Chemical composition on essential oils from needles of Pinus sylvestris L. grown in northern Lithuania

Content and composition of needle essential oils of Pinus sylvestris (Scots pine) grown in the north of Lithuania have been studied. Volatile components of dried current-year and 1 year old needles were extracted by simultaneous hydrodistillation-extraction and analyzed by GC and GUMS. The most predominant fraction was found to be monoterpene hydrocarbons (26.4-41.3%), with the major constituents alpha-pinene (7.0-16.1 %) and delta-3-carene (5.2-14.3 %) in it. Among the oxygenated monoterpenes bornyl acetate was tire most dominant constituent (1.1-3.9 %). Sesquiterpene hydrocarbons formed 19.4-26.0 % of the oils; amounts of main sesquiterpenes beta-caryophyllene and delta-cadinene were 2.6-5.8 % and 2.3-5.9 %, respectively. alpha-Cadinol (4.2-8.5 %) and epi-alpha-cadinol with epi-alpha-muurolol and alpha-muurolol (4.0-9.1 %) were the major compounds in oxygenated sesquiterpenes fraction. Diterpenoids (including and tentitatively identified compound) comprised 6.2-13.7 % of the oils. Also, differences in composition of current-year and 1 year old needles were represented in the study. Seventy-one identified component made up 89.1-98.2 % of total oil content. One sample of fresh needles was analyzed in order to compare the composition with oils obtained from dried needles. Relative amount of monoterpene hydrocarbons was significantly higher (71.0 %) in the oil of fresh needlesChemijos institutasKauno medicinos universiteta

Phytochemistry and Allelopathic Effects of <i>Tanacetum vulgare</i> L. (Tansy) Extracts on <i>Lepidium sativum</i> L. (Garden Pepper Cress) and <i>Lactuca sativa</i> L. (Lettuce)

Tanacetum vulgare is a perennial plant growing wild along roadsides, pastures, and agricultural fields. Its prevalence is due to several factors: good climatic adaptability, high self-seeding potential, phenotypic plasticity, multiplying via underground rhizomes and its allelochemicals, which influence the seed germination, root development and the overall vegetation of the surrounding plants. The phytochemistry of tansy extracts and their allelopathic activity on the seed germination and growth of garden pepper cress (Lepidium sativum L.) and lettuce (Lactuca sativa L.) were investigated. The major volatile compounds, 1,8-cineole, camphor and borneol were determined in tansy flower extracts. The leaf extracts contained appreciable amounts of 1,8-cineole and borneol. Feruloylquinic, (di)ferulic and dehydrocaffeoyl-5-caffeoylquinic acids, acacetin, ludovicin C and tanacetin were determined both in leaf and inflorescence extracts. Root extracts contained minor quantities of some terpenoids and polyphenols. Extracts of T. vulgare’s aerial parts showed strong allelopathic effects on model plants. The flower and leaf water extracts inhibited lettuce and pepper cress seed germination and growth the most. According to the fractions, the acidic solution had the strongest effect, followed by neutral and alkaline solutions. At the highest relative concentrations of 0.5 and 1.0 tansy leaf acidic fraction, lettuce seed germination and growth decreased by 89.93% (from 35.07 ± 4.79 to 3.53 ± 2.10 mm) and by 98.46% (from 35.07 ± 4.79 to 0.57 ± 0.98 mm) compared to the control, respectively. Tansy root extracts showed weak effects. Our results demonstrated that the allelopathic inhibitory potential of tansy extracts was higher on garden pepper cress than on lettuce. The presence of allelochemicals in T. vulgare may have a significant impact on plant communities and ecosystems

Changes in the essential oil composition in the needles of Scots Pine (Pinus sylvestris L.) under anthropogenic stress

Unfavorable anthropogenic factors, such as air pollution, lead to biochemical responses in trees. Changes in the amounts of secondary metabolites may be early indicators of invisible injuries. The aim of this study was to evaluate composition of the essential oils in the needles of Scots pine (Pinus sylvestris L.) growing in the areas affected by pollutant emissions of main factories in Lithuania: a nitrogen fertilizer factory (NFF), a cement factory (CF), and an oil refinery (OR). Totally, 14 pine stands were examined along transects from the factories (July 2005). Volatile components of the needles were extracted and analyzed by GC and GC/MS. Over 70 components of the essential oils were identified in current-year and 1-year-old needles. Along the CF transect for current-year needles, the percentage of diterpenes was decreasing with the increasing pH of the pine bark (r = –0.582; p < 0.05) or with the increasing concentration of SO2 (r = –0.573; p < 0.05); for 1-year-old needles, the percentage of diterpenes was decreasing with the increasing pH of the bark (r = –0.534; p < 0.05). Along the OR transect, in both the current-year and 1-year-old needles, the percentage of diterpenes was decreasing with the increasing SO2 (respectively, r = –0.773; p < 0.01; r = –0.486; p < 0.05); an opposite relation was true for sesquiterpenes (respectively, r = –0.751; p < 0.01; r = 0.785; p < 0.01). The view was different along the NFF transect. For current-year needles, the percentage of monoterpenes was decreasing with the increasing NH3 (r = –0.669; p < 0.01); while the percentage of sesquiterpenes or oxysesquiterpenes was increasing with the increasing NH3 (respectively, r = 0.540; p < 0.05 and r = 0.688; p < 0.01). For each transect, cluster analysis of the percentages of components of essential oils in the needles allowed us to distinguish the most contrasting stands according to the concentration of air pollutantsChemijos institutasKauno medicinos universitetasVytauto Didžiojo universitetasŽemės ūkio akademij

Toxic, radical scavenging, and antifungal activity of rhododendron tomentosum H. essential oils

The chemical composition of eight (seven shoot and one inflorescence) essential oils (EOs) of Rh. tomentosum H. plants growing in Eastern Lithuania is reported. The plant material was collected during different phases of vegetation (from April to October). The oils were obtained by hydrodistillation from air-dried aerial parts (leaves and inflorescences). In total, up to 70 compounds were identified by GC−MS and GC (flame-ionization detector, FID); they comprised 91.0 ± 4.7%–96.2 ± 3.1% of the oil content. Sesquiterpene hydrocarbons (54.1 ± 1.5%–76.1 ± 4.5%) were found to be the main fraction. The major compounds were palustrol (24.6 ± 2.6%–33.5 ± 4.4%) and ledol (18.0 ± 2.9%–29.0 ± 5.0%). Ascaridol isomers (7.0 ± 2.4%–14.0 ± 2.4% in three oils), myrcene (7.2 ± 0.3% and 10.1 ± 1.3%), lepalol (3.3 ± 0.3% and 7.9 ± 3.0%), and cyclocolorenone isomers (4.1 ± 2.5%) were determined as the third main constituents. The toxic activity of marsh rosemary inflorescence and shoot oils samples was evaluated using a brine shrimp (Artemia sp.) bioassay. LC50 average values (11.23–20.50 µg/mL) obtained after 24 h of exposure revealed that the oils were notably toxic. The oil obtained from shoots gathered in September during the seed-ripening stage and containing appreciable amounts of palustrol (26.0 ± 2.5%), ledol (21.5 ± 4.0%), and ascaridol (7.0 ± 2.4%) showed the highest toxic activity. Radical scavenging activity of Rh. tomentosum EOs depended on the plant vegetation stage. The highest activities were obtained for EOs isolated from young shoots collected in June (48.19 ± 0.1 and 19.89 ± 0.3 mmol/L TROLOX (6-hydroxy-2,5,7,8-tetra-methylchromane-2-carboxylic acid) equivalent obtained by, respectively, ABTS•+ (2,20-amino-bis(ethylbenzothiazoline-6-sulfonic acid) diammonium salt) and DPPH•(2,2-diphenyl-1-picrylhydrazyl) assays). Agar disc diffusion assay against pathogenic yeast Candida parapsilosis revealed the potential antifungal activity of EOs. An alternative investigation of antifungal activity employed mediated amperometry at yeast Saccharomyces cerevisiae-modified electrodes. The subjection of yeast cells to vapors of EO resulted in a three to four-fold increase of electrode responses due to the disruption of yeast cell membranes

Paprastosios pušies (Pinus sylvestris L.) jaunuolynų, augančių amoniaku užterštose vietose, spyglių eterinių aliejų pokyčiai

Tirta paprastosios pušies pirmamečių ir antramečių spyglių, surinktų azotinių trąšų gamyklos „Achema“ (Jonava) įtakos zonoje augančiuose jaunuolynuose, eterinių aliejų cheminė sudėtis. Spyglių mėginiai buvo surinkti 0,5–22 km atstumu nuo gamyklos. Hidrodistiliacijos būdu gauti eteriniai aliejai buvo analizuojami dujų chromatografijos/masių spektrometrijos metodu. Eterinio aliejaus išgava kito nuo 0,25 iki 0,47% pirmamečiuose ir nuo 0,25 iki 0,49% antramečiuose spygliuose. Monoterpeniniai angliavandeniliai vyravo visuose tirtuose aliejuose ir pirmamečiuose ir antramečiuose spygliuose sudarė atitinkamai 58,4– 72,4% ir 45,0–60,8%. Seskviterpeniniai angliavandeniliai sudarė 14,5–25,7% aliejaus pirmamečiuose ir 18,5–33,1% antramečiuose spygliuose.Eterinio aliejaus kiekis šiek tiek padidėjo spygliuose, surinktuose 5 km atstumu į šiaurės rytus nuo gamyklos augančiuose jaunuolynuose. Vyraujančių eterinių aliejų komponentų – monoterpenų a-pineno ir d-3-kareno – koncentracijos taip pat padidėjo spygliuose, surinktuose vietovėse, esančiose 5 km atstumu nuo taršos šaltinio. Pramoninės taršos sąlygomis pušys gamina daugiau terpeninių angliavandenilių, turinčių trumpesnę anglies atomų grandinę ir mažesnį kiekį lakiųjų terpeninių junginių su ilgesne atomų grandine. Ši tendencija labiau pasireiškia pirmamečiuose spygliuoseContent and composition of needle essential oils of young Scots pine stands (Pinus sylvestris L.) growing along an ammonia gradient (in the impact zone of a nitrogen fertilizer factory, JSC Achema, Jonava, Lithuania) have been studied. Eight young pine stands growing at a distance up to 22 km from the factory were chosen for sampling. Volatile components of the current-year and one-year-old needles were obtained by a simultaneous hydrodistillationextraction of dried material and analysed by GC and GC/MS. The yield of the essential oil varied from 0.25 to 0.47% and 0.25–0.49% in the current-year and one-year-old needles of pine, respectively. A slight increase of the oil yield was observed in the needles collected in pinewoods located at a distance up to 5 km from the factory. The chemical composition of the volatile oils of the dried needles collected at different distances was investigated. The most predominant fraction was found to be monoterpene hydrocarbons (58.4–72.4% and 45.0–60.8% in the current-year and one-yearold needles, respectively) with the major constituents a-pinene (19.8–35.0% and 18–28.0%) and d-3-carene (22.7%–33.7% and 19.9–25.9%). Variability of the amounts of these major constituents in the needles of the stands growing at different distances from the factory were represented. Sesquiterpene hydrocarbons were the second dominating fraction in the oils and formed 14.5– 25.7% and 18.5–33.1%, in the current-year and one-year-old needles, respectively. Under the effect of ammonia pollution, higher amounts of shorter chain terpenes and lower amounts of longer chain ones were produced, and this dependance was stronger expressed in the oils of the current-year needlesChemijos institutas, [email protected] medicinos universitetasVytauto Didžiojo universitetasŠvietimo akademijaŽemės ūkio akademij

Composition of essential oil of „Hypericum maculatum“ growing in some places of Lithuania

Genus Hypericum L. belongs to family Hypericaceae. Nowadays this family is classified as a subfamily Hypericoideae of family Clusiaceae (Guttiferae), and comprises more than 450 species. The genus Hypericum is common all over the world. In Lithuania 6 species are growing wild [1], among them 3 are included into Lithuanian Red Book data [2]. The majority of worldwide studies on this genus refer to the species Hypericum perforatum, as a consequence of its application in the traditional medicine and modern phytotherapy [3]. Essential oils of Hypericum are used for their antiviral, antifungal and antibacterial effects [4,5]. These oils are applicable externally (in form of the oil) for haemorrhoids, burns, wounds, cuts, muscular pain, sciatica, neuralgia, for newborn infant’s gastric spasms [6]. Internally (in form of the tea) Hypericum is used in case of for moderate depression, insomnia and gastrointestinal ailments (stomach ulcer, liver and bile ailments, jaundice). In folk medicine Hypericum is used as the herb with astringent, calmative properties. Nowadays special interest is taking in Hypericum antidepressant effects [7]. Essential oils are synthesized either in translucent glands or secretory ducts localized in leaves and various parts of the flowers (petals, sepals and pistil) [8] that is why organ specificity is documented in most studies of Hypericum. According to the quantity and quality, the components of essential oils may be linked with the phenological stage of the plant [9]. In addition, there is evidence about differences in essential oils of Hypericum collected in various geographical regions [10]. In Lithuania 2 species of Hypericum are widely distributed – H. perforatum and H. maculatum, although biology and biochemistry of H. maculatum has got less attention when compared to H. perforatum. [...]Biologijos katedraChemijos institutasVytauto Didžiojo universiteta

Dynamics of morphometric parameters and peculiarities of element concentration in Hypericum maculatum Crantz

Didėjantis susidomėjimas vaistiniais augalais, kaip sintetinių vaistų pakaitalais, verčia labiau domėtis jų fiziologinėmis savybėmis. Gydomasis jonažolės poveikis priklauso nuo sintetinamų medžiagų kiekio ir kokybinės jų sudėties, taip pat ir nuo tinkamo augalinės žaliavos rinkimo laiko bei paruošimo vartojimui. Darbo tikslu buvo ištirti H. maculatum produktyvumo ir morfometrinių rodiklių dinamiką vegetacijos sezono eigoje bei įvertinti jonažolės užterštumą sunkiaisiais metalais. Nustatyta organų morfologinių, organų sausosios masės, lapų paviršiaus ploto, santykinių morfometrinių-gravimetrinių rodiklių kaita vegetacijos sezono metu. Birželio mėn. keturbriaunė jonažolė reikšmingai skyrėsi nuo vėliau suriktų augalų pagal aukštį. Pagal požeminės dalies, stiebų, žiedų ir vaisių masę keturbriaunė jonažolė birželyje buvo reikšmingai mažiausios masės. Liepos mėn. keturbriaunė jonažolė pasižymėjo didžiausiu produktyvumu. Keturbriaunės jonažolės santykinis augimo greitis per birželio-rugsėjo mėn. ženkliai mažėjo: nuo 60 mg d.-1 iki 8 mg d.-1 Reikšmingai mažesniais N, P, K, Ca kiekiais išsiskyrė keturbriaunės jonažolės požeminė dalis, palyginus su stiebais. Keturbriaunės jonažolės stiebų Pb, Ni, Cd, Cr koncentracija buvo reikšmingai nuo 4,5 iki 223 kartų mažesnė už dirvožemio ir nesiekė nuodingumo augalams ribosBiologijos katedraChemijos institutasVytauto Didžiojo universitetasŽemės ūkio akademij

Allelopathic Activity of Canadian Goldenrod (<i>Solidago canadensis</i> L.) Extracts on Seed Germination and Growth of Lettuce (<i>Lactuca sativa</i> L.) and Garden Pepper Cress (<i>Lepidium sativum</i> L.)

Native to N. America, Canadian goldenrod (Solidago canadensis L.) was introduced to Europe as an ornamental plant and quickly spread here and in other parts of the world. The rapid spread of the plant is due to several reasons: phenotypic plasticity, broad climatic tolerance, propagation via underground rhizomes and seeds that mature in large numbers, etc. Additionally, the success of Canadian goldenrod’s invasion is determined by its allelochemicals that affect seed germination, root formation and whole growth of nearby plants. Allelopathy of various extracts and essential oils (EOs) of S. canadensis on seed germination and growth of lettuce (Lactuca sativa L.) and garden pepper cress (Lepidium sativum L.) was evaluated and compared with other Solidago species (S. virgaurea, S. × niederederi) collected from the same growing locality in Lithuania. Soil characteristics (conductivity, pH and major elements) of the collecting site were determined. Aqueous flower extracts of all studied Solidago species showed the highest inhibitory effect on model plants. Canadian goldenrod leaf water/diethyl ether extract showed highest inhibitory effect in all relative concentrations (1.0; 0.1; 0.01) suppressing growth of L. sativa (from 0 to 2.3 mm compared with 22.7 mm for control samples) and L. sativum (from 0.5 to 16.8 mm compared with 35.3 mm in control). It was noticed that garden pepper cress was more susceptible to Solidago spp. inhibitory effects than lettuce. S. canadensis root EOs comprised mainly of limonene (35.0%) and β-pinene (26.2%) and inflorescence oils containing α-pinene (21.6%), germacrene D (15.1%), limonene (10.2%) and lupenyl acetate (9.8%) exhibited the highest inhibitory effect on lettuce and garden pepper cress growth. Relative germination and vigor index of model plants was conducted. Chemical composition of extracts and EOs was determined by HPLC/DAD/TOF and GC/MS techniques

Peculiarities of stem nitrogen concentration of "Hypericum perforatum L." and "Hypericum maculatum Crantz"

Biologijos katedraChemijos institutasVytauto Didžiojo universitetasŽemės ūkio akademij

Palladium-Catalyzed Synthesis of Cyclopropylthiophenes and Their Derivatization

The cyclopropylthiophene moiety has attracted the attention of the scientific community for its potential pharmaceutical applications. However, synthesis of the compounds containing this framework remains challenging, has rarely been reported and remains unresolved. Here we provide optimized syntheses for cyclopropylthiophenes and their derivatives, containing carbonyl, acetyl, carboxylic acid, methyl carboxylate, nitrile, bromide and sulfonyl chloride moieties