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Rheumatoid arthritis (RA) is a chronic systemic autoimmune disease with predominant synovitis that has no complete cure or preventive treatment. Citrus essential oils, used in natural fragrances, contain a variety of functional ingredients that are worthy of investigation for their potential as natural anti-inflammatory drug sources. In this study, essential oils were hydro distilled from the peels of four citrus species: Citrus sinensis (L.) Osbeck (CSEOs), Citrus paradisi Macfad. (CPEOs), Citrus limon (L.) Osbeck (CLEOs) and Citri Reticulatae Pericarpium (CREOs). Altogether, 81 compounds were identified using gas chromatography-mass spectrometry (GC-MS), of which d-limonene (17.96%-94.66%) was an abundant component of all four oils. The stable 1,1-diphenyl-2-pyrrole hydrazine (DPPH) free radical test showed that all four essential oils had excellent antioxidant properties (IC

Background In 2019, a number of allergens (haptens), henceforth, "the audit allergens," were considered as potential additions to the European Baseline Series (EBS), namely, sodium metabisulfite, 2-bromo-2-nitropropane-1,3-diol, diazolidinyl urea, imidazolidinyl urea, Compositae mix II (2.5% or 5% pet), linalool hydroperoxides (lin-OOH), limonene hydroperoxides (lim-OOH), benzisothiazolinone (BIT), octylisothiazolinone (OIT), decyl glucoside, and lauryl glucoside; Evernia furfuracea (tree moss), was additionally tested by some departments as well. Objectives To collect further data on patch test reactivity and clinical relevance of the audit allergens in consecutive patients across Europe. Methods Patch test data covering the audit allergens in 2019 and 2020 were collected by those departments of the European Surveillance System on Contact Allergies testing these, as well as further collaborators from the EBS working group of the European Society of Contact Dermatitis (ESCD), and the Spanish Grupo Espanol de Investigacion en Dermatitis de Contacto y Alergia Cutanea. As patch test outcome, reactions between day (D) 3 and D5 were considered. Results Altogether n = 12 403 patients were tested with any of the audit allergen. Positive reactions were most common to lin-OOH 1% pet. (8.74% [95%CI: 8.14-9.37%]), followed by lin-OOH 0.5% pet., and lim-OOH 0.3% pet (5.41% [95% CI: 4.95-5.89%]). Beyond these terpene hydroperoxides, BIT 0.1% pet. was the second most common allergen with 4.72% (95% CI: 4.2-5.28%), followed by sodium metabisulfite 1% pet. (3.75% [95%CI: 3.32-4.23%]) and Compositae mix 5% pet. (2.31% [95% CI: 1.84-2.87%]). For some allergens, clinical relevance was frequently difficult to ascertain. Conclusions Despite many positive patch test reactions, it remains controversial whether lin- and lim-OOH should be tested routinely, while at least the two preservatives BIT and sodium metabisulfite appear suitable. The present results are a basis for further discussion and ultimately decision on their implementation into routine testing among the ESCD members.

Onychomycosis, the most prevailing affliction of the nail, accounts for approximately 90% of the toenail infection worldwide. Owing to this infection, the affected patients experience reduced quality of their life as its awful appearance undermines their daily activities and social interactions. Onychomycosis is notoriously strenuous to cure. Systemic therapy, though effective, possess severe complication of toxicities, contra-indication, and drug-drug interaction. Albeit topical therapy is favorable to its localized effect, its potency relates to the effective concentration of the antifungal drugs achieved at the infection site. An approach to accomplish this goal would be acquiring benefits from the terpenes as penetration enhancers from natural sources. This investigation aimed to study the effectiveness of six terpenes, namely safranal, lavandulol, rose oxide, 3-methyl-2-butene-1-ol, linalool, and limonene, as potential penetration enhancers for improved nail permeation of fluconazole through the human nail.Ex vivo permeation experiments were carried out by soaking the nail clippings of human volunteers in control and working solutions containing fluconazole (5 mg/ml) per se and fluconazole (5 mg/ml) with 6% of each terpene, including safranal, lavandulol, rose oxide, 3-methyl-2-butene-1-ol, linalool, and limonene, respectively, for 48 h. The amount of fluconazole in nail clippings was quantified using an HPLC method.Statistical analysis showed that fluconazole transungual permeation was influenced by the studied terpenes in the following order: safranallavandulol acetatelimonenerose oxide (p-value0.05) while the other terpenes showed no significant difference with the control group and safranal represents as the most effective permeation enhancer for the transungual delivery of fluconazole.It is concluded that the safranal can be successfully used as a safe and potential permeation enhancer to enhance the transungual delivery of fluconazole for the treatment of onychomycosis.

Limonene-1,2-diol is a limonene oxygenated metabolite that possesses eight different stereoisomers, which could result in different biological properties. Nonetheless, the relation between its spatial configuration and biological function is still little explored. The present study aimed to perform the stereoisomers identification using nuclear magnetic resonance (NMR) investigation of the limonene-1,2-diol produced via R-(+)- and S-(-)-limonene biotransformation by Colletotrichum nymphaeae and S-(-)-limonene biotransformation by Fusarium oxysporum 152B. Besides, in vitro antiproliferative activity was evaluated against human tumor and nontumor cell lines. The NMR analysis showed that R-(+)-limonene biotransformation afforded exclusively (+)-(1S,2S,4R-limonene-1,2-diol), whereas S-(-)-limonene biotransformation afforded exclusively (-)-(1R,2R,4S-limonene-1,2-diol) independent on the fungi used. Despite no significant cytostatic effects, a possible influence of stereogenic center on the antiproliferative activity of these limonene biotransformation products was evidenced. Moreover, the lack of in vitro antiproliferative effect of limonene-1,2-diol against nontumor cells suggested a safe dose range for further in vivo evaluations, including food applications.

BACKGROUND: Contact allergy to oxidized (ox.) linalool and ox. limonene has been reported to have a high prevalence, raising the question of inclusion into the baseline series. However, several important issues should be clarified and further investigated before inclusion can be warranted.OBJECTIVES: To report the trends of ox. terpenes allergy in patients with dermatitis, features of the patch test reactions, and clinical characteristics of the patients.METHODS: A retrospective analysis of 5773 patients was performed. All patients were patch tested with baseline series, individual ingredients of fragrance mix I and II, ox. linalool, and ox. limonene from 2013 to 2020.RESULTS: The prevalence rates of contact allergy to ox. linalool and ox. limonene were 7.0% and 5.1%, respectively. Significantly increasing trends of contact allergy were observed. More than 95% of contact allergy cases were identified on Day 3/4. Patients with contact allergy to ox. linalool and ox. limonene were significantly younger than those with contact allergy to other fragrances and were predominantly female. Strong reactions were associated with older age and multiple fragrance allergies.CONCLUSIONS: Contact allergy to ox. linalool and ox. limonene is becoming increasingly important, and findings show intriguing features. More studies concerning the clinical relevance before recommending these substances for screening are required. (Less)

Acknowledging the importance of medicinal compounds, flavonoids, and phenolic acids in plants and human health; understanding the best time to harvest plants to get the most potentially therapeutic biological activity; and predicting and controlling the quality of medicinal plants are very useful. The rich chemical composition of medicinal lavender, as well as its antioxidant activity, has led to its wide application in the pharmaceutical, cosmetic, and food industries. In the current research, seasonal differences in phenolic content; the main constituents of essential oil, essential oil yield, and antioxidant activity; and flavonoid content were evaluated. In this investigation, for all the investigated factors, three replications were considered as completely randomized designs. The predominant natural components were α-pinene, camphene, 1,8-cineole, limonene, camphor, borneol, cryptone, isobornyl formate, cumin aldehyde, carvone, caryophyllene oxide, and epi-α-cadinol. The highest rate of 1,8-cineole was seen in summer, while camphor and borneol showed their highest percentages in the cold season. Some of the compounds such as caryophyllene oxide, isobornyl formate, and cumin aldehyde showed their highest amounts in the spring with the activation of some important plant enzymes such as peroxidase. The total content of flavonoids and some phenolic compounds (coumarin and p-coumaric acid) increased when plants received sunlight for a longer time than in the colder to warmer seasons. On the other hand, increases in chlorogenic acid and vanillin were observed in spring. Also, the highest antioxidant activity was observed in lavender, which was accompanied by an increase in the important phenolic composition of rosmarinic acid in the cold season. Generally, this investigation provides beneficial evidence about the most appropriate harvest time for lavender to produce the most favorable constituents for optimization in food, pharmaceutical, and herbal products.

Magnolia grandiflora is an aromatic plant widely distributed around the world. In Colombia, and more specifically in Bogotá, M. grandiflora has been introduced as part of urban forestry programs, and their specimens are therefore subjected to several environments. Nevertheless, there are no previous studies on the chemical composition of such plants. Hence, the characterization of the essential oil from 20 specimens of M. grandiflora from Bogotá, Colombia, by GC/MS was carried out here. Two different chemotypes were found. While one was characterized by monoterpenes α-pinene, β-pinene, and limonene, the other contained mainly sesquiterpenes β-elemene, bicyclogermacrene, and germacrene D. Multivariate statistical analyses confirmed their existence and helped to identify variations within and between chemotypes. Furthermore, differential expression of genes encoding the terpene synthases Mg25 and Mg17 could arguably be responsible for the characteristic compositions of both chemotypes, as suggested by rational biosynthetic analysis of the most contrasting metabolites.

Erigeron Canadensis L. (E. canadensis) is a widely distributed invasive weed species in China. Potentially anti-cancer qualities may exist in its essential oils (EOs). The purpose of this study was to analyze the components of the EOs of E. canadensis and their effects on the normal liver cell lines L02 and the human cervical cancer cell lines HeLa. The EOs from the upper region of E. canadensis were prepared, its components were identified by GC/MS. Cell viability, cell morphology observation, AO/EB dual fluorescence staining assay, flow cytometry, mitochondrial membrane potential, western blot, caspase inhibitor test, and oxidative stress tests were used to investigate the impact of the EOs on HeLa cells. Network pharmacological analysis was employed to study the potential mechanism of the EOs in the treatment of cervical cancer. According to the findings, the EOs had 21 chemical components, of which limonene made up 65.68 %. After being exposed to the EOs, the cell viability of HeLa and L02 dramatically declined. The inhibition of EOs was more effective than that of limonene when used in an amount equivalent to that in the EOs. L02 cells were less susceptible to the cytotoxicity of EOs than HeLa cells were. Furthermore, EOs altered the cell cycle in HeLa cells and caused oxidative stress and apoptosis. Compared with the control group, the reactive oxygen species (ROS) levels increased in HeLa cells at first and then decreased, total superoxide dismutase (SOD) and catalase (CAT) activities in HeLa cells significantly decreased. G1 phase cells decreased whereas G2/M phase cells increased. The rate of apoptosis rose. Reduced mitochondrial membrane potential and Caspase-3, -9, and -12 protein expression were both observed. Nerolidol, dextroparaffinone, and α-pinene were shown to be the primary components for the suppression of HeLa cells, according to the results of the prediction of pharmacologic targets. In conclusion, findings of this study indicated the EOs may have the potential to curb the growth of cervical cancer cells. Further research is needed to explore the in vivo effect of EOs.

(R)-Limonene, a renewable terpene, and its epoxidized derivatives, i. e. limonene epoxides, have prompted growing attention over the last decade as building blocks for the synthesis of biobased monomers and polymers. With the goal of replacing petroleum-based polymers several polymerization techniques have been applied on limonene oxide and limonene dioxide monomers. This paper aims to contribute to the literature by presenting a review dedicated to limonene oxide and dioxide as raw monomers of renewable origin for the development of biobased polymers. The polymerization techniques described are namely the homopolymerization, the copolymerization with carbon dioxide and anhydrides, and the copolymerization of limonene epoxide-based monomers. Limonene oxide polymerizations will be investigated first, followed by limonene dioxide polymerizations.

Fish oil rich in long‐chain polyunsaturated fatty acids, vitamin D3 and carotenoid pigments have been sustainably extracted from anchovy fillet leftovers using biobased limonene. The oil is conveniently stabilized by adsorption on periodic mesoporous silicas. The simplicity of the process, the high load of fish oil, and the biocompatible nature of mesoporous silica support numerous forthcoming applications of this new class of “Omeg@Silica” materials., Sustainable extraction: Fish oil rich in long‐chain polyunsaturated fatty acids, vitamin D3 and carotenoid pigments have been sustainably extracted from anchovy fillet leftovers using biobased limonene. The oil is conveniently stabilized by adsorption on periodic mesoporous silicas. The simplicity of the process, the high load of fish oil, and the biocompatible nature of mesoporous silica support numerous forthcoming applications of this new class of “Omeg@Silica” materials.

BACKGROUND The rice weevil, Sitophilus oryzae (L., 1763) (Coleoptera: Curculionidae), is a stored grain/seed pest of several crops. Botanicals represent an option to manage this pest, especially those with high toxicity determined by its structure and physicochemical properties and low residue left behind on treated grains/seeds. Enantiomers are bioactive molecules in organic processes. The aim of this study was to evaluate the insecticidal activity of two enantiomeric forms of the monoterpenes citronellal, limonene, linalool, menthone and α-pinene against S. oryzae adults through contact, fumigant and repellent assays. RESULTS All results were compared with absolute acetone as the negative control and those from contact assays also with malathion as the positive control. (S)-(-)-linalool was the most toxic by contact to S. oryzae and (S)-(-)-menthone through fumigation, while the two enantiomeric forms of menthone and α-pinene were the best repellents. CONCLUSIONS The high toxicity of only one of the two monoterpene enantiomers showed the importance of form and percentage of enantiomer in the commercial product, which affect the success of the product to controlling S. oryzae. © 2021 Society of Chemical Industry.

In this research, phytochemical properties of lemon verbena and oxidative stability of the fat component in cookies (contain lemon verbena powder and EO) were investigated. The essential oil (EO) profile and polyphenol compounds were identified by GC/MS and HPLC, respectively. Different concentrations of lemon verbena powder and EO were added to the cookies in comparison with TBHQ. The oxidative stability of fat component in cookies (peroxide value, p‐Anisidine, TOTOX value), along with the physicochemical (pH, acidity, weight loss, and moisture content) and sensory properties of the cookies were evaluated over a period of 6 months during storage at room temperature. The main constituents of EO are geranial (27.21%), neral (20.01%), spathulenol (7.28%), and limonene, while trans‐Ferulic acid (6.71 mg/g), Hesperidin (1.87 mg/g), and ρ‐Coumaric acid (0.04 mg/g) were measured as main phenolic compounds. The peroxide value increased in all samples for the first 2 months of storage and then decreased as hydroperoxide was converted to secondary oxidation products. The p‐Anisidine value increased in all samples during storage. This parameter was lower in cookies containing lemon verbena EO and TBHQ treatments. Sensory evaluations of cookies showed that lemon verbena EO had positive effects on the aroma and taste of cookies during storage, whereas lemon verbena powder had adverse effects on mouthfeel and consumer acceptance. The results showed that lemon verbena can increase the eating quality, prolong the shelf life, and maintain the integrity of bakery products with high‐fat content.

This study aimed to determine the chemical compositions of crude aquatic extracts of M. pulegium L. and R. idaeus L., and their anti‐Toxoplasma activity. Crude aquatic extraction of aerial parts of R. idaeus L. and M. pulegium L. was performed. GC‐MS and HTPLC analyses were carried out. MTT assay was performed on Vero cells treated by different concentrations (Log −10 from 10−1 to 10−6) of the extracts. The anti‐Toxoplasma activity of the concentrations was investigated using vital staining. Menthol (99.23%) and limonene (0.227%) were the major compounds of the aquatic extract of M. pulegium L. Phytochemical compositions of R. idaeus L. were terpenoids, esterols, and flavonoids. The cell toxicity of M. pulegium L. was lower than R. idaeus L. (CC50 > 10−2 versus. ≥ 10−4). Aquatic extract of M. pulegium L. showed higher anti‐Toxoplasma activity (LC50 ≥ 10−6) than R. idaeus L. (LC50 ≥ 10−5). Statistically significant cell toxicity and anti‐Toxoplasma activity (p

The effect of different drying procedures on the quality characteristics of Pistacia atlantica subsp. kurdica is addressed in this work. Using five different drying methods include microwave, oven (40 and 60°C), sun, and shade, P. atlantica were dried. The variations in moisture content, drying rate, major components of essential oil, and texture property were assessed at the start and at the end points of the drying process. Comparison of the drying methods indicated that microwave drying to be most effective in lowering moisture content, while the shade drying had the lowest rate among methods. In the case of microwave, the dried seeds had highest brittleness, while the highest score for the penetration force was observed in oven 40°C. Regarding major elements of the essential oil (α‐pinene, α‐terpinen‐4‐ol, myrcene, β‐ocimene, β‐caryophyllene, and limonene), there were no significant differences between the five drying techniques, nor compared to the fresh sample. To model the drying process, six thin‐layer drying kinetic models were chosen. It was found that the Midilli–Kucuk model was the most suitable for explaining the drying curve of oven 40 and 60°C, microwave, and sun methods; Wang and Singh model was excellent to explain thin‐layer shade drying behavior of the P. atlantica seeds. In conclusion, in this study, an opportunity is represented to apply the most effective procedures to decrease the drying period and to achieve a product with appropriate safety and quality features., The Midilli–Kucuk model was found to be the most suitable for describing drying curve of oven 40 and 60°C, microwave, and sun methods; and Wang and Singh model was found to best explain thin‐layer shade drying behavior of the P. atlantica seeds. This study represents an opportunity to apply the most effective procedures to reduce the drying period.

The selective catalytic synthesis of limonene‐derived monofunctional cyclic carbonates and their subsequent functionalisation via thiol–ene addition and amine ring‐opening is reported. A phosphotungstate polyoxometalate catalyst used for limonene epoxidation in the 1,2‐position is shown to also be active in cyclic carbonate synthesis, allowing a two‐step, one‐pot synthesis without intermittent epoxide isolation. When used in conjunction with a classical halide catalyst, the polyoxometalate increased the rate of carbonation in a synergistic double‐activation of both substrates. The cis isomer is shown to be responsible for incomplete conversion and by‐product formation in commercial mixtures of 1,2‐limomene oxide. Carbonation of 8,9‐limonene epoxide furnished the 8,9‐limonene carbonate for the first time. Both cyclic carbonates underwent thiol–ene addition reactions to yield linked di‐monocarbonates, which can be used in linear non‐isocyanate polyurethanes synthesis, as shown by their facile ring‐opening with N‐hexylamine. Thus, the selective catalytic route to monofunctional limonene carbonates gives straightforward access to monomers for novel bio‐based polymers., Biopolymers: The selective catalytic synthesis of limonene‐derived monofunctional cyclic carbonates and their subsequent functionalisation via thiol–ene addition and amine ring‐opening is reported. The selective catalytic route to monofunctional limonene carbonates gives straightforward access to monomers for novel bio‐based polymers.

The deep‐frying process for plenty of fried products using vegetable oils needs safe and effective antioxidants. In the present exploration, the nutmeg essential oil (NEO) was employed as a potential antioxidant for sunflower oil during the deep‐frying of Chinese Maye at 180°C for 30 hr. In the comparative study, the additions for NEO at 0.12 g/kg, TBHQ at 0.12 g/kg, BHA at 0.08 g/kg, and BHT at 0.08 g/kg to sunflower oil were able to obviously improve its oxidative stability during the deep‐frying process, and their antioxidant effects were in the relative order: TBHQ at 0.12 g/kg > NEO at 0.12 g/kg > BHA at 0.08 g/kg > BHT at 0.08 g/kg (p, The deep‐frying process for plenty of fried products using vegetable oils needs safe antioxidants. In the present study, the nutmeg essential oil (NEO) and limonene were demonstrated to be effective in inhibiting the oxidation of sunflower oil during the deep‐frying of Chinese Maye at 180°C for 30 hr and improving the sensory properties of the fried products, Chinese Maye. Therefore, both of them could be used as antioxidants in the deep‐frying process of sunflower oil.

Metabolons consisting of cellular structure elements and sequential metabolic enzymes are expected to be involved in diverse biological processes. However, direct visualization of metabolons in prokaryotic cells is still challenging. In this study, we report direct visualization of concentrated subcellular regions of limonene synthesis inside single engineered Escherichia coli by using hyperspectral stimulated Raman scattering (hSRS) microscopy. Equipped with spectral unmixing, hSRS imaging provides a reliable method to quantify intracellular limonene content. In E. coli strains with a complete limonene synthesis pathway, intracellular limonene is found locally concentrated and colocalized with proteins. Furthermore, dual-modality SRS and two-photon fluorescence imaging showed colocalization of limonene and GFP-fused limonene synthase.Significance StatementMonitoring biosynthesis activity at the single-cell level is key to metabolic engineering but is still difficult to achieve in a label-free manner. Using hyperspectral stimulated Raman scattering imaging in the 670-900 cm−1 region, we visualized localized limonene synthesis inside engineered E. coli. The colocalization of limonene and GFP-fused limonene synthase was confirmed by co-registered stimulated Raman scattering and two-photon fluorescence images. Our finding suggests a limonene synthesis metabolon with a polar distribution inside the cells. This finding expands our knowledge of de novo limonene biosynthesis in engineered bacteria and highlights the potential of SRS chemical imaging in metabolic engineering research.

Limonene and linalool are major components in many essential oils, and both may autoxidize under certain conditions to form terpene hydroperoxides (THPs), which are reported to be sensitizers that may cause allergic contact dermatitis. This laboratory previously reported that peroxyhemiacetals (PHAs) may be present in some citrus oils, formed by reaction of THPs with endogenous aldehydes. It was also shown that PHAs can dissociate back to the corresponding THPs in polar solvation environments. Because of this potential for reversion to THPs, the analysis of PHAs is important in the context of measuring peroxide values in products. The fragrance industry currently utilizes iodometric titration to monitor THP levels in many raw materials; the currently accepted method requires that THPs in the sample are allowed to oxidize excess added iodide to molecular iodine for a one‐minute reaction time. The iodine generated is then titrated with thiosulfate to give the peroxide value. This paper reports on the iodide reaction time required for PHAs to be quantitatively measured by such an iodometric titration technique, and on the implications to citrus oil raw material testing.

BACKGROUND Microemulsions have been proposed as delivery systems for different lipophilic substances in transparent water-based systems. The chemical stability of the delivered compounds is a key factor to broaden the application of microemulsions in the food sector. The stability of a model beverage containing a microemulsion delivering β-carotene and lemon oil was tested under increasing light intensity up to 6000 lx at 20 °C. RESULTS The transparent microemulsion resulted physically stable during storage indicating that no coalescence phenomenon occurred. On the contrary, both colour and flavour of the microemulsion degraded as a consequence of limonene and β-carotene oxidation. Kinetic data obtained at increasing light intensity were used to estimate the light dependence of beverage spoilage and the mathematical relationship obtained was used to predict spoilage rate under different light conditions. Finally, a shelf life predictive model was proposed. CONCLUSIONS Transparent microemulsions can be successfully used to deliver flavoured oil and colourants into beverages. However, the photostability of the delivered compounds should be carefully studied to estimate product shelf life. To this aim, the availability of models predicting shelf life as a function of enlightening conditions could largely contribute to speed up the process. © 2019 Society of Chemical Industry.

Background The growing area has a substantial effect on plants, affecting secondary metabolism. For hops, different authors have studied the effect of growing area on the chemical composition of cones with the aim of verifying and understanding the changes in hop characters. Despite the scant literature the subject receives increasing attention by brewers and hop growers. The present study aimed to characterize, using gas chromatography-mass spectrometry (GC-MS), and high-performance liquid chromatography with ultraviolet detection (HPLC-UV), cones of hop (Humulus lupulus L.) cultivar Cascade. Plant material was obtained from nine different areas of Italy and compared with Cascade samples grown in the United States, Germany and Slovenia. Results Differences in bitter acids and xanthohumol content were observed. Nevertheless, no correlation between bitter acids and xanthohumol production, on the one hand, and rainfall, temperatures and latitude, on the other hand, were observed in our samples. The Slovenia samples were richer in molecules that confer hoppy, woody and flower notes; USA2 samples were more characterized by woody, earthy, grassy and floral aroma, quite different characters if compared to USA1, which had the lowest presence of grassy aromatic compounds. In the Italian samples, TRENTINO was the genotype most characterized by limonene presence. Conclusion The results of this study are indicative of the importance for hop users to know and characterize hops coming from different growing regions. The study pays special attention to the characterization of the differences in chemical characters of Cascade hop in Italy, where hop cultivation has developed only recently, but is in continuous expansion. © 2019 Society of Chemical Industry.

Bergamot (Citrus × bergamia) is mainly cultivated in Calabria area (Italy) for its essential oil that is widely used in cosmetics, food and medicine. The harvest season (November to February) affects the quality of essential oil, consequently the aim of our study was to evaluate the composition of volatile fractions at different harvesting stages. Two different cultivars, Femminello and Fantastico, were collected in November, December and January and their volatile compounds composition was determined by SPME GC/MS. Fourty‐two compounds were identified. Monoterpenes were the preponderant group; limonene was the most representative compound with similar concentrations in the varieties and at the three harvesting times. β‐Ocimene, β‐mircene and α‐terpinene showed higher concentration in Femminello than Fantastico, while trans‐α‐bergamotene, α‐pinene and citronellal were mostly concentrated in Fantastico. The concentration of β‐pinene in Fantastico and Femminello was higher in December and January, respectively, and γ‐terpinene concentration was higher in Femminello in November and January and in Fantastico in December. Linalool was the most preponderant monoterpene alcohol with a significantly higher concentration in Femminello than in Fantastico, but without significant differences during ripening. cis‐γ‐Bisabolene was the most preponderant sesquiterpene; it was more concentrated in Fantastico than in Femminello and showed a significantly higher concentration in December and January than in November. Linalyl and neryl acetate were the most abundant esters, with a significantly higher concentration in Fantastico. Fantastico seems to be the variety that produces higher volatile organic compounds in essential oil; moreover, the volatile compound concentration was higher at the second and third harvest time.

Most of the essential oils (EO) known for mosquitocidal activity contain terpenes as part of their chemical constituents. In this study, four monoterpenes namely γ-terpinene (T), R-(+)-limonene (L), carvacrol (C), and trans-anethole (A) were screened against late third instar Aedes aegypti Linn. larvae singly and in combination to find out the synergistic interaction. The monoterpenes γ-terpinene, R-(+)-limonene, trans-anethole, and carvacrol showed larvicidal activity with LC50 values of 9.76, 11.88, 50.19, 48.57 ppm and LC90 values of 16.99, 17.78, 65.21, 75.02 ppm, respectively for Ae. aegypti when tested individually. Prepared binary combinations at LC20 values and studied the synergistic interactions based on cotoxicity factor (CTF) and found that all the binary combinations showed synergistic interactions (CTF > 20). Further, the binary (1:1), ternary (1:1:1), and quaternary (1:1:1:1) terpene combinations on equal weight basis were prepared, evaluated against Ae. aegypti larvae and synergistic interactions were studied by Wadley's method. Among the eight combinations two combinations viz. LC (LC50 10.42 ppm) and LA (LC50 11.86 ppm) were showing synergistic interactions (R > 1.5) and others were exhibiting additive effect (1.5 ≥ R > 0.5) and none of the combinations showed antagonism (R

Tetranychus urticae is a major agricultural pest with worldwide distribution that has caused considerable damage to vegetable crops in north‐eastern Brazil. The aim of the present study was to investigate the chemical and lethal/sublethal effects of essential oils from the peels of the lime (Citrus aurantiifolia), lemon (C. limon), mandarin orange (C. reticulata) and (C. reticulata × C. sinensis) as well as selected constituents (linalool, α‐terpineol, α‐pinene, β‐pinene, terpinolene and limonene) against T. urticae. The greatest yield was achieved with the mandarin and tangerine peel oils. The chemical analysis (gas chromatography‐mass spectrometry) of the essential oils from the Citrus fruit peels enabled the identification of 127 compounds, revealing a predominance of monoterpenes. Limonene was the major constituent, and α‐pinene, β‐pinene, linalool and α‐terpineol were found in substantial quantities. Regarding the susceptibility of T. urticae, the Citrus oils and selected constituents were more effective by fumigation than residual contact. The C. reticulata oil was the most toxic by fumigation, and the C. limon oil was the most toxic by residual contact. The constituent α‐terpineol exhibited the highest toxicity with both methods. At a sublethal concentration, the oils and selected constituents had significant effects on the fecundity, feeding preference and oviposition of the mite. Citrus oils and their constituents are potentially useful for the future integrated management of T. urticae due to their lethal and sublethal properties. However, further studies are needed to evaluate the action of these essential oils against non‐target organisms and determine the cost–benefit ratio for the formulation of an acaricide harvested from agro‐industrial waste from citric fruit processing activities for use in the integrated control of T. urticae.

Cold plasma is known as a novel nonthermal processing method for decontamination of medicinal and aromatic plants (MAPs); however, there are little research studies about its effects on active ingredients of these plants. The aim of this research was to investigate the influence of low‐pressure cold plasma (LPCP) treatments (1, 3, and 5 min) on the essential oil (EO) content and composition of lemon verbena leaves. The EO content was determined using hydro‐distillation, and the composition of the extracted EOs was quantified using gas chromatography and gas chromatography–mass spectrometry techniques. The results showed that by increasing the LPCP treatment duration, the EO content was reduced from 1.2 to 0.9 (% v/w). The highest content of monoterpene hydrocarbons (e.g., limonene) and oxygenated sesquiterpenes (e.g., spathulenol and globulol) was also observed in LPCP‐treated ones, whereas the oxygenated monoterpenes (e.g., citral) content of control was measurably higher than those treated with LCPC.

BACKGROUND Contact allergy to oxidized limonene, with hydroperoxides of limonene (Lim-OOHs) as the main allergens, is common. However, high proportions of weak positive and doubtful patch test reactions have been reported. OBJECTIVES To determine the clinical relevance, elicitation threshold and dose-response relationship of Lim-OOHs in individuals with a positive or doubtful patch test reaction to standard Lim-OOHs 0.3% pet. METHODS A multicentre 3-week double-blind vehicle-controlled repeated open application test (ROAT) study with a simulated fine fragrance containing Lim-OOHs at 1260, 420 and 140 ppm, equal to a dose/area per application of Lim-OOHs of 3.0, 0.99 and 0.33 μg/cm2 , was performed. RESULTS Among 11 subjects allergic to Lim-OOHs, 11 (100%), 7 (64%), and 3 (27%), respectively, reacted to the applied doses. No reactions were seen in 17 healthy controls exposed to the highest dose. This difference in reactivity was statistically significant (P

Five batches of resin from the Pili tree (Canarium ovatum Engl.) were distilled, and their essential oils and hydrosols were analyzed by gas chromatography. The oils, obtained in yields of 13.4-19.7 % v/m, featured α-phellandrene in high proportions (50-65 %), alongside limonene, β-phellandrene and para-cymene. Chiral GC analysis confirmed that both phellandrenes were in fact >95 % (S)-(+) enantiomers, while the other monoterpenes featured less pronounced enantiomeric excesses. The hydrosols were rich in α-phellandrene oxidation products including cis-α-phellandrene epoxide and a series of para-menth-5-ene-1,2-diol isomers. Both essential oils and hydrosols were tested for their antibacterial activity against Escherichia coli and Staphylococcus aureus and exhibited MIC90 of less than 5 and 0.5 mg/mL of total volatiles, respectively. The essential oil features some potential as a source of readily available natural (S)-(+)-α-phellandrene.

Warburgia salutaris, known as 'Pepper bark', is an ethnomedicinally important tree found in the southern regions of Africa. A total of 75 fresh leaf specimens of W. salutaris (n=40 wild and 35 cultivated) were collected from the Limpopo (wild) and KwaZulu-Natal provinces (cultivated), two distinct locations in South Africa. In this study, the leaf essential oils obtained by hydrodistillation were characterized using gas chromatography coupled to mass spectrometry/flame ionization detection (GC/MS/FID). More than 15 compounds, accounting for 90-99 % of the total oil composition were identified. The analysis revealed that myrcene (0.6-65.3 %), (E)-β-ocimene (nd-56.9 %), (Z)-β-ocimene (nd-19.1 %), α-pinene (nd-19.1 %) and limonene (nd-11.7 %) are major constituents of W. salutaris essential oils. Chemometric analysis revealed two major chemotypes within the essential oils with a modeled variation of approximately 60 %. Linalool and germacrene D were revealed as markers associated with the wild-harvested oils, while cultivated oils were distinguished by higher levels of limonene and α-humulene. The intra-population variation indicated two chemically distinct chemotypes from three different populations, however, the season of harvest did not have a direct influence on the chemical profiles of the essential oils.

This study aimed to determine the relationship between volatile compounds of Picea likiangensis var. linzhiensis cone and host selection of Dioryctria abietella. During the infestation of P. likiangensis var. linzhiensis by D. abietella, their cones and branches emitted volatile compounds, which were extracted using CH2 Cl2 extraction and XAD2 adsorption methods, and were analyzed using gas chromatography-mass spectrometry. Before and after overwintering, D. abietella larva preferred annually infested cones and their extracts, and adult D. abietella preferred to lay eggs on annually infested cones and healthy cones of the year, and the oviposition rate of adult D. abietella was 72% on branches with healthy cones of the year, and no egg was laid on branches with annually healthy cones or branches without cones. The volatile compounds after infestation, α- and β-pinene, were significantly higher in cones than those in other tissues; however, myrcene in cones was significantly lower than those in other tissues. The annually infested cones produced β-caryophyllene and (1S)-(-)-β-pinene, while the annually healthy cones and branches produced myrcene and 3-carene. The annually infested cones and their extracts attracted D. abietella larvae, while that of healthy cones and annually infested cones attracted the adults, indicating that the terpene compounds: α-pinene, β-pinene, (1S)-(-)-β-pinene, limonene, and β-caryophyllene are attractive to D. abietella, and the terpene compounds-myrcene and 3-carene-from the branch tissues may be repulsive to D. abietella.

BACKGROUND: Hydroperoxides of limonene and linalool are potent sensitizers.OBJECTIVES: To investigate the prevalence of contact allergy to both hydroperoxides of limonene and hydroperoxides of linalool, to report clinical relevance, and to investigate patient demographics.METHODS: A total of 821 patients (35.6% male, mean age 42.4 years ± 17.8 years) were consecutively patch tested with our departmental baseline series and our fragrance series, including hydroperoxides of limonene 0.3% pet. and hydroperoxides of linalool 1.0% pet. The clinical relevance was assessed for all positive reactions.RESULTS: Positive patch test reactions to hydroperoxides of limonene and to hydroperoxides of linalool were observed in 77 patients (9.4%, 95% confidence interval [CI]: 7.4%-11.4%) and in 96 patients (11.7%, 95%CI: 9.5%-13.9%), respectively; 38 of these patients (4.6%, 95%CI: 3.2%-6.0%) reacted to both. Most reactions were considered to be possibly or probably clinically relevant (66.3% and 68.8%, respectively), and a small proportion were deemed to be of certain clinical relevance (18.2% and 19.8%, respectively).CONCLUSION: As compared with previous studies, high numbers of positive reactions to both hydroperoxides of limonene and hydroperoxides of linalool were observed, the majority of which were clinically relevant, supporting their inclusion in the European baseline series.

Summary Rice blast disease, caused by the fungus Magnaporthe oryzae, is the most devastating disease of rice. In our ongoing characterization of the defence mechanisms of rice plants against M. oryzae, a terpene synthase gene OsTPS19 was identified as a candidate defence gene. Here, we report the functional characterization of OsTPS19, which is up‐regulated by M. oryzae infection. Overexpression of OsTPS19 in rice plants enhanced resistance against M. oryzae, while OsTPS19 RNAi lines were more susceptible to the pathogen. Metabolic analysis revealed that the production of a monoterpene (S)‐limonene was increased and decreased in OsTPS19 overexpression and RNAi lines, respectively, suggesting that OsTPS19 functions as a limonene synthase in planta. This notion was further supported by in vitro enzyme assays with recombinant OsTPS19, in which OsTPS19 had both sesquiterpene activity and monoterpene synthase activity, with limonene as a major product. Furthermore, in a subcellular localization experiment, OsTPS19 was localized in plastids. OsTPS19 has a highly homologous paralog, OsTPS20, which likely resulted from a recent gene duplication event. We found that the variation in OsTPS19 and OsTPS20 enzyme activities was determined by a single amino acid in the active site cavity. The expression of OsTPS20 was not affected by M. oryzae infection. This indicates functional divergence of OsTPS19 and OsTPS20. Lastly, (S)‐limonene inhibited the germination of M. oryzae spores in vitro. OsTPS19 was determined to function as an (S)‐limonene synthase in rice and plays a role in defence against M. oryzae, at least partly, by inhibiting spore germination.

Propolis is a complex mixture that honey bees produce from the exudates of various plants and presents many medicinal properties. Its chemical composition varies according to the phytogeography characteristics of each region, among others. The aim of this study was to identify and characterize the volatile organic compounds (VOCs) present in Venezuelan propolis and compare with reference samples such as Brazilian and Argentinian propolis.; Results: A total of 90 VOCs were identified in a series of propolis samples using both solid-phase microextraction and dynamic headspace (DHS), both coupled to a gas chromatograph-electron ionization mass spectrometer. In the case of Venezuelan propolis, sesquiterpenes, esters, aromatic compounds, and aliphatic hydrocarbons were identified. Limonene was found only in Venezuelan samples, this being the first time it has been identified in samples from this country. In the case of green propolis, β-caryophyllene and nerolidol were the major compounds. As for the Argentinian samples, prenyl acetate, benzyl acetate, and 2-phenylethyl acetate were detected only in these samples.; Conclusions: Possible chemical markers of natural sources such as limonene were detected using DHS extraction. Several compounds have also been identified for the first time in Venezuelan propolis. Cluster analysis allowed the relating of the propolis VOCs profile to their provenance. © 2017 Society of Chemical Industry.; © 2017 Society of Chemical Industry.

Lymphomatoid contact dermatitis is an uncommon inflammatory disorder of the skin that is classified as a pseudolymphoma. It is probably an under‐reported entity, combining the clinical and histological features of cutaneous T cell lymphoma (CTCL) with some characteristics of allergic contact dermatitis. Aetiologically, it has been linked to several haptens, such as phosphorus sesquisulfide 1, 2, gold, nickel, dimethyl fumarate, methylisothiazolinone, and azo dyes. Delayed‐type hypersensitivity is regarded as the key in pathogenesis; avoidance of the hapten usually leads to resolution, and clonality cannot be proven in most cases. We report on the first case of lymphomatoid contact dermatitis in relation to limonene hydroperoxides (LimOOHs).