigenin-7-O-glucoside, apigenin-4'-O-glucoside, apigenin-7-O-gentiobioside, luteolin-4'-O-glucoside, rutin, narcissin, chlorogenic and 1,5-dicaffeoylquinic acid. With exception of apigenin and rutin, all isolated compounds are reported for the first time in the representatives of genus Jurinea. The distribution of flavonoids was discussed from chemotaxonomic point of view.

El extracto de metanol de la especie endémica de los Balcanes Jurinea tzar-ferdinandii Davidov demostró una actividad antioxidante débil contra DPPH• y ABTS+• y un bajo potencial inhibidor contra las enzimas acetilcolinesterasa (8.3% Inh.) tirosinasa (IC50 = 208 ± 8 µg/mL). La investigación fitoquímica del extracto condujo al aislamiento e identificación de apigenina, luteolina, apigenina-7-Oglucósido, apigenina-4'-O-glucósido, apigenina-7-O-gentiobiósido, luteolina-4'-O-glucósido, rutina, narcissin, clorogénico y ácido 1,5- dicafeoilquinico. Con excepción de la apigenina y la rutina, todos los compuestos aislados se informan por primera vez en el género Jurinea. La distribución de flavonoides se discute desde el punto de vista quimiotaxonómico.

Essential oil composition of the Balkan endemic Thymus longedentatus (Degen & Urum. ) Ronniger / Composición del aceite esencial de Thymus longedentatus (Degen & Urum. ) Ronniger endemic de los Balcanes

The chemical composition of essential oil obtained from the aerial parts of the Balkan endemic species Thymus longedentatus was studied by GC-MS. Twenty eight compounds, consisting 98.2% of the total components were detected in amounts exceeding 0.1%. The oil was characterized by relatively high concencentration of oxygentated monoterpenes (78.7%), among which citral isomers neral (27.5%) and geranial (30.3%) were the principal ones. In addition, 1,8-cineole (7.8%), trans-ß-ocimene (7.5%), and ß-myrcene (3.7%) were detected in significant ammounts. Germacrene D (4.4%) was found to be the main sesquiterpene in the essential oil.

Se estudió mediante GC-MS la composición química del aceite esencial obtenido de las partes aéreas de Thymus longedentatus, especie endémica de los Balcanes. Se detectaron veintiocho compuestos, que representaban un 98,2% del total de compuestos y que se encontraban en cantidades superiores al 0,1%. El aceite se caracterizó por una concentración relativamente alta de monoterpenos oxigenados (78.7%), entre los cuales los isómeros de citral, neral (27.5%) y geranial (30.3%) eran los principales. Además, se detectó 1,8-cineol (7,8%), trans-ß-ocimeno (7,5%) y ß-mirceno (3,7%) en cantidades significativas. Se encontró que Germacreno D (4.4%) es el principal sesquiterpeno en el aceite esencial.

Furanocoumarin Content, Antioxidant Activity, and Inhibitory Potential of Heracleum verticillatum, Heracleum sibiricum, Heracleum angustisectum, and Heracleum ternatum Extracts against Enzymes Involved in Alzheimer's Disease and Type II Diabetes.

Hexane extracts of Heracleum verticillatum, H. sibiricum, H. angustisectum, and H. ternatum were studied for their furanocoumarin content antioxidant potential and acetylcholinesterase and α-amylase inhibitory activities. Quantification of the furanocoumarins was performed by 1 H-NMR. Pimpinellin was found to be the main component in the roots of all studied species. Bergapten and imperatorin were the major compounds in the fruits of H. sibiricum and H. verticillatum, respectively, while byakangelicol dominated in H. angustisectum and H. ternatum fruits. The leaf and fruit extracts of H. angustisectum demonstrated the highest DPPH radical scavenging activity and TEAC (IC50 0.58 mg/mL and 1.83 mm, respectively). The root extracts of H. verticillatum and H. angustisectum were found to be the most effective against acetylcholinesterase (IC50 0.30 and 0.34 mg/mL, respectively). The studied extracts were not active or demonstrated a weak inhibitory effect (%Inh. up to 29.7) towards α-amylase.

Phenolic Profile of Artemisia alba Turra.

The aim of this study was to evaluate flower and leaf methanol extracts of Artemisia alba Turra for their total phenolic and flavonoid contents, antioxidant capacity and to investigate their phenolic composition. The flower extract was richer in total phenolics and flavonoids and possessed higher antioxidant activity through DPPH and ABTS assays. The UHPLC-PDA-MS analysis of the flower and leaf methanol extracts revealed similar phenolic profile and allowed identification of 31 phenolic compounds (flavonoids, coumarins, and phenolic acids) by comparison with the respective reference compounds or tentatively characterized by their chromatographic behavior, UV patterns, and MS fragmentations. The presence of hispidulin, jaceosidin, desmethoxycentaureidin, and dicaffeoyl esters of quinic acid in A. alba is reported herein for the first time. The distribution of flavonoids in A. alba from different origins was discussed from chemotaxonomic point of view.

Essential oil composition of Inula britannica L. from Bulgaria.

The separately distilled flowers (F) and leaves' (L) essential oils of Inula britannica L. were investigated using capillary gas chromatography-flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC-MS). A total of 83 constituents, representing 96.91% (F) and 96.73% (L) of the total oils, were registered. The oils were rich in terpenoids (57.85% and 77.28%), of which sesquiterpenoids dominated. The main constituents of the essential oils were viridiflorol (7.17%-8.20%) and himachalol (3.45%-8.71%) followed by 6,10,14-trimethyl-2-pentadecanone (5.43%-2.95%), 13-tetradecanolide (3.93%-4.87%) and 3-methyl-4-propyl-2,5-furandione (4.06%-0.29%).

Phytochemical Profile of Inula britannica from Bulgaria.

The flower heads of Inula britannica L. of Bulgarian origin afforded sesquiterpene lactones (gaillardin, britannin, I1, 13-dihydroinuchinenolide B, ivalin, pulchellin C), triterpenoids (3-0-palmitates of 160-hydroxylupeol, 16ß-hydroxy-ß-amyrin, and faradiol) and flavonoids (quercetin, luteolin, luteolin-7-0- glucoside). All compounds are known and they were identified by spectral methods. The observed differences in the chemical content of the chloroform and methanol extracts were also reflected in their free radical scavenging activity, evaluated by DPPH and ABTS assays. Intraspecific variability of L britannica is discussed.

Developmental and Environmental Effects on Sesquiterpene Lactones in Cultivated Arnica montana L.

The amount of sesquiterpene lactones and the lactone profile of Arnica montana L. in flowering and seed formation stages in vitro and in vivo propagated from seeds of German, Ukrainian, and Austrian origin and grown in two experimental fields were studied. It was found that in vitro propagated 2-year plants in full flowering stage accumulated higher amount of lactones in comparison to in vivo propagated 3-year plants and to the seed formation stage, respectively. Helenalins predominated in in vivo propagated 2-year or in vitro propagated 3-year plants. 2-Methylbutyrate (2MeBu) was the principal ester in the samples with prevalence of helenalins, while isobutyrate (iBu) was the major one in the samples with predominance of 11,13-dihydrohelenalins. The results revealed that the environmental conditions on Vitosha Mt. are more suitable for cultivation of A. montana giving higher content of lactones.

Highly oxygenated sesquiterpenes in Artemisia alba Turra.

Ten new sesquiterpene alcohols of which seven germacranes, a eudesmane, a guaiane and an oplopane were isolated from the aerial parts of Artemisia alba Turra. Their structures and relative stereochemistry were elucidated by spectral methods ((1)H and (13)C NMR, COSY, HSQC, HMBC, NOESY, and MS). In addition, the known 7-hydroxycadin-4-en-3-one, centaureidin and axillarin were found for the first time in the studied species.

New pseudoguaiane derivatives from Inula aschersoniana Janka var. aschersoniana.

The aerial parts of Inula aschersoniana Janka var. aschersoniana afforded parthenolide, diepoxycostunolide, inusoniolide, chrysosplenol C and four new pseudoguaiane-type sesquiterpenoids. Their structures were determined using spectral methods and relative stereochemistry by NOESY correlations.

Sideritis scardica Griseb., an endemic species of Balkan peninsula: traditional uses, cultivation, chemical composition, biological activity.

ETHNOPHARMACOLOGICAL RELEVANCE: Sideritis scardica Griseb. is an endemic species in the Balkan Peninsula. It is used in traditional medicine as a loosening agent in bronchitis and bronchial asthma; against the common cold and lung emphysema; in the treatment of inflammation, gastrointestinal disorders and coughs; and as an active constituent of dietary supplements for the prevention of anemia. This review aims to provide a comprehensive overview of the traditional use, phytochemistry, biological activity, cultivation, and extraction of Sideritis scardica and to highlight the gaps in our knowledge which deserves further research. MATERIALS AND METHODS: The present review is based on information collected from scientific journals, books, and electronic search. These sources include Scopus, Pubmed, Web of Science, and Google scholar as well as local books on ethnopharmacology and botany of this plant. RESULTS: The reported data on phytochemical studies, biological activity, cultivation, extraction, and traditional uses have been reviewed. Variability in essential oil composition of wild growing and cultivated taxa depending on ecological conditions was discussed. Flavonoids, phenylethanoids, diterpenoids, aliphatic compounds, etc. identified so far have been summarized. A comparative study on the effectiveness of different methods, solvents, and parameters of extraction has also been discussed. A broad range of activities of plant extracts and fractions as antimicrobial, anti-inflammatory, cytotoxic, antioxidant, gastroprotective, antiglioma, and triple monoamine reuptake inhibition as well as cultivation of the species as an approach for conservation of the natural habitats and provision of herb with high and permanent quality has also been presented. CONCLUSIONS: Sideritis scardica has become very popular and widely advertised herb in Europe. Although some of ethnobotanical uses have been proved through in vitro experiments, further studies of the individual compounds or chemical class of compounds responsible for the pharmacological effects and the mechanisms of action are necessary. In addition, the toxicity and the side effects from the use of Sideritis scardica as well as clinical trails need attention. The variability in the chemical composition of this medicinal plant depending on the origin requires development of a protocol for its standardization. For the practice it is important to improve cultivation conditions in order to increase the accumulation of biologically active compounds and to obtain herb with permanent and good quality.

A new cembrane glycoside in Asterothamnus centrali-asiaticus from Gobi Desert.

A new cembrane glycoside, nephthenol 15-O-ß-d-quinovoside, was isolated from the aerial parts of Asterothamnus centrali-asiaticus. Its structure was elucidated by 1D and 2D NMR spectroscopic analysis, as well as by mass spectrometry. This is the first report of the occurrence of a cembrane glycoside in vascular plants.

Variability in the essential-oil composition of Sideritis scardica GRISEB. from native Bulgarian populations.

The essential-oil composition of six native populations of Sideritis scardica from Bulgaria was studied by GC-FID and GC/MS analyses. Altogether, 37 components, representing 73.1 to 79.2% of the total oil content were identified. Among them, α-pinene (4.4-25.1%), ß-pinene (2.8-18.0%), oct-1-en-3-ol (2.3-8.0%), phenylacetaldehyde (0.5-9.5%), ß-bisabolene (1.3-11.0%), benzyl benzoate (1.1-14.3%), and m-camphorene (1; 0.3-12.4%) were the main compounds. All samples were characterized by low contents of oxygenated mono- and sesquiterpenes (≤1.6 and 2.3%, resp.). Principal component analysis (PCA) and cluster analysis (CA) showed a significant variability in the chemical composition of the studied samples as well as a correlation between the oil profiles and the ecological conditions of the natural habitats of S. scardica.

Cytokinin and auxin effect on the terpenoid profile of the essential oil and morphological characteristics of shoot cultures of Artemisia alba.

The influence of plant growth regulators (PGR) on the essential oil composition and in vitro development of A. alba shoot cultures was studied. Two types of oils were determined, based on their terpenoid content. Close relations between the morphogenetic effects of PGR and the essential oil profile of the species were observed Predominance of root over shoot development was connected with a drop in the amounts of sesquiterpenoids and the direction of biosynthesis towards oxygenated monoterpenoids in the PGR-free control medium, as well in those with 1.0 mg L(-1) indole-3-butyric acid (IBA) supplementation. On the contrary, lack of root formation and stimulated callusogenesis caused by the addition of 0.2 mg L(-1) 6-benzyladenine (BA), irrespectively of the presence of IBA (either 0.5 mg L(-1) or 1.0 mg L(-1)), resulted in the strong prevalence of sesquiterpenoids in the oils. These results are indicative that the morphological development ofA. alba shoot cultures affects the terpenoid biosynthetic pathway bringing out the hypothesis for a possible root to shoot signaling.

Composition and antimicrobial activity of Achillea distans essential oil.

The essential oil of Achillea distans W. et K. flower heads was analyzed by GC and GC-MS. Altogether 43 components in concentrations more than 0.1% were identified representing 93.5% of the oil composition. The main constituents were 1,8-cineole (16.8%), trans-thujone (9.8%), sabinene (8.2%), borneol (7.5%), beta-pinene (6.5%), and camphor (5.8%). The oil showed moderate activity against Staphylococcus aureus and Candida albicans, and weak activity against Salmonella typhimurium, Proteus vulgaris, and Escherichia coli.

Quantitative analysis of sesquiterpene lactones in extract of Arnica montana L. by 1H NMR spectroscopy.

(1)H NMR spectroscopy was used as a method for quantitative analysis of sesquiterpene lactones present in a crude lactone fraction isolated from Arnica montana. Eight main components - tigloyl-, methacryloyl-, isobutyryl- and 2-methylbutyryl-esters of helenalin (H) and 11α,13-dihydrohelenalin (DH) were identified in the studied sample. The method allows the determination of the total amount of sesquiterpene lactones and the quantity of both type helenalin and 11α,13-dihydrohelenalin esters separately. Furthermore, 6-O-tigloylhelenalin (HT, 1), 6-O-methacryloylhelenalin (HM, 2), 6-O-tigloyl-11α,13-dihydrohelenalin (DHT, 5), and 6-O-methacryloyl-11α,13-dihydrohelenalin (DHM, 6) were quantified as individual components.

Flavonoid constituents and free radical scavenging activity of Alchemilla mollis.

Antioxidant capacity of the methanolic extract of Alchemilla mollis was measured by its ability to scavenge the DPPH radical. The EtOAc fraction obtained after partition of the total extract was found to be the most active radical scavenger (IC50 9.8 +/- 1.8 microg/mL) and was subjected to fractionation by Sephadex LH-20 CC. Further purification by RP-18 CC led to the isolation of eight flavonoid glycosides: cis- and trans-tiliroside (1 and 2), rhodiolgin (3), hyperoside (4), isoquercitrin (5), miquelianin (6), sinocrassoside D2 (7), and gossypetin-3-O-beta-D-galactopyranosyl-7-O-alpha-L-rhamnopyranoside (8). It was found that 8 is a new compound and its antioxidant activity is also reported. Identification of the isolated compounds was carried out by spectroscopic and spectrometric analysis (1D and 2D NMR, UV and MS).

Chemical composition of the essential oils of Rhodiola rosea L. of three different origins.

Rhodiola rosea L. (Crassulaceae), or "rose root" is a perennial herbaceous plant, distributed in the Northern Hemisphere. Pharmacological studies have shown that R. rosea exhibits different biological activities - antioxidant, antidepressant, anticancer, etc. The aim of this study was to compare the chemical composition of essential oils from rhizomes of three commercial samples of R. rosea originated from Bulgaria (sample 1), China (sample 2) and India (sample 3). The oils were analyzed by GC and GC-MS. Thus, the main volatile component in the Bulgaria and Chinese R. rosea was geraniol, followed by myrthenol in sample 1 or octanol in sample 2. Phenethylalcohol was a principal constituent in the Indian oil. Myrtenol and octanol were in significant amounts too. Aliphatic hydrocarbons were characteristic of the latter sample. It is notable that cinnamyl alcohol, which was present in large concentration in Bulgarian sample, was not detected in the other two samples. The obtained results showed considerable differences in the composition of the studied three origins of R. rosea.