Constituents Of Plant Essential Oils Research Articles

Hologram quantitative structure-activity relationship on the gas chromatographic retention index of plant essential oil constituents

The gas chromatography retention index (RI) is an important parameter for the identification of different types of compounds in the field of chromatographic analysis; however, the experimental collection of RI values is a extremely cumbersome process. Thus, there is an urgent need for the establishment of a simple, efficient, and accurate model for the prediction of the RI values of compounds. In this study, first, the experimental RI values for 60 plant essential oil constituents were obtained. Next, a model describing the hologram quantitative structure-activity relationship (HQSAR) between the structural properties of the essential oil constituents and their RI values was investigated and constructed. The optimal HQSAR model was established by setting the model parameters "fragment size", "fragment distinction", "hologram length" and "principal components" to "1-4", "C, Ch", "199", and "4", respectively. Finally, the predictive ability of the model was verified using external test set validation and leave-one-out cross-validation (LOO-CV). The experimental results were as follows, the root mean square error of prediction (RMSEP), predictive determination coefficient ([Formula: see text]), concordance correlation coefficient (CCC), and mean relative error (MRE) for external test set validation were 40.45, 0.984, 0.968, and 2.20%, respectively. Meanwhile, the root mean square error of cross validation (RMSECV) and MRE for LOO-CV were 72.56 and 4.17%, respectively. These findings demonstrate that the established HQSAR model has a good predictive ability and can accurately predict the RI values of plant essential oil constituents. In addition, the molecular contribution maps of the HQSAR model revealed that the RI values of aromatic compounds increase when hydroxyl groups are connected to their alkyl chains. Aliphatic compounds feature long chain alkyl groups, which can lead to an increase in RI values. The above phenomena highlight the promising application prospects of HQSAR for studying the RI values of plant essential oil constituents. Therefore, this study provides a reliable theoretical basis for predicting the RI values of other essential oil constituents.

Plant essential oil constituents enhance deltamethrin toxicity in a resistant population of bed bugs (Cimex lectularius L.) by inhibiting cytochrome P450 enzymes

Plant essential oils (EOs) are secondary metabolites derived from aromatic plants that are composed of complex mixtures of chemical constituents. EOs have been proposed as one of the alternative methods for bed bug (Cimex lectularius L.) control. In insecticide resistant mosquitoes and tobacco cutworm, EOs synergize pyrethroid toxicity by inhibiting detoxification enzymes. However, whether EOs and their constituents enhance pyrethroid toxicity in C. lectularius has remained unknown. Therefore, this study was designed to (i) determine the effects of binary mixtures of deltamethrin (a pyrethroid insecticide) with EOs or EO constituents or EcoRaider® (an EO-based product) on mortality of insecticide resistant and susceptible bed bugs, and (ii) evaluate the effects of EO constituent pre-treatment on detoxification enzyme activities of resistant and susceptible populations. Topical bioassays with binary mixtures of deltamethrin and individual EOs (e.g., thyme, oregano, clove, geranium or coriander oils) or their major constituents (e.g., thymol, carvacrol, eugenol, geraniol or linalool) or EcoRaider® at doses that kill approximately 25% of bed bugs caused significant increases in mortality of resistant bed bugs. However, in the susceptible population, only coriander oil, EcoRaider®, thymol, and carvacrol significantly increased the toxicity of deltamethrin. Detoxification enzyme assays with protein extracts from bed bugs pre-treated with EO constituents suggested selective inhibition of cytochrome P450 activity in the resistant population, but no impacts were observed on esterase and glutathione transferase activities in either population. Inhibition of P450 activity by EO constituents thus appears to be one of the mechanisms of deltamethrin toxicity enhancement in resistant bed bugs.

The Larvicidal and Adulticidal Effects of Selected Plant Essential Oil Constituents on Greater Wax Moths.

Some plant essential oil constituents, such as monoterpenoids and phenylpropanoids, are promising insecticides in some situations and for certain insect pests. They vary in their toxicity, depending on the target insect. Moths (Lepidoptera) appear susceptible to these compounds, making them of promise for use against greater wax moths (Galleria mellonella Fabricius, (Lepidoptera: Pyrallidae), GWM), an important pest of western honey bee (Apis mellifera Linnaeus. (Hymenoptera: Apidae)) colonies. We determined the LC50 for GWM larvae or LD50 for GWM adults of select compounds (thymol, carvacrol, (S)-(+)-carvone, estragole, citral, linalool, (S)-(-)-limonene, and γ-terpinene). Concentrations between 8 and 2,266 µg/cm3 were mixed into the diets of GWM larvae and doses ranging between 0.08 and 70.3 mg per adult were applied topically to the abdomens of GWM adults. Lethal concentrations and doses were calculated after of 72 h of exposure. All eight compounds showed insecticidal activity against all tested stages of GWMs. Thymol (LC50 µg/cm3 (95% CI) = 21 [9-56], carvacrol = 46 [26-79], citral = 63 [30-134], and carvone = 76 [33-201]) had the highest toxicity toward GWM larvae. The hydrocarbons limonene (296 [231-377]), estragole (466 [354-611]), and γ-terpinene (729 [630-857]) had the lowest toxicity toward GWM larvae. Thymol had the highest toxicity towards GWM adults (LD50 (CI) = 0.5 [0.4-0.8] mg/adult). However, carvacrol (11.6 [10.1-13.6]), linalool (12.9 [9.3-17.8]), and limonene (15.8 [13.1-19.2]) were less toxic to GWM larvae. Our data show that select plant essential oil constituents are promising controls of GWM.

Sulfenate Esters of Simple Phenols Exhibit Enhanced Activity against Biofilms.

The recalcitrance exhibited by microbial biofilms to conventional disinfectants has motivated the development of new chemical strategies to control and eradicate biofilms. The activities of several small phenolic compounds and their trichloromethylsulfenyl ester derivatives were evaluated against planktonic cells and mature biofilms of Staphylococcus epidermidis and Pseudomonas aeruginosa. Some of the phenolic parent compounds are well-studied constituents of plant essential oils, for example, eugenol, menthol, carvacrol, and thymol. The potency of sulfenate ester derivatives was markedly and consistently increased toward both planktonic cells and biofilms. The mean fold difference between the parent and derivative minimum inhibitory concentration against planktonic cells was 44 for S. epidermidis and 16 for P. aeruginosa. The mean fold difference between the parent and derivative biofilm eradication concentration for 22 tested compounds against both S. epidermidis and P. aeruginosa was 3. This work demonstrates the possibilities of a new class of biofilm-targeting disinfectants deploying a sulfenate ester functional group to increase the antimicrobial potency toward microorganisms in biofilms.

Combination of mild heat and plant essential oil constituents to inactivate resistant variants of Escherichia coli in buffer and in coconut water

The growing demand for minimally processed foods with clean labels has stimulated research into mild processing methods and natural antimicrobials to replace intensive heating and conventional preservatives, respectively. However, we have previously demonstrated that repetitive exposure of some bacteria to mild heat or subinhibitory concentrations of essential oil constituents (EOCs) may induce the emergence of mutants with increased resistance to these treatments. Since the combination of mild heat with some EOCs has a synergistic effect on microbial inactivation, we evaluated the potential of such combinations against our resistant E. coli mutants. While citral, carvacrol and t-cinnamaldehyde synergistically increased heat inactivation (53.0 °C, 10 min) of the wild-type MG1655 suspended in buffer, only the combination with carvacrol (200 μl/l) was able to mitigate the increased resistance of all the mutants. Moreover, the combination of heat and carvacrol acted synergistically inactivating heat-resistant variants of E. coli O157:H7 (ATCC 43888). This combined treatment could synergistically achieve more than 5 log10 reductions of the most resistant mutants in coconut water, although the temperature had to be raised to 57.0 °C. Therefore, the combination of mild heat with carvacrol appears to hold promise for mild processing, and it is expected to counteract the development of heat resistance.

Toxicity and neurophysiological impacts of plant essential oil components on bed bugs (Cimicidae: Hemiptera)

Bed bugs (Cimex lectularius L.) are globally important human parasites. Integrated pest management (IPM) approaches, which include the use of essential oil-based insecticidal compounds, have been proposed for their control. This study aimed to define insecticidal activity and neurophysiological impacts of plant essential oil constituents. The topical and fumigant toxicity of 15 compounds was evaluated against adult male bed bugs. Neurological effects of the 6 most toxicologically active compounds were also determined. In both topical and fumigant bioassays, carvacrol and thymol were the most active compounds. The potency of bifenthrin (a pyrethroid insecticide) in topical bioassays was 72,000 times higher than carvacrol, while vapors of dichlorvos (an organophosphate insecticide) were 445 times more potent than thymol. Spontaneous electrical activity measurements of the bed bug nervous system demonstrated neuroinhibitory effects of carvacrol, thymol and eugenol, whereas linalool produced an excitatory effect. Although citronellic acid and (±)-camphor increased baseline activity of the nervous system their effects were not statistically significant. Bifenthrin also caused neuroexcitation, which is consistent with its known mode of action. These comparative toxicity and neurological impact findings provide new information for formulating effective essential oil-based insecticides for bed bug IPM and conducting mode-of-action studies on individual essential oil components.

Cyanobacterial production of plant essential oils.

Synechocystis (a cyanobacterium) was employed as an alternative host for the production of plant essential oil constituents. β-Phellandrene synthase (PHLS) genes from different plants, when expressed in Synechocystis, enabled synthesis of variable monoterpene hydrocarbon blends, converting Synechocystis into a cell factory that photosynthesized and released useful products. Monoterpene synthases are secondary metabolism enzymes that catalyze the generation of essential oil constituents in terrestrial plants. Essential oils, including monoterpene hydrocarbons, are of interest for their commercial application and value. Therefore, heterologous expression of monoterpene synthases for high-capacity essential oil production in photosynthetic microorganism transformants is of current interest. In the present work, the cyanobacterium Synechocystsis PCC 6803 was employed as an alternative host for the production of plant essential oil constituents. As a case study, β-phellandrene synthase (PHLS) genes from different plants were heterologously expressed in Synechocystis. Genomic integration of individual PHLS-encoding sequences endowed Synechocystis with constitutive monoterpene hydrocarbons generation, occurring concomitant with photosynthesis and cell growth. Specifically, the β-phellandrene synthase from Lavandula angustifolia (lavender), Solanum lycopersicum (tomato), Pinus banksiana (pine), Picea sitchensis (Sitka spruce) and Abies grandis (grand fir) were active in Synechocystis transformants but, instead of a single product, they generated a blend of terpene hydrocarbons comprising β-phellandrene, α-phellandrene, β-myrcene, β-pinene, and δ-carene with variable percentage ratios ranging from < 10 to > 90% in different product combinations and proportions. Our results suggested that PHLS enzyme conformation and function depends on the cytosolic environment in which they reside, with the biochemical properties of the latter causing catalytic deviations from the products naturally observed in the corresponding gene-encoding plants, giving rise to the terpene hydrocarbon blends described in this work. These findings may have commercial application in the generation of designer essential oil blends and will further assist the development of heterologous cyanobacterial platforms for the generation of desired monoterpene hydrocarbon products.

Toxic essential oils. Part V: Behaviour modulating and toxic properties of thujones and thujone-containing essential oils of Salvia officinalis L., Artemisia absinthium L., Thuja occidentalis L. and Tanacetum vulgare L.

Neurotoxic thujones (α- and β-diastereoisomers) are common constituents of plant essential oils. In this study, we employed a statistical approach to determine the contribution of thujones to the overall observed behaviour-modulating and toxic effects of essential oils (Salvia officinalis L., Artemisia absinthium L., Thuja occidentalis L. and Tanacetum vulgare L.) containing these monoterpene ketones. The data from three in vivo neuropharmacological tests on rats (open field, light-dark, and diazepam-induced sleep), and toxicity assays (brine shrimp, and antimicrobial activity against a panel of microorganisms), together with the data from detailed chemical analyses, were subjected to a multivariate statistical treatment to reveal the possible correlation(s) between the content of essential-oil constituents and the observed effects. The results strongly imply that the toxic and behaviour-modulating activity of the oils (hundreds of constituents) should not be associated exclusively with thujones. The statistical analyses pinpointed to a number of essential-oil constituents other than thujones that demonstrated a clear correlation with either the toxicity, antimicrobial effect or the activity on CNS. Thus, in addition to the thujone content, the amount and toxicity of other constituents should be taken into consideration when making risk assessment and determining the regulatory status of plants in food and medicines.

Penetration-enhancement underlies synergy of plant essential oil terpenoids as insecticides in the cabbage looper, Trichoplusia ni

Many plant essential oils and their terpenoid constituents possess bioactivities including insecticidal activity, and they sometimes act synergistically when mixed. Although several hypotheses for this have been proposed, the underlying mechanism has not been fully elucidated thus far. In the present study, we report that in larvae of the cabbage looper, Trichoplusia ni, most synergistic or antagonistic insecticidal activities among mixtures of plant essential oil constituents are pharmacokinetic effects, owing to changes in solubility as well as spreadability on a wax layer. Among the major constituents of rosemary (Rosmarinus officinalis) oil, in vitro analysis revealed up to a 19-fold increase in penetration of camphor in a binary mixture with 1,8-cineole through the larval integument, suggesting increased penetration as the major mechanism for synergy. A total of 138 synergistic or antagonistic interactions among 39 compounds were identified in binary mixtures via topical application, and these were highly correlated to changes in surface tension as measured by contact angle of the mixtures on a beeswax layer. Among compounds tested, trans-anethole alone showed evidence of internal synergy, whereas most of remaining synergistic or antagonistic combinations among the three most active compounds were identified as penetration-related interactions, confirmed via a divided-application bioassay.

Effects of rosemary, thyme and lemongrass oils and their major constituents on detoxifying enzyme activity and insecticidal activity in Trichoplusia ni

Although there have been many reports on the synergistic interactions among the major constituents of plant essential oils regarding insecticidal activity, their underlying mechanism of synergy is poorly understood. In our previous studies, we found each of the two most abundant constituents of rosemary (Rosmarinus officinalis L.), thyme (Thymus vulgaris L.) and lemongrass (Cymbopogon citratus Stapf.) essential oils can be synergistic against the larvae of the cabbage looper, Trichoplusia ni at their natural proportion or equivalent blending ratios. In the present study, we investigated whether the enhanced toxicity between the major constituents could be the result of inhibited enzyme activity of cytochrome P450s, general esterases or glutathione S-transferases which are highly related to the development of insecticide resistance. Overall, although some combinations showed mild inhibitory activity, at least for these essential oils and their major constituents, inhibition of detoxication enzyme activity is unlikely to be a direct cause of increased toxicity in the cabbage looper. The results point to other factors, such as multiple modes-of-action or enhanced penetration through the cuticular layer, playing important roles in the elevated insecticidal activity. Moreover, application of enzyme inhibitors sometimes resulted in decreased activity when mixed with the target compounds, but these antagonistic interactions disappeared when they were applied separately, suggesting that the enzyme inhibitors can sometimes influence the penetrations of toxicants.

A Review on Terpenes as Skin Penetration Enhancers in Transdermal Drug Delivery

The skin itself hinders the widespread use of transdermal drug delivery (TDD) for administration of medication. Despite the different strategies devised and employed to reversibly overcome the skin barrier, this non-invasive delivery mode is restricted to potent, low molar mass therapeutic agents. The use of chemical penetration enhancers is the conventional approach to modify the skin structure and lower its resistance for increased drug permeation. Over the years, extensive screening and testing have identified different classes of chemicals as potential adjuvants. Among these, terpenes (constituents of plant essential oils) have been widely investigated as skin penetration enhancers for both hydrophilic and hydrophobic drugs. In particular, monoterpenes were generally more effcacious probably due to their small molecular sizes. The main mechanisms of action of terpenes on the skin as determined by several analytical techniques were lipid extraction and phase separation. Terpenes such as limonene and menthol in experimental patch formulations were demonstrated to be safe on the skin and effective in improving drug delivery across the skin.

Influence of essential oils on toxicity and pharmacokinetics of the plant toxin thymol in the larvae of Trichoplusia ni

AbstractThe present study was undertaken to determine the influence of some major constituents of plant essential oils on the toxicity and fate of thymol, a phenolic monoterpene from garden thyme (Thymus vulgaris L.) (Lamiaceae), following topical administration to the cabbage looper, Trichoplusia ni (Hubner) (Lepidoptera: Noctuidae). Tested individually, trans-anethole (LD50 = 71.2 µg/larva) and methyl salicylate (93.6 µg/larva) were the most toxic, whereas phenylethyl propionate (555.8 µg/larva) and mineral oil (2279.3 µg/larva) were the least toxic. However, when coadministered, mineral oil was the most synergistic (synergy ratio, SR = 25). A proprietary blend of essential oils (A4 Blend) was strongly synergistic (SR = 9), as was trans-anethole (SR = 5), while the majority of the other compounds tested yielded SRs of 2–3. Based on experiments using tritiated thymol as a radiotracer, the fate of this plant toxin within 60 min of topical administration varied widely with the essential oil carrier. Some carriers facilitated rapid disappearance of thymol from the insects' integument and rapid appearance internally, whereas others prolonged the tenure of thymol on the integument and delayed entry into the insect. The highest internal levels of radioactivity were observed when phenylethyl propionate was the carrier (47% of the topical dose), the lowest when rosemary oil was the carrier (9%). The highest proportion of the dose was excreted when eugenol was the carrier (20% of the topical dose), the lowest when mineral oil was the carrier (4%). Overall, there are no apparent trends linking the fate of thymol in the different carrier oils to the synergies observed or to the relative polarities of the carriers.