Identification of Mushroom and Murine Tyrosinase Inhibitors from Achillea biebersteinii Afan. Extract

Growing scientific evidence indicates that Achillea biebersteinii is a valuable source of active ingredients with potential cosmetic applications. However, the data on its composition and pharmacological properties are still insufficient. This study aims to optimize the extraction procedure of the plant material, evaluate its phytochemical composition, and compare anti-tyrosinase potential of A. biebersteinii extracts obtained by various methods. In order to identify compounds responsible for the tyrosinase inhibitory activity of A. biebersteinii, the most active anti-tyrosinase extract was fractionated by column chromatography. The fractions were examined for their skin lightening potential by mushroom and murine tyrosinase inhibitory assays and melanin release assay. HPLC-ESI-Q-TOF-MS/MS analysis of the total extract revealed the presence of several phenolic acids, flavonoids, flavonoid glucosides, and carboxylic acid. Among them, fraxetin-8-O-glucoside, quercetin-O-glucopyranose, schaftoside/isoschaftoside, gmelinin B, 1,3-dicaffeoylquinic acid (1,3-DCQA), and ferulic acid were found in the fractions with the highest skin lightening potential. Based on obtained qualitative and quantitative analysis of the fractions, it was assumed that the caffeoylquinic acid derivatives and dicaffeoylquinic acid derivatives are more likely responsible for mushroom tyrosinase inhibitory activity of A. biebersteinii extracts and fractions. Ferulic acid was proposed as the most active murine tyrosinase inhibitor, responsible also for the reduced melanin release from B16F10 murine melanoma cells.     

Essential Oil Composition of Four <Emphasis Type="Italic">Achillea</Emphasis> Species from the Balkans and Its Chemotaxonomic Significance

The chemical composition of the essential oils of Achillea clavennae L., Achillea holosericea Sibth. & Sm., Achillea lingulata W. & K., and Achillea millefolium L. from the Balkans was determined by GC and GC/MS analyses. The main components were 1,8-cineole in A. holosericea, camphor in A. clavennae, β-pinene in A. millefolium, and τ-cadinol in A. lingulata. A detailed chemotaxonomic discussion is presented. __________ Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 555–558, November–December, 2005.     

Comparison of the Phenolic Compound Profile and Antioxidant Potential of Achillea atrata L. and Achillea millefolium L.

In the present study, Achillea atrata L. and A. millefolium L. were compared for the first time with regard to their phenolic compound profile and antioxidant activity by applying the 2,2-diphenyl-picryl hydrazyl radical assay. For this purpose, aerial plant parts were consecutively extracted with solvents of increasing polarity (dichloromethane, n-butanol, ethyl acetate), revealing that the A. atrata ethyl acetate fraction showed the highest antioxidant activity with an IC₅₀ value of 12.2 ± 0.29 µg/mL compared to 17.0 ± 0.26 µg/mL for A. millefolium. Both species revealed the presence of luteolin, apigenin, centaureidin, and nevadensin exclusively in this most polar fraction, which are known as effective 2,2-diphenyl-picryl hydrazyl radical scavengers. The antioxidant capacity of the aforementioned fractions strikingly correlated with their total phenolic contents, which was highest in the ethyl acetate fraction of A. atrata. Characterization of the metabolite profiles of both Achillea species showed only marginal differences in the presence of key compounds, whereas the concentrations of individual compounds appeared to be species-specific. Our results suggest that A. atrata, based on its compound pattern and bioactivity characteristics, has similar qualities for phytotherapy as A. millefolium.     

Volatile chemical composition and bioactivity of six essential oils against the stored food insect Sitophilus zeamais Motsch. (Coleoptera Dryophthoridae)

Essential oils (EOs) of Achillea millefolium, Myrtus communis, Rosmarinus officinalis, Helichrysum italicum, Foeniculum vulgare and Lavandula angustifolia were analysed with GC-FID and GC-MS in order to define their aromatic profiles and then their toxicity and repellent activity against Sitophilus zeamais Motsch. (Coleoptera Dryophthoridae) with specific bioassays were evaluated. Results from topical applications on insects showed that all EOs had variable and significant insecticidal activity. Mortality rate never exceeded 76%. Results of repellency tests are indicated for M. communis and L. angustifolia EOs, displaying high repellent activity to S. zeamais adults.     

Spirodepressolide: an unusual bis-norsesquiterpene lactone from Achillea depressa Janka

A new bis-norsesquiterpene lactone, spirodepressolide (1), has been isolated from the aerial parts of Achillea depressa Janka and its structure determined by spectroscopic methods to have a new 4-methyl-7-methylethyl-spirobicyclo[4,4]nonane skeleton.     

Chemical composition, antioxidant and antibacterial properties of Achillea collina Becker ex Heimerl s.l. and A. pannonica Scheele essential oils

The in vitro antioxidant and antimicrobial activities of two Achillea millefolium (Adanson) Koch s.l species essential oils (A. collina Becker ex Heimerl s.l. and A. pannonica Scheele, Asteraceae) originating from the Golija and Radan mountains (Serbia) were investigated. The chemical profiles of the essential oils were evaluated by GC-MS. Antioxidant activity was assessed as free radical scavenging capacity (RSC) towards 2,2-diphenyl-1-picrylhydrazil (DPPH) radicals, together with effects on lipid peroxidation (LP). Antibacterial activity was examined on 21 bacterial strains. Based on the chemical composition of the essential oil, A. collina s.l. from Mount Golija was classified as a chamazulene chemotype (tetraploid). The high percentage of oxygenated monoterpenes and absence of azulene in the essential oil obtained from A. pannonica from Radan pointing that this population is octaploid. Essential oil of A. pannonica expressed stronger antimicrobial activity on almost all tested bacteria. Furthermore, this essential oil expressed higher scavenging effects on DPPH radical (IC(50) = 0.52 comparing to 0.62 mug/mL). Only in the LP evaluation, essential oil of A. collina s.l. from Golija exhibited stronger antioxidant activity (IC(50) = 0.75 comparing to 2.12 mug/mL).     

Chemical Characterization and Antibacterial Activity of Essential Oil of Medicinal Plants from Eastern Serbia

The objective of this study was to evaluate wild growing Satureja kitaibelii, Thymus serpyllum, Origanum vulgare, Achillea millefolium and Achillea clypeolata with respect to their essential oil (EO) content, composition and antimicrobial activity. The five species were collected at Mt. Rtanj and the village of Sesalac, Eastern Serbia. The main EO constituents of Lamiaceae plants were p-cymene (24.4%), geraniol (63.4%) and germacrene D (21.5%) in Satureja kitaibelii, Thymus serpyllum and Origanum vulgare ssp. vulgare, respectively. A. millefolium EO had multiple constituents with major ones being camphor (9.8%), caryophyllene oxide (6.5%), terpinen-4-ol (6.3%) and 1,8-cineole (5.6%), while the main EO constituents of A. clypeolata were 1,8-cineole (45.1%) and camphor (18.2%). Antimicrobial testing of the EO showed that Staphylococcus aureus (Gram-positive) was more sensitive to all of the tested EOs than Escherichia coli (Gram-negative). S. kitaibelii EO showed the highest antimicrobial activity against both tested bacterial strains. This is the first study to characterize the EO composition and antimicrobial activity of these five medicinal species from Eastern Serbia in comparison with comprehensive literature data. The results can be utilized by the perfumery, cosmetics, food and pharmaceutical industries, but also for healing purposes in self-medication.     

Chemical composition and antimicrobial activity of essential oil of Achillea cretica L. (Asteraceae) from Turkey

Hydrodistilled volatile oil from the aerial parts of Achillea cretica L. (Asteraceae) was analysed by a combination of GC and GC/MS. Seventy-six components were identified, constituting 86.4% of the oil. The main constituents of the essential oil were caryophylladienol-II (13.4%), β-maaliene (6.1%), neo-intermedeol (6.0%), carvone (4.9%), spathulenol (4.5%), palmitic acid (3.3%) and selina-3,11-dien-6α-ol (3.2%). The antimicrobial activity was evaluated by the broth-dilution method on nine microbial strains and showed to be quite strong against the Gram-positive bacteria Staphylococcus aureus and Bacillus cereus. The antibacterial properties of A. cretica justify its use in traditional medicine for the treatment of wounds, contaminated through bacterial infections.     

Influence of Extraction Solvent on the Phenolic Profile and Bioactivity of Two Achillea Species

The phenolic composition, as well as the antioxidant and antimicrobial activities of two poorly investigated Achillea species, Achillea lingulata Waldst. and the endemic Achillea abrotanoides Vis., were studied. To obtain a more detailed phytochemical profile, four solvents with different polarities were used for the preparation of the plant extracts whose phenolic composition was analyzed using UHPLC-MS/MS (ultra-high performance liquid chromatography-tandem mass spectrometry). The results indicate that both of the investigated Achillea species are very rich in both phenolic acids and flavonoids, but that their profiles differ significantly. Chloroform extracts from both species had the highest yields and were the most chemically versatile. The majority of the examined extracts showed antimicrobial activity, while ethanolic extracts from both species were potent against all tested microorganisms. Furthermore, the antioxidant activity of the extracts was evaluated. It was found that the ethanolic extracts possessed the strongest antioxidant activities, although these extracts did not contain the highest amounts of detected phenolic compounds. In addition, several representatives of phenolic compounds were also assayed for these biological activities. Results suggest that ethanol is a sufficient solvent for the isolation of biologically active compounds from both Achillea species. Moreover, it was shown that the flavonoids naringenin and morin are mainly responsible for these antimicrobial activities, while caffeic, salicylic, chlorogenic, p-coumaric, p-hydroxybenzoic, and rosmarinic acid are responsible for the antioxidant activities of the Achillea extracts.     

Achillinin B and C,new sesquiterpene dimers isolated from Achillea millefolium

Two novel sesquiterpene dimers, achillinin B and C, were isolated from the flowers of Achillea millefolium. The structures were elucidated by extensive spectroscopic analysis. A plausible biosynthetic pathway of achillinin B and C by Diels–Alder reaction of the corresponding guaiane sesquiterpenoids is also discussed.     

Diversity of the Chemical Profile and Biological Activity of Capsicum annuum L. Extracts in Relation to Their Lipophilicity

Ethanol extracts of two types of pepper (sweet and hot) were separated into fractions with increasing lipophilicity. After drying the extracts and fractions, their chemical composition, anti-radical activity in the DPPH radical system, and cytotoxic activity against PC-3 and HTC-116 cells were determined. A detailed qualitative analysis of the fractions was performed with the LC-QTOF-MS method. It was found that the chemical composition of pepper fractions did not always reflect their biological activity. The highest antiradical activity was detected in the fraction eluted with 40% methanol from sweet pepper. The highest total content of phenolic compounds was found in an analogous fraction from hot pepper, and this fraction showed the strongest cytotoxic effect on the PC-3 tumour line. The LC-MS analysis identified 53 compounds, six of which were present only in sweet pepper and four only in hot pepper. The unique chemical composition of the extracts was found to modulate their biological activity, which can only be verified experimentally.     

Comparative Studies on Essential Oil and Phenolic Content with In Vitro Antioxidant,Anticholinesterase, Antimicrobial Activities of Achillea biebersteinii Afan. and A. millefolium subsp. millefolium Afan. L. Growing in Eastern Turkey

The potential applications of Achillea species in various industries have encouraged the examination of their phytochemical components along with their biological potential. In the present study, phenolic contents and essential oil compositions together with the in vitro biological activities of the aerial parts from Achillea biebersteinii Afan. and Achillea millefolium subsp. millefolium Afan. collected from Turkey were evaluated. Different solvent extracts (n-hexane, chloroform, methanol, water) were prepared and their antimicrobial, anticholinesterase, and antioxidant activities were studied. The LC-MS/MS results revealed the presence of 16 different phenolic compounds, including chlorogenic acid, rutin, quercetin, and luteolin glycosides, in methanolic extracts. According to GC-FID and GC/MS results, the primary components of the oils were identified as 1,8-cineole (32.5%), piperitone (14.4%), and camphor (13.7%) in A. biebersteinii and 1,8-cineole (12.3%) and β-eudesmol (8.9%) in A. millefolium subsp. millefolium. The infusion and methanolic extracts of both species were found to be rich in their total phenolic content as well as their antioxidant and anticholinesterase activity. In contrast, the n-hexane and chloroform extracts of both species showed strong antimicrobial activity with MIC values ranging from 15 to 2000 μg/mL. Our findings suggest that the investigated Achillea species could be evaluated as potent natural agents, and further studies into the promising extracts are needed.     

Composition of the Essential Oils of Two Endemic Species from Turkey: Achillea lycaonica and A. ketenoglui

The hydrodistilled essential oils ofAchillea lycaonicaBoiss. & Heldr. andA. ketenogluiH. Duman were analyzed by GC/MS. The main components in the oils were trans-sabinene hydrate (9.3%) inA. lycaonicaand borneol (14.1%) and terpinen-4-ol (14.5%) inA. ketenoglui     

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.     

Phosphatase activities of fractions of the venom of Renard's viperVipera ursini renardi

The separation of the venom of Renard's viper by filtration through Sephadex G-75 gel has been performed and phosphatase activities have been determined in the fractions and in the course of separation. The bulk of the activity of the phosphatases investigated was concentrated in the high-molecular-weight fractions I and II. A correlation has been found in the distribution of the DNase and ATP-pyrophosphatase activities with the phosphodiesterase activity in the venom fractions. There is no correlation in the distribution of the RNase and phosphodiesterase activity.Institute of Biochemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 783–786, November–December, 1985.     

Essential oil composition of five collections of Achillea biebersteinii from central Turkey and their antifungal and insecticidal activity

The composition of the essential oils hydrodistilled from the aerial parts of five Achillea biebersteinii Afan samples, collected in central Turkey from Konya, Isparta and Ankara, were analyzed both by gas chromatography (GC-FID) and gas chromatography-mass spectrometry (GC-MS). Eighty-four components were identified, representing 87 to 99% of the total oil composition. The identified major components were 1,8-cineole (9-37%), camphor (16-30%) and p-cymene (1-27%). Two samples differed in piperitone (11%) and ascaridol (4%) content. The five A. biebersteinii essential oils were subsequently evaluated for their antifungal activity against the strawberry anthracnose-causing fungal plant pathogens Colletotrichum acutatum, C. fragariae and C. gloeosporioides using the direct overlay bioautography assay. The essential oils showed no antifungal activity at 80 and 160 microg/spot. In addition, A. biebersteinii oils and their major compounds were subsequently investigated against Aedes aegypti first instar larvae in a high throughput bioassay. Among the oils, only one sample from Ankara showed a notable larvacidal effect on Ae. aegypti larvae. The major compounds, 1,8-cineole, camphor and p-cymene, exhibited low mosquito larval activity, and thus the minor compounds are probably responsible for the observed activity against Ae. aegypti larvae. The oils showed weak activity against adult Ae. aegypti.     

Absolute configuration of ageratriol : A germacranic sesquiterpene from Achillea ageratum L.

On the basis of chemical evidence, the stereostructure 7 is proposed for ageratriol, a germacranic sesquiterpene isolated from Achillea ageratum L.     

Analysis and Comparison Constituent of the Essential Oil from Three Different Species of Achillea L. in the Northern Slope of Tianshan Mountains

Moscow University Chemistry Bulletin - The genus Achillea L. (Family: Asteraceae) is a kind of perennial plant, mostly distributed in north western region of China, especially in Tianshan Mountains...     

Ene Reaction of Pummerer-Type Reaction Intermediate and Synthesis of Achillea Amide

Pummerer-type reaction intermediate 2 of methyl α-(methylthio)acetate (1) has been found to react with 1-alkenes to afford ene adducts 3 . Achillea amide 5 was synthesized from the adduct 3g .     

Distribution and chemical polymorphism of the essential oils of Achillea cartilaginea growing wild in Lithuania

The essential oils from 14 Achillea cartilaginea samples (leaves and flowers) collected from natural habitats in Lithuania were analysed by GC-MS. In total, 97 compounds were identified, 69 of which have not been reported previously in this species. In general, the essential oils of A. cartilaginea were rich in oxygenated monoterpenes. Remarkable chemical polymorphism was observed within the population of A. cartilaginea in Lithuania. It was observed that 1,8-cineole, camphor, cis-chrysanthenol, β-thujone, sabinol, chrysanthenone, terpinen-4-ol, bornyl acetate and β-sesquiphellandrene were the major constituents in the oils of the analysed plants. Hierarchical cluster analysis, which was based on the 19 major components exceeding 5% in the total oil, indicates the presence of several main chemical groups in the analysed plant populations.