A global LC-MS2 -based methodology to identify and quantify anionic phospholipids in plant samples.

Anionic phospholipids (PS, PA, PI, PIPs) are low-abundant phospholipids with impactful functions in cell signaling, membrane trafficking and cell differentiation processes. They can be quickly metabolized and can transiently accumulate at defined spots within the cell or an organ to respond to physiological or environmental stimuli. As even a small change in their composition profile will produce a significant effect on biological processes, it is crucial to develop a sensitive and optimized analytical method to accurately detect and quantify them. While thin-layer chromatography (TLC) separation coupled with gas chromatography (GC) detection methods already exist, they do not allow for precise, sensitive, and accurate quantification of all anionic phospholipid species. Here we developed a method based on high-performance liquid chromatography (HPLC) combined with two-dimensional mass spectrometry (MS2 ) by MRM mode to detect and quantify all molecular species and classes of anionic phospholipids in one shot. This method is based on a derivatization step by methylation that greatly enhances the ionization, the separation of each peak, the peak resolution as well as the limit of detection and quantification for each individual molecular species, and more particularly for PA and PS. Our method universally works in various plant samples. Remarkably, we identified that PS is enriched with very long chain fatty acids in the roots but not in aerial organs of Arabidopsis thaliana. Our work thus paves the way for new studies on how the composition of anionic lipids is finely tuned during plant development and environmental responses.

A combination of plasma membrane sterol biosynthesis and autophagy is required for shade-induced hypocotyl elongation.

Plant growth ultimately depends on fixed carbon, thus the available light for photosynthesis. Due to canopy light absorption properties, vegetative shade combines low blue (LB) light and a low red to far-red ratio (LRFR). In shade-avoiding plants, these two conditions independently trigger growth adaptations to enhance light access. However, how these conditions, differing in light quality and quantity, similarly promote hypocotyl growth remains unknown. Using RNA sequencing we show that these two features of shade trigger different transcriptional reprogramming. LB induces starvation responses, suggesting a switch to a catabolic state. Accordingly, LB promotes autophagy. In contrast, LRFR induced anabolism including expression of sterol biosynthesis genes in hypocotyls in a manner dependent on PHYTOCHROME-INTERACTING FACTORs (PIFs). Genetic analyses show that the combination of sterol biosynthesis and autophagy is essential for hypocotyl growth promotion in vegetative shade. We propose that vegetative shade enhances hypocotyl growth by combining autophagy-mediated recycling and promotion of specific lipid biosynthetic processes.

Comparative Study of Fig Volatile Compounds Using Headspace Solid-Phase Microextraction-Gas Chromatography/Mass Spectrometry: Effects of Cultivars and Ripening Stages.

Aroma is one of the essential parameters that determine fruit quality. It is also an important feature of varietal characterization and so valuable for agro-biodiversity identification and preservation. In order to characterize changes in the aroma fingerprint through fig development, the main objective of the present research was to study the volatile organic compound (VOC) profiles of figs (Ficus carica L.) from three cultivars, Taamriwthe (TH), Azegzaw (AZ), and Averkane (AV), at three ripening stages (unripe, ripe, and fully ripe). Analyses was performed using Headspace Solid-phase Microextraction and gas chromatography coupled with mass spectrometry. Results revealed the presence of 29 compounds that were grouped into different chemical classes. Aldehydes comprised the most abundant VOCs identified in all the studied figs, while alcohols, ketones, and terpenes comprised the minor compounds found in TH, AZ, and AV figs, respectively. Different aroma descriptors were identified throughout the ripening stages of figs; fruity and green aromas were dominant in all cultivars, while a fatty aroma scarcely occurred in figs. A gallery plot representation demonstrated that certain VOCs differentiate the studied cultivars and the different ripening stages of figs. Principal component analysis findings demonstrated characteristic VOCs of distinct ripening stages and cultivars, those VOCs can be used as fingerprints to distinguish different cultivars and/or ripening stages.

Use of Essential Oils and Volatile Compounds as Biological Control Agents.

Plants containing essential oils have been used for centuries as spices, remedies or for their pleasant odor [...].

Phytochemical Investigation and Biological Activities of Lantana rhodesiensis.

Lantana rhodesiensis Moldenke is a plant widely used to treat diseases, such as rheumatism, diabetes, and malaria in traditional medicine. To better understand the traditional uses of this plant, a phytochemical study was undertaken, revealing a higher proportion of polyphenols, including flavonoids in L. rhodesiensis leaf extract and moderate proportion in stem and root extracts. The antioxidant activity of the extracts was also determined using three different assays: the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity, the FRAP method (Ferric-reducing antioxidant power) and the ß-carotene bleaching test. The anti-malarial activity of each extract was also evaluated using asexual erythrocyte stages of Plasmodium falciparum, chloroquine-sensitive strain 3D7. The results showed that the leaf extract exhibited higher antioxidant and anti-malarial activities in comparison with the stem and root extracts, probably due to the presence of higher quantities of polyphenols including flavonoids in the leaves. A positive linear correlation was established between the phenolic compound content (total polyphenols including flavonoids and tannins; and total flavonoids) and the antioxidant activity of all extracts. Furthermore, four flavones were isolated from leaf dichloromethane and ethyl acetate fractions: a new flavone named rhodescine (5,6,3',5'-tetrahydroxy-7,4'-dimethoxyflavone) (1), 5-hydroxy-6,7,3',4',5'-pentamethoxyflavone (2), 5-hydroxy-6,7,3',4'-tetramethoxyflavone (3), and 5,6,3'-trihydroxy-7,4'-dimethoxyflavone (4). Their structures were elucidated by 1H, 13CNMR, COSY, HSQC, HMBC, and MS-EI spectral methods. Aside from compound 2, all other molecules were described for the first time in this plant species.

Identification of a Proanthocyanidin from Litchi Chinensis Sonn. Root with Anti-Tyrosinase and Antioxidant Activity.

This work follows an ethnobotanical study that took place in the island of Mayotte (France), which pointed out the potential properties of Litchi chinensis Sonn. roots when used to enhance skin health and appearance. Through in vitro testing of a crude methanolic extract, high anti-tyrosinase (skin whitening effect) and antioxidant activities (skin soothing effect) could be measured. HPLC successive bio-guided fractionation steps allowed the purification of one of the compounds responsible for the biological activities. The isolated compound was characterized by UV, IR, MS and 2D-NMR, revealing, for the first time in Litchi chinensis Sonn. roots, an A-type proanthocyanidin and thus revealing a consensus among the traditional use shown by the ethnobotanical study, in vitro biological activities and chemical characterization.

Simple liquid chromatography-electrospray ionization ion trap mass spectrometry method for the quantification of galacto-oxylipin arabidopsides in plant samples.

A simple and sensitive method to quantify five different arabidopsides by HPLC-ion trap mass spectrometry in complex plant samples was developed and validated. Arabidopsides are oxidized galactolipids first described in Arabidopsis thaliana but also produced by other plant species under stress conditions. External calibration was performed using arabidopsides purified from freeze-thawed Arabidopsis leaves. Lipids were extracted and pre-purified on an SPE silica column before HPLC-MS analysis. Arabidopsides were separated on a C18 column using a gradient of mQ water and acetonitrile:mQ water (85:15) supplemented with formic acid (0.2%) and ammonium formate (12 mM). The method was validated according to European commission decision 2002/657/CE. LOD, LOQ, linearity, intra-day and inter-day precision and accuracy, selectivity, matrix effects and recoveries were determined for the five metabolites. The established method is highly selective in a complex plant matrix. LOD and LOQ were, respectively, in the range 0.098-0.78 and 0.64-1.56 µM, allowing the arabidopside quantification from 25.6-62.4 nmol/g fresh weight. Calibration curve correlation coefficients were higher than 0.997. Matrix effects ranged from -2.09% to 6.10% and recoveries between 70.7% and 109%. The method was successfully applied to complex plant matrixes: Arabidopsis thaliana and Nasturtium officinale.

Seasonal Effect on the Chemical Composition, Insecticidal Properties and Other Biological Activities of Zanthoxylum leprieurii Guill. & Perr. Essential oils.

This study focused, for the first time, on the evaluation of the seasonal effect on the chemical composition and biological activities of essential oils hydrodistillated from leaves, trunk bark and fruits of Zanthoxylum leprieurii (Z. leprieurii), a traditional medicinal wild plant growing in Côte d'Ivoire. The essential oils were obtained by hydrodistillation from fresh organs of Z. leprieurii growing on the same site over several months using a Clevenger-type apparatus and analyzed by gas chromatography-mass spectrometry (GC/MS). Leaf essential oils were dominated by tridecan-2-one (9.00 ± 0.02-36.80 ± 0.06%), (E)-ß-ocimene (1.30 ± 0.50-23.57 ± 0.47%), ß-caryophyllene (7.00 ± 1.02-19.85 ± 0.48%), dendrolasin (1.79 ± 0.08-16.40 ± 0.85%) and undecan-2-one (1.20 ± 0.03-8.51 ± 0.35%). Fruit essential oils were rich in ß-myrcene (16.40 ± 0.91-48.27 ± 0.26%), citronellol (1.90 ± 0.02-28.24 ± 0.10%) and geranial (5.30 ± 0.53-12.50 ± 0.47%). Tridecan-2-one (45.26 ± 0.96-78.80 ± 0.55%), ß-caryophyllene (1.80 ± 0.23-13.20 ± 0.33%), ?-humulene (4.30 ±1.09-12.73 ± 1.41%) and tridecan-2-ol (2.23 ± 0.17-10.10 ± 0.61%) were identified as major components of trunk bark oils. Statistical analyses of essential oil compositions showed that the variability mainly comes from the organs. Indeed, principal component analysis (PCA) and hierarchical cluster analysis (HCA) allowed us to cluster the samples into three groups, each one consisting of one different Z. leprieurii organ, showing that essential oils hydrodistillated from the different organs do not display the same chemical composition. However, significant differences in essential oil compositions for the same organ were highlighted during the studied period, showing the impact of the seasonal effect on essential oil compositions. Biological activities of the produced essential oils were also investigated. Essential oils exhibited high insecticidal activities against Sitophilus granarius, as well as antioxidant, anti-inflammatory and moderate anti-plasmodial properties.

Composition, Seasonal Variation, and Biological Activities of Lantana camara Essential Oils from Côte d'Ivoire.

This work aims to study the variations in the composition of Lantana camara leaf, flower, and stem essential oils over two years. L. camara organs were harvested in Bregbo (East Côte d'Ivoire) each month from June 2015 to June 2017. The essential oils were obtained by hydrodistillation and characterized by GC-MS and 13C NMR. Eighty-four compounds accounting for 84.4-99.1% of the essential oils have been identified. The essential oils hydrodistillated from L. camara are dominated by sesquiterpenes such as (E)-ß-caryophyllene and α-humulene, which were found in all samples. Some monoterpenes such as thymol, sabinene, and α-pinene were also present. Statistical analysis (principal component analysis and clustering) revealed a high variability in essential oil composition between the different organs and also within the studied periods, as the thymol proportion was higher during flowering and fruiting months. In addition, the stem, flower, and fruit essential oils were more concentrated in thymol than the leaf essential oils. The proportions of (E)-ß-caryophyllene and α-humulene were strictly inverted with the thymol proportion throughout the harvest period or vegetative cycle. The antioxidant, anti-inflammatory and insecticidal activities of leaves and flowers essential oils were also studied. Results showed that L. camara leaf and flower essential oils displayed high antioxidant, anti-inflammatory and insecticidal activities.

Insights into the Relationships Between Herbicide Activities, Molecular Structure and Membrane Interaction of Cinnamon and Citronella Essential Oils Components.

Since the 50's, the massive and "environmental naïve" use of synthetic chemistry has revolutionized the farming community facing the dramatic growth of demography. However, nowadays, the controversy grows regarding the long-term harmful effects of these products on human health and the environment. In this context, the use of essential oils (EOs) could be an alternative to chemical products and a better understanding of their mode of biological action for new and optimal applications is of importance. Indeed, if the biocidal effects of some EOs or their components have been at least partly elucidated at the molecular level, very little is currently known regarding their mechanism of action as herbicides at the molecular level. Here, we showed that cinnamon and Java citronella essential oils and some of their main components, i.e.,, cinnamaldehyde (CIN), citronellal (CitA), and citronellol (CitO) could act as efficient herbicides when spread on A. thaliana leaves. The individual EO molecules are small amphiphiles, allowing for them to cross the mesh of cell wall and directly interact with the plant plasma membrane (PPM), which is one of the potential cellular targets of EOs. Hence, we investigated and characterized their interaction with biomimetic PPM while using an integrative biophysical approach. If CitO and CitA, maintaining a similar chemical structure, are able to interact with the model membranes without permeabilizing effect, CIN belonging to the phenylpropanoid family, is not. We suggested that different mechanisms of action for the two types of molecules can occur: while the monoterpenes could disturb the lipid organization and/or domain formation, the phenylpropanoid CIN could interact with membrane receptors.

Antioxidant and Lipoxygenase Inhibitory Activities of Essential Oils from Endemic Plants of Côte d'Ivoire: Zanthoxylum mezoneurispinosum Ake Assi and Zanthoxylum psammophilum Ake Assi.

Zanthoxylum mezoneurispinosum Ake Assi and Zanthoxylum psammophilum Ake Assi are species endemic to Côte d'Ivoire. In this study, we determined, for the first time, the composition and biological activities of essential oils obtained from each of these plants. Essential oils were obtained by hydrodistillation from different organs of each plant with a Clevenger-type apparatus and analyzed by gas chromatography-mass spectrometry (GC-MS). Thirty-four components, accounting for more than 99.9% of the overall composition, were identified in the oils. The Z. psammophilum leaf and trunk bark oils exhibited two unusual methylketones, undecan-2-one and tridecan-2-one, whereas the root oil was rich in thymol and sesquiterpenoids. The Z. mezoneurispinosum leaf and trunk bark oils were rich in monoterpenoids, whereas sesquiterpenoids were predominant in the root oil. These samples produced, for the first time, some new chemical profiles of essential oils. The oils' antioxidant activities were determined using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging capacity and ferric reducing antioxidant power (FRAP) assays. The results showed that the essential oil isolated from roots of Z. mezoneurispinosum had the highest antioxidant activity, which is in accordance with the high thymol content of that oil. We also determined the lipoxygenase inhibitory activities of the essential oils. The results showed that all of the tested oils displayed high and close lipoxygenase inhibitory activities.

Is It Possible to Predict the Odor of a Molecule on the Basis of its Structure?

The olfactory sense is the dominant sensory perception for many animals. When Richard Axel and Linda B. Buck received the Nobel Prize in 2004 for discovering the G protein-coupled receptors' role in olfactory cells, they highlighted the importance of olfaction to the scientific community. Several theories have tried to explain how cells are able to distinguish such a wide variety of odorant molecules in a complex context in which enantiomers can result in completely different perceptions and structurally different molecules. Moreover, sex, age, cultural origin, and individual differences contribute to odor perception variations that complicate the picture. In this article, recent advances in olfaction theory are presented, and future trends in human olfaction such as structure-based odor prediction and artificial sniffing are discussed at the frontiers of chemistry, physiology, neurobiology, and machine learning.