Showing papers on "Terpene published in 2013"

Progress in Renewable Polymers from Natural Terpenes, Terpenoids, and Rosin

Abstract: The development of sustainable renewable polymers from natural resources has increasingly gained attention from scientists, engineers as well as the general public and government agencies. This review covers recent progress in the field of renewable bio-based monomers and polymers from natural resources: terpenes, terpenoids, and rosin, which are a class of hydrocarbon-rich biomass with abundance and low cost, holding much potential for utilization as organic feedstocks for green plastics and composites. This review details polymerization and copolymerization of terpenes such as pinene, limonene, and myrcene and their derivatives, terpenoids including carvone and menthol, and rosin-derived monomers. The future direction on the utilization of these natural resources is discussed.

Natural products : phytochemistry, botany and metabolism of alkaloids, phenolics and terpenes

Abstract: Part I Alkaloids: General Biology and Biotechnology.- Part II Alkaloids: Classes - Occurrence, Biosynthesis, Structure and Chemistry, Distribution.- Part III Alkaloids: Methods of Analysis.- Part IV Alkaloids: Pharmacology.- Part V Phenolics: General Biology and Biotechnology.- Part VI Phenolics: Classes - Occurrence, Biosynthesis, Structure and Chemistry, Distribution.- Part VII Phenolics: Methods of Analysis.- Part VIII Phenolics: Biological Activity and Bioavailability.- Part IX Phenolics: Nutraceuticals and Functional Foods.- Part X Terpenes: General Biology and Biotechnology.- Part XI Terpenes: Classes - Occurrence, Biosynthesis, Structure and Chemistry, Distribution.- Part XII Terpenes: Methods of Analysis.- Part XIII Terpenes: Pharmacology and Bioavailability.- Part XIV Terpenes: Parapharmaceutical Uses.

Terpenoids of plant origin inhibit morphogenesis, adhesion, and biofilm formation by Candida albicans.

Abstract: Biofilm-related infections caused by Candida albicans and associated drug resistant micro-organisms are serious problems for immunocompromised populations Molecules which can prevent or remove biofilms are needed Twenty-eight terpenoids of plant origin were analysed for their activity against growth, virulence attributes, and biofilms of C albicans Eighteen molecules exhibited minimum inhibitory concentrations of <2 mg ml(-1) for planktonic growth Selected molecules inhibited yeast to hyphal dimorphism at low concentrations (0031-05 mg ml(-1)), while adhesion to a solid surface was prevented at 05-2 mg ml(-1) Treatment with 14 terpenoids resulted in significant (p < 005) inhibition of biofilm formation, and of these, linalool, nerol, isopulegol, menthol, carvone, α-thujone, and farnesol exhibited biofilm-specific activity Eight terpenoids were identified as inhibitors of mature biofilms This study demonstrated the antibiofilm potential of terpenoids, which need to be further explored as therapeutic strategy against biofilm associated infections of C albicans

Current and Potential Use of Citrus Essential Oils

Abstract: Since the Middle Ages, citrus essential oils (EOs) have been widely used for their bactericidal, virucidal, fungicidal, antipara- sitical, insecticidal, medicinal and cosmetic proprieties. Also nowadays, they find important applications in pharmaceutical, sanitary, cosmetic, agricultural and food industries. The best method to extract EOs from citrus plant tissue is steam distillation because of a vari- ety of extracted volatile molecules such as terpenes and terpenoids, phenol-derived aromatic components and aliphatic components. In vitro physicochemical assays classify most of them as antioxidants.

Functional Genomics Reveals That a Compact Terpene Synthase Gene Family Can Account for Terpene Volatile Production in Apple

Abstract: Terpenes are specialized plant metabolites that act as attractants to pollinators and as defensive compounds against pathogens and herbivores, but they also play an important role in determining the quality of horticultural food products. We show that the genome of cultivated apple (Malus domestica) contains 55 putative terpene synthase (TPS) genes, of which only 10 are predicted to be functional. This low number of predicted functional TPS genes compared with other plant species was supported by the identification of only eight potentially functional TPS enzymes in apple ‘Royal Gala’ expressed sequence tag databases, including the previously characterized apple (E,E)-α-farnesene synthase. In planta functional characterization of these TPS enzymes showed that they could account for the majority of terpene volatiles produced in cv Royal Gala, including the sesquiterpenes germacrene-D and (E)-β-caryophyllene, the monoterpenes linalool and α-pinene, and the homoterpene (E)-4,8-dimethyl-1,3,7-nonatriene. Relative expression analysis of the TPS genes indicated that floral and vegetative tissues were the primary sites of terpene production in cv Royal Gala. However, production of cv Royal Gala floral-specific terpenes and TPS genes was observed in the fruit of some heritage apple cultivars. Our results suggest that the apple TPS gene family has been shaped by a combination of ancestral and more recent genome-wide duplication events. The relatively small number of functional enzymes suggests that the remaining terpenes produced in floral and vegetative and fruit tissues are maintained under a positive selective pressure, while the small number of terpenes found in the fruit of modern cultivars may be related to commercial breeding strategies.

Volatile terpenes from actinomycetes: a biosynthetic study correlating chemical analyses to genome data.

Abstract: The volatile terpenes of 24 actinomycetes whose genomes have been sequenced (or are currently being sequenced) were collected by use of a closed-loop stripping apparatus and identified by GC/MS. The analytical data were compared against a phylogenetic analysis of all 192 currently available sequences of bacterial terpene cyclases (excluding geosmin and 2-methylisoborneol synthases). In addition to the several groups of terpenes with known biosynthetic origin, selinadienes were identified as a large group of biosynthetically related sesquiterpenes that are produced by several streptomycetes. The detection of a large number of previously unrecognised side products of known terpene cyclases proved to be particularly important for an in depth understanding of biosynthetic pathways to known terpenes in actinomycetes. Interpretation of the chemical analytical data in the context of the phylogenetic tree of bacterial terpene cyclases pointed to the function of three new enzymes: (E)-β-caryophyllene synthase, selina-3,7(11)-diene synthase and aristolochene synthase.

Citrus Leaf Volatiles as Affected by Developmental Stage and Genetic Type

Abstract: Major volatiles from young and mature leaves of different citrus types were analyzed by headspace-solid phase microextraction (HS-SPME)-GC-MS. A total of 123 components were identified form nine citrus cultivars, including nine aldehydes, 19 monoterpene hydrocarbons, 27 oxygenated monoterpenes, 43 sesquiterpene hydrocarbons, eight oxygenated sesquiterpenes, two ketones, six esters and nine miscellaneous. Young leaves produced higher amounts of volatiles than mature leaves in most cultivars. The percentage of aldehyde and monoterpene hydrocarbons increased, whilst oxygenated monoterpenes and sesquiterpenes compounds decreased during leaf development. Linalool was the most abundant compound in young leaves, whereas limonene was the chief component in mature ones. Notably, linalool content decreased, while limonene increased, during leaf development in most cultivars. Leaf volatiles were also affected by genetic types. A most abundant volatile in one or several genotypes can be absent in another one(s), such as limonene in young leaves of lemon vs. Satsuma mandarin and β-terpinene in mature leaves of three genotypes vs. the other four. Compositional data was subjected to multivariate statistical analysis, and variations in leaf volatiles were identified and clustered into six groups. This research determining the relationship between production of major volatiles from different citrus varieties and leaf stages could be of use for industrial and culinary purposes.

Chemical characterisation and biological effects of Juniperus foetidissima Willd. 1806

Abstract: The present study was designed to define the phenolic and terpene profile, antioxidant and anti-inflammatory activity of methanol extracts and essential oils of the leaves and seed cones of Juniperus foetidissima species, on which there has been little previous research. The content of 44 phenolics in extracts was determined using LC–MS/MS. A comparable qualitative composition, including dominant compounds catechin, quercitrin, epicatechin, rutin and quercetin-3- O -glucoside, was found in both extracts. GC–MS analysis showed a simple terpene composition, with monoterpenes dominant and sabinene most abundant compound, 39.9% in leaves and 29.9% in seed cones. Antioxidant activity was determined by several assays. All results of antioxidant tests were comparable to BHT, a well-known synthetic antioxidant. A novel method for estimation of anti-inflammatory potential by means of inhibition of COX-1 and 12-LOX activity was described. Essential oils showed significant anti-inflammatory activity, especially of leaves. To conclude, J. foetidissima showed great bio potential, and its usage in production of food and beverages should be considered.

Enzymatic biotransformation of terpenes as bioactive agents.

Abstract: The plant-derived terpenoids are considered to be the most potent anticancer, anti-inflammatory and anticarcinogenic compounds known. Enzymatic biotransformation is a very useful approach to expand the chemical diversity of natural products. Recent enzymatic biotransformation studies on terpenoids have resulted in the isolation of novel compounds. 14-hydroxy methyl caryophyllene oxide produced from caryophyllene oxide showed a potent inhibitory activity against the butyryl cholinesterase enzyme, and was found to be more potent than parent caryophyllene oxide. The metabolites 3β,7β-dihydroxy-11-oxo-olean-12-en-30-oic acid, betulin, betulonic acid, argentatin A, incanilin, 18β glycyrrhetinic acid, 3,11-dioxo-olean-12-en-30-oic acid produced from 18β glycyrrhetinic acid were screened against the enzyme lipoxygenase. 3,11-Dioxo-olean-12-en-30-oic acid, was found to be more active than the parent compound. The metabolites 3β-hydroxy sclareol 18α-hydroxy sclareol, 6α,18α-dihydroxy sclareol, 11S,18α-dihydroxy sc...

Use of cannabinoids and terpenes for treatment of organophosphate and carbamate toxicity

Abstract: Pharmaceutical compositions in which isolated cannabinoid receptor modulators are optionally combined with terpene blends in a pharmaceutically acceptable carrier. Methods for treating or preventing a disease, disorder, dysfunction or condition caused by exposure to an organophosphate or carbamate acetylcholineesterase inhibitor with the inventive compositions are also disclosed.

Cytotoxic activity of ursolic acid derivatives obtained by isolation and oxidative derivatization.

Abstract: Structure-activity relationships of ursane-type pentacyclic triterpenes obtained from natural sources and by chemical derivatization are reviewed. Ursolic acid, corosolic acid, and a new ursane-type pentacyclic triterpene, 7,24-dihydroxyursolic acid, were isolated from the methanolic extract of the leaves of the Bangladeshi medicinal plant, Saurauja roxburghii. Derivatization of ursolic acid by oxidation with dioxoruthenium (VI) tetraphenylporphyrins was investigated. Oxidation selectivity on the terpene structure was modulated by the auxiliaries introduced on the tetraphenylporphyrin. The natural triterpenes and oxidized derivatives were tested for cytotoxicity against the C6 rat glioma and A431 human skin carcinoma cell lines. Although they have the same ursane-type pentacyclic triterpene cores, the position and numbers of hydroxyls on the terpene structures significantly affected the activity and the selectivity towards the tested cell lines.

Pseudomonas: a promising biocatalyst for the bioconversion of terpenes.

Abstract: The Pseudomonas genus is one of the most diverse and ecologically significant groups of known bacteria, and it includes species that have been isolated worldwide in all types of environments. The bacteria from this genus are characterized by an elevated metabolic versatility, which is due to the presence of a complex enzymatic system. Investigations since the early 1960s have demonstrated their potential as biocatalysts for the production of industrially relevant and value-added flavor compounds from terpenes. Although terpenes are often removed from essential oils as undesirable components, its synthetic oxy-functionalized derivatives have broad applications in flavors/fragrances and pharmaceutical industries. Hence, biotransformation appears to be an effective tool for the structural modification of terpene hydrocarbons and terpenoids to synthesize novel and high-valued compounds. This review highlights the potential of Pseudomonas spp. as biocatalysts for the bioconversion of terpenes and summarizes the presently known bioflavors that are obtained from these processes.

A sensitive method for determination of allergenic fragrance terpene hydroperoxides using liquid chromatography coupled with tandem mass spectrometry

Abstract: Different compositions of monoterpenes are utilized for their pleasant scent in cosmetics and perfumes. However, the most commonly used fragrance terpenes easily oxidize upon contact with air, forming strongly skin-sensitizing hydroperoxides. Due to their thermolability and low UV absorbance, detection methods for hydroperoxides are scarce. For the first time, a simple and sensitive method using LC/ESI-MS/MS was developed to quantitatively determine hydroperoxides from the common fragrance compounds linalool, linalyl acetate, and limonene. The method was applied to autoxidized petitgrain oil and sweet orange oil. A separation was accomplished using a C3 column. The method LOD for the investigated hydroperoxides in the essential oils was below 0.3 μg/mL, corresponding to 0.3 ppm. For prevention purposes and according to EU regulations, concentrations in cosmetics exceeding 100 ppm in "rinse-off" and 10 ppm in "stay-on" products of linalool and limonene must be labeled. However, the products may still contain allergens, such as hydroperoxides, formed by oxidative degradation of their parent terpenes. The sensitivity and selectivity of the presented LC/MS/MS method enables detection of hydroperoxides from the fragrance terpenes linalool, linalyl acetate, and limonene. However, for routine measurements, the method requires further validation.

Highly variable chemical signatures over short spatial distances among Scots pine (Pinus sylvestris) populations.

Abstract: Understanding within-species variability in terpenoid content and composition is highly relevant for predicting species adaptive potential to biotic stresses, but there is still limited information on terpene variations even for widespread species. We studied the foliage content and composition of terpenoids, foliage structure, and carbon (C) and nitrogen (N) contents in Pinus sylvestris L. in four Estonian sites ranging from dry forest to raised bog. In the bogs, samples were taken along the environmental gradient from drier margins towards wetter central parts. A chiral column was used to gain insight into the variation in terpene composition. We hypothesized that terpene contents increase and the composition becomes more diverse in more strongly N-limited sites (greater C/N ratio) and that terpene signatures cluster together in sub-sites with similar conditions (drier/wetter). Altogether 37 terpenes were quantified across the sites. Extremely large variability of terpene contents, 48-62% for monoterpenes and 61-89% for sesquiterpenes, was observed. According to the amounts of α-pinenes and (+)-3-carene, we distinguished two different 'pine chemotypes'. Contrary to the hypothesis, terpene contents and variability were the greatest in the dry site with the lowest C/N ratio. However, individual terpenoids correlated differently with C or N in different sites, indicating site effects on terpene composition. Moreover, correlations between the terpenoids and C or N depended on the pine chemotype. The sub-sites with different water regime were more strongly clustered together within the site than across the sites. The study demonstrates extensive variations in terpene contents and composition among the populations and over short spatial distances within the populations, suggesting a large among- and within-population adaptive capacity of P. sylvestris.

Unique Biosynthesis of Sesquarterpenes (C35 Terpenes)

Abstract: To the best of my knowledge, only 19 cyclic and 8 linear C35 terpenes have been identified to date, and no family name was assigned to this terpene class until recently. In 2011, it was proposed that these C35 terpenes should be called sesquarterpenes. This review highlights the biosynthesis of two kinds of sesquarterpenes (C35 terpenes) that are produced via cyclization of a linear C35 isoprenoid in Bacillus and Mycobacterium species. In Bacillus species, a new type of terpene cyclase that has no sequence homology with any known terpene synthases, as well as a bifunctional terpene cyclase that biosynthesizes two classes of cyclic terpenes with different numbers of carbons as natural products, have been identified. On the other hand, in Mycobacterium species, the first bifunctional Z-prenyltransferase has been found, but a novel terpene cyclase and a unique polyprenyl reductase remain unidentified. The identification of novel enzyme types should lead to the discovery of many homologous enzymes and their products including novel natural compounds. On the other hand, many enzymes responsible for the biosynthesis of natural products have low substrate specificities in vitro. Therefore, to find novel natural products present in organisms, the multifunctionality of enzymes in the biosynthetic pathway of natural products should be analyzed.

Using volatile organic compounds to enhance atrazine biodegradation in a biobed system

Abstract: The effect of the terpenes α-pinene, eucalyptol, and limonene, individually and as mixtures, on atrazine (ATZ) biodegradation and on biological activity in a biobed biomixture was evaluated Additionally, terpenes emitted from the biomixture were captured using solid-phase microextraction Terpenes added individually at relatively low concentrations (50 μg kg−1) significantly enhanced ATZ degradation and biological activity during the first incubation days No significant effect on ATZ degradation was found from adding the terpene mixture, and, interestingly, an inhibitory effect on phenoloxidase activity was found during the first 20 days of incubation when mixed terpenes were present at 100 μg kg−1 Capturing terpenes demonstrated that during the first hour of incubation a significant fraction of the terpenes was volatilized These results are the first to demonstrate the feasibility of using terpenes to enhance the degradation of a pesticide However, successive applications of terpenes or the addition of materials that slowly release terpenes could sustain the ATZ degradation enhancement

Determination of Terpenoids in Plant Leaves by GC-MS: Development of the Method and Application to Ocimum basilicum and Nicotiana langsdorffii

Abstract: In this work a simple and sensitive analytical method was developed for the determination of terpenoids in plants using gas chromatography coupled to mass spectrometry (GC-MS). Three extraction methods were tested on Ocimum basilicum leaves to maximize terpene extraction: Steam Distillation, Ultrasound-Assisted Extraction, and Microwave-Assisted Extraction (MAE). Best results, both in number of identified compounds and in their concentration, were obtained with MAE, which was used in all subsequent analyses. In particular five terpenoids (α-pinene, β-pinene, limonene, linalool, and α-terpineol) were chosen for the quantitative determination, performed in Selected Ion Monitoring mode. Calibration curves using dodecane as internal standard were drawn, showing good correlation coefficients (0.9981–0.9993). All figures of merit were satisfactory; limits of detection were in the range 14–27 ng for all analytes. The method was also applied to some specimens of wild-type and transgenic (GR and rolC) Nicotiana la...

Structural Requirements for Potent Direct Inhibition of Human Cytochrome P450 1A1 by Cannabidiol: Role of Pentylresorcinol Moiety

Abstract: Our recent work has shown that cannabidiol (CBD) exhibits the most potent direct inhibition of human cytochrome P450 1A1 (CYP1A1) among the CYP enzymes examined. However, the mechanism underlying this CBD inhibition remains to be clarified. Thus, to elucidate the structural requirements for the potent inhibition by CBD, the effects of CBD and its structurally related compounds on CYP1A1 activity were investigated with recombinant human CYP1A1. Olivetol, which corresponds to the pentylresorcinol moiety of CBD, inhibited the 7-ethoxyresorufin O-deethylase activity of CYP1A1; its inhibitory effect (IC50=13.8 µM) was less potent than that of CBD (IC50=0.355 µM). In contrast, d-limonene, which corresponds to the terpene moiety of CBD, only slightly inhibited CYP1A1 activity. CBD-2'-monomethyl ether (CBDM) and CBD-2',6'-dimethyl ether inhibited CYP1A1 activity with IC50 values of 4.07 and 23.0 µM, respectively, indicating that their inhibitory effects attenuated depending on the level of methylation on the free phenolic hydroxyl groups in the pentylresorcinol moiety of CBD. Cannabidivarin inhibited CYP1A1 activity, although its inhibitory potency (IC50=1.85 µM) was lower than that of CBD. The inhibitory effects of Δ(9)-tetrahydrocannabinol and cannabielsoin (IC50s ≈10 µM), which contain a free phenolic hydroxyl group and are structurally constrained, were less potent than that of CBDM, which contains a free phenolic hydroxyl group and is rotatable between pentylresorcinol and terpene moieties. These results suggest that the pentylresorcinol structure in CBD may have structurally important roles in direct CYP1A1 inhibition, although the whole structure of CBD is required for overall inhibition.

Increased production of terpenes and terpenoids

Abstract: This invention provides recombinant cells and methods for producing terpenes and terpenoids by increasing production or accumulation or both of isoprenoid precursors thereof.

Volatiles, A Glutarimide Alkaloid and Antimicrobial Effects of Croton pullei (Euphorbiaceae)

Abstract: Chemical investigation of Croton pullei (Euphorbiaceae) collected in the Brazilian Amazon region was revisited. The chemical composition of the essential oils of leaves and stems was analyzed by GC/MS. It was found that both the oils comprise mainly terpenes, among which linalool was the major one (24.90 and 39.72%, respectively). Phytochemical investigation of the stem methanol extract led to the isolation of a new natural product from the glutarimide alkaloid group named N-[2,6-dioxo-1-(2-phenylethyl)-3-piperidinyl]-acetamide, confirming that C. pullei is a rich source of this class of alkaloids. The hexane and methanol extracts of the stems of C. pullei showed moderate antibacterial and antifungal activity and the highest inhibition was observed when the methanol extract was tested against Staphylococcus aureus CCMB 262 and CCMB 263.