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A greenhouse pot experiment was conducted to evaluate the impact of zinc supply (0, 1, and 2 mM Zn as ZnSO

The present study aims to investigate the effect of copper (as CuSO4, 5H2O) supply (0, 25 and 50 μM) on performance of cilantro (Coriandrum sativum L.) plants grown under hydroponic conditions. All applied Cu concentrations drastically reduced the biomass production, length of the shoots and the roots and disturbed the ions (Cu, Ca, Fe, Zn and Mg) homeostasis. Either Cu-starvation (0 μM) or Cu-toxicity (25 and 50 μM) significantly reduced the net photosynthetic rate, stomatal conductance and transpiration rate resulting in reduced water use efficiency. Under Cu-toxicity, the variations in gas exchange parameters were associated with a remarkable decline in the photosynthetic pigments including Chlorophyll a, Chlorophyllb, Chlorophyll (a + b) and carotenoids. Additionally, an enhanced lipid peroxidation (evaluated as Malondialdehyde (MDA) contents) with a concomitant increase in proline, total soluble sugars and melanoidins contents were observed under these conditions. The increased MDA levels resulted in decrease in total lipid content and alteration of the fatty acid profiles in both shoots and roots with a general tendency toward the accumulation of saturated fatty acids that mirrors a decline in the desaturases activity. Although the increased activity of enzymatic antioxidants including catalase (CAT), gaiacol peroxidase (GPX) and ascorbate peroxidase (APX), the oxidative-induced injuries caused by 25 and 50 μM Cu were found to be irreversible and the optimal growth parameters were not achieved.

Natural plant extracts are primarily used as raw materials in the cosmetic and perfumery industry. However, adulterations with petrochemical products are occurring in the market, leading to non-100% natural products. Several analytical techniques such as impurity detection or enantioselective ratio assessments have been previously described as good indicators to detect any addition of synthetic products, but these techniques are ineffective with novel type of synthetic pathways such as semisynthesis. In order to improve authentication, development of advanced analytical strategies such as δ

The effects of cement dust on the yield and chemical composition of the essential oil were investigated in Cupressus sempervirens. Exposure to cement dust resulted in a significant increase in the essential oil yields. Significant factory distance-related changes in qualitative and quantitative composition of the essential oil were observed. Increasing pollution with dust increased the content of monoterpene hydrocarbons concomitant to increase of α-pinene, suggesting a redirection of the secondary metabolism of C. sempervirens towards biosynthesis of monoterpenes. In contrast, oxygenated monoterpenes and sesquiterpene hydrocarbons were strongly reduced. These results provide an overall picture of the different responses of monoterpenes and sesquiterpenes to air pollution caused by cement dust. They also reveal the suitability of using C. sempervirens in the creation of green areas around cement factories and encourage the use of dusted plants as potential source of valuable natural products. Keywords: Cement dust, Cupressus sempervirens, Essential oil, Monoterpenes, Environmental pollution

Phenolic and substituted phenol based resoles are commonly used in the formulation of can coatings. However, migration analyses of these coatings are very little described compared to other coating technologies. While epoxy and polyester have well known migrants with defined formation mechanisms, Non-Intentionally Added Substances (NIAS) specifically related to the phenolic resin are hardly studied in the literature. The goal of the publication is to further explore the influence of the phenolic resole, used in the formulation of can coatings, on extracted NIAS's nature. Six different model polyester-phenolic can coatings were formulated each with a specific phenol, cresol or tertbutylphenol-based resole. Can coating films were extracted for 24 h at 40 °C in acetonitrile before analysis. NIAS identification was done using gas chromatography separation coupled to high resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) spectroscopy analyses. Cyclic polyester oligomers were found in all extracts, with oligomers found in a range of 10 μg/dm

Three new compounds, a dihydrobenzofuran (coumaran) derivative (compound 1) and two pterocarpans (compounds 2 and 3) were isolated from a root extract of Calicotome villosa growing wild in Corsica. Their structures were elucidated using 1D and 2D NMR spectroscopy and MS/MS as 2-(1-methylethenyl)-5-hydroxy-6-carbomethoxy-2,3-dihydro-benzofuran, 4,9-dihydroxy-3-methoxy-2-dimethylallylpterocarpan, and 4,9-dihydroxy-3′,3′-dimethyl-2,3-pyranopterocarpan.

Neroli essential oil (EO), extracted from bitter orange blossoms, is one of the most expensive natural products on the market due to its poor yield and its use in fragrance compositions, such as cologne. Multiple adulterations of neroli EO are found on the market, and several authentication strategies, such as enantioselective gas chromatography (GC) and isotope ratio mass spectrometry (IRMS), have been developed in the last few years. However, neroli EO adulteration is becoming increasingly sophisticated, and analytical improvements are needed to increase precision. Enantiomeric and compound-specific isotopic profiling of numerous metabolites using multidimensional GC and GC-C/P-IRMS was carried out. These analyses proved to be efficient for geographical tracing, especially to distinguish neroli EO of Egyptian origin. In addition, δ2H values and enantioselective ratios can identify an addition of 10% of petitgrain EO. These results demonstrate that enantioselective and stable isotopic metabolite fingerprint determination is currently a necessity to control EOs.

Royal jelly, a honey bee secretion, plays a critical role in caste determination in honey bees because it serves as the source of nutrition for young larvae destined to become queens. It is also fe...

Changes in fatty acid profile, lipid quality, essential oil composition, total phenolic (TPC) and flavonoid (TFC) contents, radical scavenging, antibacterial and insecticidal activities were studied during the maturation of Schinus terebinthifolius Raddi fruits. Total lipids showed their maximum at the earlier and intermediate stage (green and half-red) of maturation, whereas, the highest levels of the main components linoleic and oleic acids were found at the late stage (red). Mature fruits were also distinguished by their high lipid quality as revealed by the lower values of n-3/n-6 ratio, calculated oxidizability (Cox), oxidative susceptibility (OS), atherogenic index (AI) and thromobogenic index (TI). The contents of monoterpenes decreased while those of sesquiterpenes increased during maturation. With the exception of α-pinene which dropped remarkably from immature to mature fruits, the content of the other main components (α-phellandrene, β-phellandrene and limonene) showed irregular variations. The TPC in intact and hydrodistilled fruits was higher at the last stage of maturation, while the maximum of TFC was recorded in the intermediate stage. Concomitantly, extract from residual hydrodistilled fruits was found as the most potent radical scavengers, whereas, the oils were found as the least scavengers. Nevertheless, they showed an appreciable antibacterial activity against Enterococcus feacium and Streptococcus agalactiae and exert a strong insecticidal activity against Spodoptera littoralis and Phthorimaea operculella . Collectively, these results suggest that the fruits of S. terebinthifolius could be considered as consolidated source of lipid and essential fatty acids, which may provide some health benefits to consumers. They also showed that the essential oils of S. terebinthifolius fruits can potentially be used in S. littoralis and P. operculella control in association with integrated pest management practices. Moreover, the use of extracts from intact or hydrodistilled residual fruits for the development of functional ingredients and the production of bio-based preservatives is encouraged.

In this study, peroxidases (PODs) from three waste by-products: broad bean pods (BBP), pea pods (PP), and artichoke stems (ARS) were purified and their optimal conditions were determined for the first time. The purification process resulted in 4.32, 7.21, and 8.9% of POD recoveries for PP, ARS, and BBP, respectively. They were purified 2.12-, 32.97-, and 10-fold with specific activities of 27.26, 266.43, and 27 U/mg of protein, respectively. Analysis of their optimal conditions showed that POD purified from BBP and PP exhibited the highest activity at 60 °C temperature and pH 6 and 8 with strong affinity with catechol substrate (Km of 0.356 and 0.189 mM; Vmax of 0.08 and 0.041 μM/min for BBP and PP, respectively). The highest activity of ARS POD was obtained under the following conditions: temperature at 50 °C, pH from 6 to 8, and guaiacol as substrate (Km 0.375 mM; Vmax 0.012 μM/min). Apart from giving the opportunity for recycling the food industry wastes, the studied waste by-products could represent an alternative source of PODs that could find several applications in the biotechnological, chemical, and food industries.

Four Semi-Interpenetrating Networks (semi-IPN) based on polydimethylsiloxane (PDMS) were developed for the sorptive extraction of polar phenolic compounds (log Kow ≤ 3). Their preparation is based on the hydrosilylation crosslinking reaction of dihydrosilane terminated polydimethylsiloxane with its homologue divinyl, followed by the addition of inert various polyethylene oxide derivatives (PEO). The physico-chemical properties of the semi-IPN were controlled by Differential Scanning Calorimetry (DSC), Scanning Electronic Microscopy (SEM), RAMAN spectroscopy and contact angle measurements, showing the homogeneity of the semi-IPN and their higher hydrophilicity. Under optimum extraction conditions of phenolic molecules as target analytes and using liquid chromatography as analysis techniques, the novel modified PDMS phases showed good extraction rate against polar analytes with an excellent relative recovery average (69–100 %) for phenolic molecules. The higher retention rates were obtained with 30 % interpenetrated copolymer PEO/PPO in PDMS. Moreover, five adsorption/desorption cycles led to a loss of 5.8 % of the adsorption efficiency, showing a good stability of these PDMS-based IPN phases.

International audience; Plant-based remedies have been widely used for the management of variable diseases due to their safety and less side effects. In the present study, we investigated Saussurea lappa CB. Clarke. (SL) given its largely reported medicinal effects. Specifically, our objective was to provide an insight into a new polymethyl methacrylate based nanocapsules as carriers of SL essential oil and characterize their biologic functions. The nanoparticles were prepared by nanoprecipitation technique, characterized and analyzed for their cytotoxicity, anti-inflammatory, anti-Alzheimer and antidiabetic effects. The results revealed that the developed nanoparticles had a diameter around 145 nm, a polydispersity index of 0.18 and a zeta potential equal to +45 mV and they did not show any cytotoxicity at 25 μg·mL−1. The results also showed an anti-inflammatory activity (reduction in metalloprotease MMP-9 enzyme activity and RNA expression of inflammatory cytokines: TNF-α, GM-CSF and IL1β), a high anti-Alzheimer’s effect (IC50 around 25.0 and 14.9 μg·mL−1 against acetylcholinesterase and butyrylcholinesterase, respectively), and a strong antidiabetic effect (IC50 were equal to 22.9 and 75.8 μg·mL−1 against α-amylase and α-glucosidase, respectively). Further studies are required including the in vivo studies (e.g., preclinical), the pharmacokinetic properties, the bioavailability and the underlying associated metabolic pathways.

International audience; In the present work, we propose the synthesis of a new family of sugar derived 1,4:3,6-dianhydrohexitol based AA/AB-type monomers. Unprecedented diacids based on Isomannide and Isoidide were elaborated with high yields and showed interestingly high melting point ranges (240-375 degrees C). Optimization of reaction conditions (temperature, time of reaction, and reactant ratios) has been investigated to synthesize the key intermediate of a set of AB monomers with acid, ester, and acid chloride functionalities. Isosorbide based ether benzoic acid AB monomer was polymerized and characterized by NMR and DSC techniques. The results show a semicrystalline behavior of the obtained polymer thanks to the controlled stereoregular arrangement of the AB starting monomer.

In a stricter legislative context, greener detergent formulations are developed. In this way, synthetic surfactants are frequently replaced by bio-sourced surfactants and/or used at lower concentrations in combination with enzymes. In this paper, a LC-MS/MS method was developed for the identification and quantification of enzymes in laundry detergents. Prior to the LC-MS/MS analyses, a specific sample preparation protocol was developed due to matrix complexity (high surfactant percentages). Then for each enzyme family mainly used in detergent formulations (protease, amylase, cellulase, and lipase), specific peptides were identified on a high resolution platform. A LC-MS/MS method was then developed in selected reaction monitoring (SRM) MS mode for the light and corresponding heavy peptides. The method was linear on the peptide concentration ranges 25-1000 ng/mL for protease, lipase, and cellulase; 50-1000 ng/mL for amylase; and 5-1000 ng/mL for cellulase in both water and laundry detergent matrices. The application of the developed analytical strategy to real commercial laundry detergents enabled enzyme identification and absolute quantification. For the first time, identification and absolute quantification of enzymes in laundry detergent was realized by LC-MS/MS in a single run. Graphical Abstract Identification and quantification of enzymes by LC-MS/MS.

RATIONALE To develop more eco-friendly laundry detergents, renewable surfactants synthesized from vegetal sources are increasingly being used. In a more stringent regulation context, the determination of bio-sourced surfactant origin thus appears essential to assess the claims of detergent manufacturers. Radiocarbon determination, the standard method for the analysis of bio-sourced materials, is an expensive technique, so there is a need for a cheaper method. METHODS Here, the use of an elemental analyzer linked to isotope-ratio mass spectrometry (EA/IRMS) is evaluated as an alternative approach to the official method. The δ(18) O, δ(13) C and δ(2) H isotope-ratio values were determined to investigate the bio-sourced origin of surfactant raw materials and mixtures. RESULTS A sample library of 26 commercial surfactants representative of detergent raw materials was first analyzed by EA/IRMS. The δ(18) O, δ(13) C and δ(2) H values allowed discrimination of synthetic and bio-sourced surfactants. Moreover, in this latter group, C4 plant-derived surfactants were distinguished by their δ(13) C values. Binary and ternary mixtures made of synthetic and bio-sourced surfactants were also analyzed and indicated a linear relationship between mixture isotope-ratio values and surfactant proportions. CONCLUSIONS IRMS represents a viable alternative to radiocarbon determination for the evaluation of surfactant bio-sourced origin. It is a faster and cheaper technique, allowing discrimination of petroleum- and biomass-derived surfactants and identification of their carbon sources (C4 or C3 plants).

The composition of the fatty acids of the roots and aerial parts of Aritolochia longa (Aristolacheae) and Bryonia dioica (Cucurbutaceae) was analyzed by gas chromatography (GC-FID) and gas chromatography-mass spectrometry (GC-MS). The oils extracted from the aerial parts of both species were rich in polyunsaturated fatty acids with the essential linolenic and linoleic acids being the most prominent compounds. Oleic and linoleic acids were the majors fatty acids in the roots of both species. Whatever the plant part analyzed and the species, the saturated fatty acids were predominantly composed of palmitic and stearic acids. The antibacterial activity, minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of the lipid extracts were determined against a panel of five bacterial strains. The results showed that the sensitivity to the lipid extracts was different for the test bacterial strains, and the susceptibility of gram positive bacteria was found to be greater than gram negative bacteria. The antibacterial activity of the root lipid extracts was particularly important against Enterococcus feacium (CMI value of 125 µg/mL; CMB values > 250 µg/mL) and Streptococcus agalactiae (CMI value of 125 µg/mL; CMB values 250 µg/mL for A. longa roots). These results indicate that A. longa and B. dioica could be considered as good sources of essential fatty acids which can act as natural antibacterial agents.

Enzyme-assisted extraction has emerged as an attractive green, cost-effective and high bioactive yielding technology by which desired bioactives with preserved or better efficacy are released. In the present study, the ability of cellulase, hemicellulase and their binary mixture (cellulase:hemicellulase; 1:1) in improving the extraction of essential oils from coriander (Coriandrum sativum L.) seeds, or the residue by-products from the distillation process containing value-added phytochemicals (fatty acids and phenolics) were evaluated. Cellulase and the binary mixture improved the extraction of essential oils by 44.2 and 40%, respectively. Application of enzymes was associated with increased amount of oxygenated terpenes in the essential oils derived from enzyme-treated samples. Linalool, camphor and geranyl acetate were the prominent compounds. From the hydrodistillation residues, a better recovery of petroselinic-rich oil with a good nutritional quality was also observed in enzyme-treated seeds. They also contained an appreciable amount of polyphenols and showed an improved antioxidant activity as revealed by the DPPH, FRAP and cellular antioxidant activity assays. The results suggested that enzyme pre-treatment allowed better recovery without alteration of the essential oil composition. The hydrodistillation residues obtained could be potentially exploited for the development of functional food ingredients and nutraceuticals.

The fatty acid, essential oil compositions and their respective antioxidant and antibacterial activities was determined in Schinus terebinthifolius Raddi leaves and twigs. The lipid content ranged from 1.75 to 4.65% in twigs and leaves, respectively. Thirteen fatty acids were identified with α-linolenic (C18:3), palmitic (C16:0) and linoleic (C18:2) acids being the main components. The essential oils of both organs were characterized by a high amount of monoterpene hydrocarbons (68.91–74.88%) with α-phellandrene (33.06–36.18%), α-pinene (14.85–15.18%) and limonene (6.62–8.79%) being the chief components. The DPPH˙ radical scavenging assay revealed that both oils have a very weak antiradical activity. In contrast, they showed an appreciable antibacterial activity against the gram-positive Enterococcus feacium (ATCC 19434) and Streptococcus agalactiae (ATCC 13813) bacteria. These results suggest that leaves and twigs of S. terebinthifolius could be considered as an important dietary source of health promoting phytochemicals and has a good potential for use in food industry and pharmacy. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s13197-018-3049-6) contains supplementary material, which is available to authorized users.

International audience; Bay leaves (Laurus nobilis L.) are widely used as a condiment and their therapeutic benefits are well known. These biological properties were attributed to a plethora of highly bioactive secondary metabolites namely essential oils and phenolics. However, their recovery from plant matrix is generally limited by the presence of physical barrier (cell wall). Thus, the use of novel extraction procedures to enhance their release is particularly important. Therefore, the aim of this work is to assess the potential use of enzyme treatment (cellulase, hemicellulase, xylanase end the ternary mixture of them) as a tool to improve the extraction efficiency of bioactive compounds from bay leaves. Results showed that enzyme pre-treatment resulted in 243, 227, 240.54 and 0.48% increase in the essential oil yields in samples treated with cellulase, hemicellulase, xylanase and the ternary mixture, respectively. Compositional analysis by GC and GC MS revealed remarkable enrichment of the essential oils derived from enzyme-treated samples with oxygenated monoterpenes, leading hence to better antioxidant activity as revealed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) and azino-bis-(3-ethylbenzothiolzoline 6-sulphonic acid) (ABTS) assays. The 1,8-cineole, alpha-terpinyl acetate, methyl eugenol, linalool, a-pinene, sabinene and beta-pinene were found as the most prominent components in all essential oils. Most importantly, enzyme treatment did not induce transformation of the volatile components, but it contributes to the liberation of some glycosidically bound volatiles. Moreover, it significantly enhances the release of phenolic compounds from the hydro distilled residual leaves and consequently their antioxidant activity. These results suggest that enzyme pre-treatment could be useful for extracting valuables components, and hold good potential for use in food, cosmetic and pharmaceutical industries.

An emerging body of evidence indicates that oleuropein, a biophenol usually found in olive leaves, extra-virgin olive oil and in some species of the Oleaceae family has potent biological and pharmacological properties. Its main pharmacological activities such as anticancer, cardioprotective, neuroprotective, gastroprotective, hepato-protective, anti-diabetes, anti-obesity and radioprotective, among others, are in large part attributed to its putative antioxidant and anti-inflammatory effects. This mini-review collects and discusses the scattered data available in the literature concerning oleuropein and/or oleuropein-rich extracts and highlights its chemistry, biosynthesis, biological activities and its possible mechanisms of action.

Root essential oil of Pulicaria mauritanica Coss. (Asteraceae) collected from western Algeria was analysed using a combination of chromatographic (CC, GC/FID, GC(RI)] and spectroscopic [GC–MS, 13C-NMR] techniques. Thirty-eight compounds accounting for 90.4% of the whole composition were identified. The oil composition was dominated by thymyl derivatives (2,5-dimethoxy-p-cymene (37.2%), 6-methoxythymyl isobutyrate (14.2%), 10-isobutyryloxy-8,9-dehydrothymyl isobutyrate (4.8%) and thymyl isobutyrate (3.1%)), as well as by neryl isobutyrate (11.1%). A new natural compound was isolated and the structure was elucidated as 1S,2S,5S,8S-modhephan-3-one (relative stereochemistry). Copyright © 2014 John Wiley & Sons, Ltd.

International audience; The chemical composition of Cyperus rotundus L. tubers essential oil from the South of Tunisia was analyzed using GC-FID and GC-MS. Fifty compounds were identified representing 84.6 % of the total oil. A new chemotype was found in Tunisia. This essential oil was characterized by sesquiterpenes abundance (78.3 %) mainly represented by cyperene (15.2 %) and cyperotundone (19.7 %). The essential oil (EO) was further fractionated into three fractions (F1: n-pentane, F2: n-pentane/diethyl ether (95/5) and F3: diethyl ether). The antioxidant activity of the EO and its fractions was tested using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging test and beta-carotene bleaching method. Results showed that the whole EO was more active than the fractions with an effective concentration (EC50) of 0.85 +/- 0.03 mg/mL and an antioxidant activity coefficient (AAC) of 396.0 +/- 2.4. The antimicrobial activity of the EO and its fractions was evaluated using the disc diffusion method against six foodborne pathogens and results showed that Staphylococcus aureus was the most inhibited bacterium with an inhibition diameter of 15.2 +/- 0.8 mm for the whole EO.

Air-, oven- and freeze-dried garlic bulbs were hydrodistilled and the resulting essential oils were analyzed by gas chromatography (GC) and GC/mass spectrometry (GC/MS). The highest yields were 0.6 and 0.5% (w/w) for freeze- and oven-dried samples, respectively. The essential oils were characterized by a high amount of sulfur compounds (84.3–98.9%) with diallyl trisulfide (37.3–45.9%), diallyl disulfide (17.5–35.6%) and methyl allyl trisulfide (7.7–10.4%) being the major components. Remarkable qualitative and quantitative differences between the investigated oils owing to the drying procedure were found and a set of marker components was established to differentiate between them.

International audience; Volatile oil constituents of Tunisian sweet orange (Citrus sinensis Osbeck) cv. Meski (MES), Valencia Late (VAL), Thomson Navel (THN) and Maltaise Blanc (MAB); mandarin (Citrus reticulate Blanco); sour orange (Citrus aurantium L cv. Amara (AM)) and pummelo (Citrus grandis Osbeck) were obtained by hydrodistillation and analysed by gas chromatography (GC) combined with a flame ionisation detector (FID) and mass spectrometry (MS). A total of 41 components accounting for more than 95% of the total essential oils were identified, and oxygenated monoterpenes (69.5-99.9%) were found as the most prominent fraction in all oil samples. The main constituents were linalool (3.1-73%), isoborneol (0-55.8%) and tepinen-4-ol (1.1-19.2%). A high degree of inter-and intraspecific chemical variability between species and cultivars was found to be genetically determined, and a set of distinctive traits (chemical markers) in the essential oils profile was established. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) of all identified components grouped the oils into two main chemotypes (linalool/isoborneol and isoborneol/linalool).

International audience; A comprehensive study on the volatile oil and phenolic constituents of Ailanthus altissima Swingle (Simaroubaceae) leaves was performed. Methanolic extracts of leaves and their hydrodistilled residues were screened for their antioxidant, antimicrobial and phytotoxic properties. The results showed that the leaf volatile oils were a complex mixture of more than a hundred components, mainly composed by non-terpenic compounds (tetradecanol, heneicosane, tricosane and docosane) and sesquiterpene hydrocarbons (α-curcumene and α-gurjunene). Methanolic extracts from leaves contain the highest level of total phenolic content, while those from the hydrodistilled residues showed the highest total flavonoid content. The most frequent phenolic compounds identified by HPLC-DAD-MS were gallic acid, chlorogenic acid, HHDP-galloylglucose, epicatechin, rutin, hyperoside and quercetin-3-galloyl hexoside. Evaluation of the antioxidant activities by using four complementary tests (DPPH, ABTS, 2-deoxyribose and FRAP) showed that both extracts exhibited strong concentration-dependent antioxidant activities. These extracts were efficient against Gram-positive bacteria, but not active against Gram-negative bacterial strains and the yeast Candida albicans. They also exhibited strong inhibitory effects on the germination and the radicle growth of the wild Daucus carota. This work provides scientific supports for the high antioxidant and phytotoxic activities of this species and thus, it may find potential applications in the development of natural herbicides and antioxidants for agro-food and pharmaceutical industries.

International audience; The main goal of the present study is to evaluate the effects of enzymatic pre-treatment on the yields, chemical composition and antimicrobial activities of the essential oils of Thymus capitatus and Rosmarinus officinalis leaves. In T. capitatus, application of cellulase, hemicellulase and combination of both enzymes induced 63.55, 23.72 and 109% increase in the essential oil yields. It also induced increment by 2.7, 31 and 38% in the amount of its main component carvacrol. In R. officinalis, enzymatic treatment resulted in enhanced oil yields by 5, 50 and 20% for cellulase, hemicellulase and the combination of both enzymes, respectively. In contrast to T. capitatus, the amount of the main component 1,8-cineole dropped by 17.73, 36.92 and 15.46% in oils extracted from cellulase, hemicellulase and cellulose/hemicellulase treated samples of R. officinalis. At the same time, the essential oils (at 1/32 and 1/4 dilution for T. capitatus and R. officinalis, respectively) were evaluated for their antimicrobial activities against 6 food-borne pathogens (Escherichia coli, Salmonella typhimurium, Streptococcus agalactiae, Staphylococcus aureus, Enterococcus feacium and Candida albicans). All investigated oils exhibited antimicrobial activity with those issued from hemicellulase treated samples being the most effective. Enzymatic pre-treatment could be useful for enhancing yield and antimicrobial activity of the essential oils, and hold a good potential for use in food and pharmaceutical industries

International audience; A reliable database is established from the analysis of 500 French royal jellies (RJ). Diversity of geographical origins, harvesting seasons, and forage sources were taken into account. Authenticity intervals for numerous physicochemical parameters have been established from French RJs, obtained without bee-feeding with artificial sugars or proteins. RJs from Italy and non-European countries, derived from feeding experiments, were analysed and compared with the database. Differences in 10-HDA, d13C and sugars (sucrose, erlose, maltose, maltotriose) contents were observed. Sucrose and erlose contents in French RJs were less than 1.8 and 0.4%, respectively, whereas they attained 3.9 and 2.0% in some commercial samples and 7.7 and 1.7% in RJs produced by sugarcane feeding. Maltose and maltotriose contents were less than 1.0 and 0.2% in French RJs, and they can attain levels of 2.6 and 0.4% in commercial samples; they can be as high as 5.5 and 1.7% in RJs obtained by bee-feeding with starch hydrolysate syrups. RJs obtained with and without feeding exhibit d13C values ranging from 26.45 to 23.73%, and from 26.05 to 14.65%, respectively. This study could be used to discriminate different production methods and provide a useful tool for identifying unknown commercial RJs. Highlights A total of 750 royal jellies (RJs) from different origins were studied. Origins included domestic, imported, obtained by bee-feeding. French RJ samples were chemically characterised. Authenticity intervals were calculated for authentic RJs. Sucrose, erlose, maltose, maltotriose and δ13C contents are bee-feeding markers.

International audience; A comprehensive analysis of the responses of Nigella sativa L. to elevated zinc concentrations was assessed in pot experiments. Zn excess supply did not affect the germination but drastically reduced radicle elongation. A concentration-dependent reduction in all growth parameters, yield, and yield components was observed. With the increasing Zn concentrations, total lipid contents decreased and changes in fatty composition toward the production of saturated ones were underscored. Despite the reduction in the seeds essential oil yield, a redirection of the terpene metabolism toward the synthesis of oxygenated compounds has been evidenced. A significant increase in the total phenols and flavonoids contents concomitant with improved antioxidant activities has also been found. Collectively, these results highlight the possible use of N. sativa L. in phytoremediation applications, on the one hand, and that Zn excess could represent an excellent alternative to improve the nutritional attributes of this important species, on the other hand.

RATIONALE The analytical composition and botanical origin of honey are basic data used to determine the quality of this foodstuff. Although proteins are used to characterise the analytical composition of honey, they can be eliminated during its ultrafiltration and, in the case of honeys not saturated with their own pollen, the use of proteins does not work well. As acidity is a well-known characteristic of honey and organic acids are present at around 0.5% in honey, we therefore investigated an alternative method to the protein-based White method, using organic acids as new internal standards instead of proteins. METHODS The qualitative and quantitative analyses of 14 organic acids were carried out by ion chromatography with an electrochemical detector. The 13C/12C isotopic ratios of the honeys, and of the organic acids extracted from them with an anion exchange resin, were determined by isotope ratio mass spectrometry. RESULTS Gluconic acid is the predominant organic acid in honey, at between 1.8 and 12.7 g/kg. For fir honey the major acid is galacturonic acid at around 4.6 g/kg. The isotopic ratios of honeys and of their acids are strongly linked. Correlations between the δ13C values of the honey and the acids were significant, and better than those obtained using proteins. CONCLUSIONS This study has provided a method to differentiate honeys from seven botanical origins, based on organic acid analysis. By combining various organic acid contents and isotopic ratio values through statistical processing by Principal Component Analysis it is possible to differentiate honey samples as a function of their botanical origin. Copyright © 2012 John Wiley & Sons, Ltd.

International audience; The effects of feeding bees artificial sugars and/or proteins on the sugar compositions and (13)C isotopic measurements of royal jellies (RJs) were evaluated. The sugars fed to the bees were two C4 sugars (cane sugar and maize hydrolysate), two C3 sugars (sugar beet, cereal starch hydrolysate), and honey. The proteins fed to them were pollen, soybean, and yeast powder proteins. To evaluate the influence of the sugar and/or protein feeding over time, samples were collected during six consecutive harvests. (13)C isotopic ratio measurements of natural RJs gave values of around -25 ‰, which were also seen for RJs obtained when the bees were fed honey or C3 sugars. However, the RJs obtained when the bees were fed cane sugar or corn hydrolysate (regardless of whether they were also fed proteins) gave values of up to -17 ‰. Sugar content analysis revealed that the composition of maltose, maltotriose, sucrose, and erlose varied significantly over time in accordance with the composition of the syrup fed to the bees. When corn and cereal starch hydrolysates were fed to the bees, the maltose and maltotriose contents of the RJs increased up to 5.0 and 1.3 %, respectively, compared to the levels seen in authentic samples (i.e., samples obtained when the bees were fed natural food: honey and pollen) that were inferior to 0.2% and not detected, respectively. The sucrose and erlose contents of natural RJs were around 0.2 %, whereas those in RJs obtained when the bees were fed cane or beet sugar were as much as 4.0 and 1.3 %, respectively. The combination of sugar analysis and (13)C isotopic ratio measurements represents a very efficient analytical methodology for detecting (from early harvests onward) the use of C4 and C3 artificial sugars in the production of RJ.

(R)-(E)-6,7-Epoxyocimene, the major constituent of the essential oil from Plectranthus tenuicaulis, as well as the racemic (Z)-isomer previously synthesized from commercial (Z)-beta-ocimene were used as starting material for the synthesis of fragrant derivatives. Among the 14 compounds obtained from these precursors (alcohols, diols, diepoxy, sulfur and carbonyl derivatives), four were described for the first time and three were enantiomerically pure. All compounds were fully characterized by one- and two-dimensional nuclear magnetic resonance analysis as well as by gas chromatography and mass spectroscopy (electron ionization). Additionally, their odour properties were evaluated

International audience; The effect of stage of maturity on total lipids, fatty acids, yields and essential oil composition and their antimicrobial and free radical scavenging activities of the Schinus molle fruits was investigated. The content of total lipids varied from 2.87 to 5.35% (w/w, dw) and were rich in unsaturated fatty acids particularly linoleic acid. As maturation progress, the essential oil yield dropped from 5.18% to 1.15%. Monoterpene hydrocarbons with α-phellandrene (35.15-40.38%), limonene + β-phellandrene (21.47-36.62%), β-myrcene (7.61-24.96%) and α-pinene (1.92-2.58%) were found to be the main components. At the same time, the essential oils were evaluated for their antimicrobial and free radical scavenging activities. They were found to be active against Bacillus subtilis, Bacillus cereus, Salmonella typhymurium and Escherichia coli but they do not inhibit the growth of Candida albicans. Conversely, they showed very weak activity against the DPPH radical. In both assay, the oil derived from the intermediate stage was reported as more efficient.

The carbon and nitrogen stable ratios of royal jelly (RJ) samples from various origins are determined using an elemental analyser linked online to an isotope ratio mass spectrometer to evaluate authenticity and adulteration. The (13)C/(12)C and (15)N/(14)N stable isotope ratios are measured in more than 500 RJs (domestic, imported and derived from feeding experiments) in order to obtain isotopic measurements that take into account seasonal, botanical and geographical effects. Authenticity intervals are established for traditional beekeeping practices, without feeding, in the range -22.48 to -27.90‰ for δ(13)C. For these samples, the δ(15)N values range from -1.58 to 7.98‰, depending on the plant sources of pollen and nectar. The δ(13)C values of the commercial samples vary from -18.54 to -26.58‰. High δ(13)C values are typical of sugar cane or corn syrups which have distinctive isotopic (13)C signatures because both plants use the C4 photosynthetic cycle, in contrast to most RJs which are derived from C3 plants. These differences in the (13)C-isotopic composition allow the detection of the addition of such sugars. RJs from traditional sources and from industrial production by sugar feeding are thus successfully distinguished.

To develop more eco-friendly laundry detergents, renewable surfactants synthesized from vegetal sources are increasingly being used. In a more stringent regulation context, the determination of bio-sourced surfactant origin thus appears essential to assess the claims of detergent manufacturers. Radiocarbon determination, the standard method for the analysis of bio-sourced materials, is an expensive technique, so there is a need for a cheaper method.Here, the use of an elemental analyzer linked to isotope-ratio mass spectrometry (EA/IRMS) is evaluated as an alternative approach to the official method. The δ(18) O, δ(13) C and δ(2) H isotope-ratio values were determined to investigate the bio-sourced origin of surfactant raw materials and mixtures.A sample library of 26 commercial surfactants representative of detergent raw materials was first analyzed by EA/IRMS. The δ(18) O, δ(13) C and δ(2) H values allowed discrimination of synthetic and bio-sourced surfactants. Moreover, in this latter group, C4 plant-derived surfactants were distinguished by their δ(13) C values. Binary and ternary mixtures made of synthetic and bio-sourced surfactants were also analyzed and indicated a linear relationship between mixture isotope-ratio values and surfactant proportions.IRMS represents a viable alternative to radiocarbon determination for the evaluation of surfactant bio-sourced origin. It is a faster and cheaper technique, allowing discrimination of petroleum- and biomass-derived surfactants and identification of their carbon sources (C4 or C3 plants).

International audience; This paper presents the analysis of surfactants in complex mixtures using Raman spectroscopy combined with signal extraction (SE) methods. Surfactants are the most important component in laundry detergents. Both their identification and quantification are required for quality control and regulation purposes. Several synthetic mixtures of four surfactants contained in an Ecolabel laundry detergent were prepared and analyzed by Raman spectroscopy. SE methods, Independent Component Analysis and Multivariate Curve Resolution, were then applied to spectral data for surfactant identification and quantification. The influence of several pre-processing treatments (normalization, baseline correction, scatter correction and smoothing) on SE performances were evaluated by experimental design. By using optimal pre-processing strategy, SE methods allowed satisfactorily both identifying and quantifying the four surfactants. When applied to the pre-processed Raman spectrum of the Ecolabel laundry detergent sample, SE models remained robust enough to predict the surfactant concentrations with sufficient precision for deformulation purpose. Comparatively, a supervised modeling technique (PLS regression) was very efficient to quantify the four surfactants in synthetic mixtures but appeared less effective than SE methods when applied to the Raman spectrum of the detergent sample. PLS seemed too sensitive to the other components contained in the laundry detergent while SE methods were more robust. The results obtained demonstrated the interest of SE methods in the context of deformulation.

Some new constituents were discovered in a very unusual spanish lavender: Lavendula luisieri (Rozeira) Riv. Mart. The essential oil of L. luisieri, which is produced on an industrial scale, was analyzed by a combination of GC and GC/MS. Many components identified were irregular monoterpenoids, with a cyclopentanic structures unique in the plant kingdom, like α-necrodyl acetate (20–25% of the oil) or α-necrodol. The new structures identified were: 3,4,4-trimethyl-2-cyclohexen-1-one, 3,4,4-trimethyl-5-hexen-2-one, 2,3,4,5-tetramethyl-2-cyclopenten-1-one, 2,3,5,5-tetramethyl-4-methylene-2-cyclopenten-1-one, 1,1,2,3-tetramethyl-4-hydroxymethyl-2-cyclopentene, 2,4,5,5-tetramethyl-cyclopentadien-1,3-carboxylic acid and selina-4,7(11)-diene. A monoterpene whose exact structure remains unknown, is present in the oil at a level of (2–4%). Other main compounds were 1,8-cineole and lavandulyl acetate.

International audience; Gas chromatography and liquid chromatography have been used simultaneously to analyze sugars in honey. After statistical processing by principal components analysis, additions of exogenous sugars could be detected by the appropriate fingerprints of adulteration. Application to acacia, chestnut and lavender honeys enabled the detection of fraud resulting from 5 to 10% addition of sugar syrups. This method may be considered as a replacement of isotopic analysis, that has some limitations.

International audience; The chemical composition of the volatile oils obtained from the roots, leaves, flowers, and stems of Thapsia garganica of Tunisian origin was investigated by GC-FID and GC/MS analyses. Sesquiterpene hydrocarbons and oxygenated monoterpenes were predominant in the oils of all plant parts. Bicyclogermacrene (21.59-35.09%) was the main component in the former compound class, whereas geranial (3.31-14.84%) and linalool (0.81-10.9%) were the most prominent ones in the latter compound class. Principal-component (PCA) and hierarchical-cluster (HCA) analyses revealed some common constituents, but also significant variability amongst the oils of the different plant parts. This organ-specific oil composition was discussed in relation to their biological and ecological functions. For the evaluation of the intraspecific chemical variability in T. garganica, the composition of the flower volatile oils from four wild populations was investigated. Bicyclogermacrene, linalool, and geranial were predominant in the oils of three populations, whereas epicubenol, -sesquiphellandrene, and cadina-1,4-diene were the most prominent components of the oil of one population. PCA and HCA allowed the separation of the flower oils into three distinct groups, however, no relationship was found between the volatile-oil composition and the geographical distribution and pedoclimatic conditions of the studied populations.

The enantiomeric distributions of linalool and linalyl acetate in various natural products are measured by enantioselective gas chromatography on alkyl-substituted cyclodextrins. Different plant cultivars were investigated by four extraction processes: steam distillation, solvent extraction, supercritical fluid extraction, and headspace analysis. Careful attention must be paid to linalool which undergoes partial racemization under certain processing conditions. In most cases, enantiomeric distribution is a powerful tool for authenticity testing.

A gas chromatography–combustion–isotope ratio mass spectrometry method for confirmation of hydrocortisone abuse in horseracing and equine sports is proposed. Urinary hydrocortisone was converted to a bismethylenedioxy derivative which presents good gas chromatographic properties and brings an extra carbon contribution of only two carbon atoms. Synthetic hydrocortisone has a different 13 C abundance from that of natural urinary horse hydrocortisone and the difference is significant, therefore exogenous and endogenous hydrocortisone can be distinguished.

The current approach to detection of doping with testosterone is based on measuring the testosterone to epitestosterone ratio (T/E) in urine by gas chromatography/mass spectrometry. The median T/E for healthy males who have not used T is about 1.0. In a single urine, a T/E lower than six leads to a negative report even though it does not exclude T administration. A value greater than six indicates possible T administration or a naturally elevated ratio. It has been shown previously that the carbon isotope ratio of urinary T changes after T administration. In this study a potential confirmation method for T abuse was optimized. Gas chromatography/combustion/carbon isotope ratio mass spectrometry (GC/C/IRMS) was used to analyze two T precursors (cholesterol and 5-androsten-3 beta, 17 beta-diol) and two T metabolites (5 alpha- and 5 beta-androstane-3 alpha, 17 beta-diol) in addition to T itself in each of 25 blind urines collected from eight healthy men before, during or after T administration. The carbon isotope ratios of T and the metabolites were lower after T administration. The relationships among the variables were studied using multivariate analysis and beginning with principal components analysis; cluster analysis revealed that the data are composed of two clusters, and classified the samples obtained after T administration in one cluster and the remainder in the other; discriminant analysis correctly identified T users. The measurement of carbon isotope ratios of urinary androgens is comparable to the T/E > 6 test and continues to show promise for resolving cases where doping with T is suspected.The current approach to detection of doping with testosterone is based on measuring the testosterone to epitestosterone ratio (T/E) in urine by gas chromatography/mass spectrometry. The median T/E for healthy males who have not used T is about 1.0. In a single urine, a T/E lower than six leads to a negative report even though it does not exclude T administration. A value greater than six indicates possible T administration or a naturally elevated ratio. It has been shown previously that the carbon isotope ratio of urinary T changes after T administration. In this study a potential confirmation method for T abuse was optimized. Gas chromatography/combustion/carbon isotope ratio mass spectrometry (GC/C/IRMS) was used to analyze two T precursors (cholesterol and 5-androsten-3 beta, 17 beta-diol) and two T metabolites (5 alpha- and 5 beta-androstane-3 alpha, 17 beta-diol) in addition to T itself in each of 25 blind urines collected from eight healthy men before, during or after T administration. The carbon isotope ratios of T and the metabolites were lower after T administration. The relationships among the variables were studied using multivariate analysis and beginning with principal components analysis; cluster analysis revealed that the data are composed of two clusters, and classified the samples obtained after T administration in one cluster and the remainder in the other; discriminant analysis correctly identified T users. The measurement of carbon isotope ratios of urinary androgens is comparable to the T/E > 6 test and continues to show promise for resolving cases where doping with T is suspected.

Volatile constituents obtained by hydrodistillation of the leaves of the Malagasy endemic plant Psiadia lucida (Cass.) Drake, were investigated by GC and GC/MS. A total of 50 constituents, representing 96.9% of the oil, were identified. The main compounds were mono- and sesquiterpene hydrocarbons: terpinolene (38.0%), limonene (10.2%) and α-humulene (21.2%). The oil was also found to possess interesting antimicrobial activities.

New biosourced chiral cross-linkers were reported for the first time in the synthesis of methyltestosterone (MT) chiral molecularly imprinted polymers (cMIPs). Isosorbide and isomannide, known as 1,4:3,6-dianhydrohexitols, were selected as starting diols. The cMIPs were synthesized following a noncovalent approach via thermal radical polymerization and monitored by Raman spectroscopy. These cross-linkers were fully characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and high-resolution mass spectrometry. The cross-polarization magic angle spinning 13C NMR, Fourier transform infrared spectroscopy, scanning electron microscopy, and specific surface areas following the Brunauer-Emmett-Teller (BET) method were used to characterize the cMIPs. The effect of stereochemistry of cross-linkers on the reactivity of polymerization, morphology, and adsorption-recognition properties of the MIP was evaluated. The results showed that the cMIP exhibited an obvious improvement in terms of rebinding capacity for MT as compared with the nonimprinted polymer (NIP). The highest binding capacity was observed for cMIP-Is (27.298 mg g−1) for high concentrations (500 mg L−1). However, the isomannide homologue cMIP-Im showed higher recovery—up to 65% and capacity for low concentrations (15 mg L−1). The experimental data were properly fitted by the Freundlich adsorption isothermal model.

This work presents two techniques for testing for the adulteration of flavors. One uses multidimensional gas chromatography on cyclodextrin derivatives to separate chiral compounds, the other uses isotope ratio mass spectrometry coupled with gas chromatography to determine stable isotope ratios. Applications to fruits and plants for the food and perfume industry are introduced.

The hydrodistilled essential oils from herbal parts of three varieties of Chrysothamnus nauseousus were analyzed by GC and GC/MS. All oils were found to consist of mainly monoterpenes. A total of 51, 46 and 59 compounds were identified from C. nauseousus var. albicaulis, C. nauseousus var. consimilis and C. nauseousus var. glabratus, respectively, representing 97.1%, 96.0% and 96.2% of each of the oils listed. The major constituents of C. nauseousus var. albicaulis were β-pinene (16.8%), limonene (18.6%) and β-phellandrene (26.0%); the main constituents of C. nauseousus var. consimilis were limonene (33.2%), β-phellandrene (18.0%) and (Z)-β-ocimene (14.6%). The major constituents of C. nauseousus var. glabratus were β-pinene (30.3%), myrcene (10.5%), limonene (16.5%) and β-phellandrene (10.9%).